,!7IB3B5-ijgibg!: Polyurethane Foam Sorbents in Separation Science

CRC REVIVALS CRC REVIVALS
Tibor Braun, James D. Navratil, A. B. Farag

Polyurethane Foam Sorbents in Separation Science
Polyurethane Foam Sorbents in
Separation Science
Tibor Braun, James D. Navratil, A. B. Farag
ISBN 978-1-315-89681-6
,!7IB3B5-ijgibg!
www.crcpress.com
Polyur ethane
Foam Sorbents
in
Separation Science
Authors
Tibor Braun, Ph.D.

Professor
Senior Research Scientist
Institute of Inorganic and Analytical Chemistry
Eotvos University
Budapest, Hungary
James D. Navratil, Ph.D.

Research and Development Chemistry
Rockwell International
Golden, Colorado
A. B. Farag, Ph.D.
Associate Professor
Department of Chemistry
Faculty of Science
Mansoura University
Mansoura, Egypt
Boca Raton London New York
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Library of Congress Cataloging in Publication Data
Braun, Tibor.
Polyurethane foam sorbents in separation science.
Bibliography: p.
Includes index.
1. Plastic foams. 2. Polyurethane. 3. Sorbents.
4. Separation (Technology) I. Navratil, James D.,
1941- . II. Farag, A. B., 1944- . III. Title.
TP1180.F6B73 1984 668.4’93 84-7701
ISBN 0-8493-6597-X
A Library of Congress record exists under LC control number: 84007701
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FOREWORD
The purpose of this book is to present in a monographic and systematized form a
review of all the literature devoted to polyurethane-based polymeric sorbents in sepa-
ration chemistry. The primary types of sorbents dealt with are polyurethane foams and
open-pore polyurethanes.
The structure of the monograph follows this dichotomy. A book of this nature
should stimulate thinking and incite its reader to consult the original literature. It will,
however, not make such a consultation superfluous.
A fair amount of the results described in this monograph constitute the main activity
of investigation which took place in the authors' laboratories during the past decade.
Notwithstanding, the authors realize the extent to which they are indebted to their
many colleagues worldwide who have also contributed largely to this topic, whose
studies are referenced in this work.
The editorial assistance of Sylvia Navratilova is greatly appreciated.
Tibor Braun
James D. Navratil
A. B. Farag
THE AUTHORS
Tibor Braun, Ph.D., D.Sc., earned his degree in Chemistry from the V. Babes Uni-
versity, Cluj, Romania. In 1956 he proceeded to the Institute of Atomic Physics, Bu-
charest, Romania, where he worked as a Research Scientist. From 1963 to the present
time Dr. Braun performs his academic activities at the Institute of Inorganic and An-
alytical Chemistry, L. Eotvos University, Budapest, Hungary where he holds the rank
of Professor of Chemistry.
From 1969 to 1971 he worked at the Institute of Nuclear Research, Lima, Peru and
from 1975 to 1976 in the Department of Chemistry at the University of the West Indies,
Kingston, Jamaica. At both places Dr. Braun served as an expert of the International
Atomic Energy Agency, Vienna, Austria. In Kingston, Jamaica Dr. Braun was ap-
pointed Visiting Professor. He is also Deputy Director of the Library of the Hungarian
Academy of Sciences.
Dr. Braun developed an interest in sorbents chemistry, radioanalytical chemistry,
and radiochemistry. He has written many articles on the subject in analytical chemistry
journals. His fields of interest include general analytical and radioanalytical chemistry,
nuclear chemistry, and scientometrics.
He is the founder and Editor-in-Chief of both the Journal of Radioanalytical and
Nuclear Chemistry Articles, and Journal of Radioanalytical and Nuclear Chemistry.
He is also founder and Managing Editor of Scientometrics.
James D. Navratil, Ph.D., earned his Ph.D. degree in Chemistry from the University
of Colorado, Boulder, and began working at Rocky Flats, operated by Rockwell Inter-
national for the U.S. Department of Energy, in 1961. He has held several positions in
the Analytical Laboratories and Research and Development. His current position is
Manager of the Chemical Research Group. From 1978 until 1981 Dr. Navratil was on
leave of absence to the International Atomic Energy Agency, Vienna, Austria. He was
named Rockwell International Scientist/Engineer of the Year in 1977.
Dr. Navratil's research interests are mainly chemical separations and actinide sepa-
rations. He is founder and Co-Editor of the journal Solvent Extraction and Ion Ex-
change and serves on the editorial board of six other journals. He is active in the
American Chemical Society and is Chairman of the ACS Subdivision of Separations
Science and Technology. He has received the ACS Colorado Section Award and In-
dustrial Research and Development IR-100 Award. Dr. Navratil has authored or co-
authored over 100 publications and co-edited six books.
A. B. Farag, Ph.D., earned his B.Sc. degree in Chemistry from the Faculty of Sci-
ence, Ain-Shams University, Cairo, in 1965. In 1966 he joined the National Research
Centre, Cairo, as a Research Assistant. In 1968 he earned his M.S. degree in Chemis-
try. In 1975 Dr. Farag obtained his Ph.D. degree in Analytical Chemistry from the
Hungarian Academy of Sciences, Budapest. From 1975 to 1977 Dr. Farag joined the
National Research Centre as a Researcher. In 1977 he moved to the Department of
Chemistry, Faculty of Science, Mansoura University, Egypt, as Lecturer. In 1981 he
was promoted to Associate Professor, a title he currently holds. He was on leave to
King Abdulaziz University, Jeddah, Saudia Arabia, as a Staff Member during 1982 to
1984.
Dr. Farag is the author of 45 scientific publications in the field of microanalysis and
foam separation methods. He is a member of the Egyptian Chemical Association and
the American Chemical Society.
TABLE OF CONTENTS
Chapter 1
Polyurethane Foam Sorbents 1
I. Quasi-Spherical Solid Membranes in Separations Chemistry 1
II. Historical Overview 2
III. Foamed Polyurethane Polymers 4
IV. Fundamental Knowledge of Foamed Polyurethanes 4
A. Foam Definition 4
B. Foam Geometry 4
C. Cell Structure 7
D. General Methods of Foam Preparation 7
1. Chemical Methods 7
a. Thermal Decomposition of a Chemical Blowing
Agent 7
b. Blowing by In Situ Chemical Reaction 7
2. Physical Methods 8
a. Low Pressure Release of Dissolved Gas 8
b. Blowing by Vapor from a Volatile Liquid 8
c. Temporary Filler 8
3. Mechanical Methods 8
a. Mechanical Entrainment of Gas 8
b. The Use of Microspheres 8
E. Polyurethane Foam Synthesis 8
V. Physical and Chemical Properties of Polyurethane Foams 11
VI. Analytical Methods for the Characterization of Polyurethane Foams 13
A. Differentiation of Polyurethane Foams from Other Plastic
Foams 13
B. Qualitative Spot Reaction for Polyester- or Polyether-Based
Polyurethane Foam 14
VII. Experimental Techniques in the Analytical Use of Polyurethane Foam
Sorbents 14
A. Preparation of Resilient Polyurethane Foam Sorbents for
Analytical Use 14
B. Collection and Retention Techniques in Aqueous Media 15
1. Batch Methods 15
2. Column Methods 15
3. Pulsating Column Methods 16
C. Collection and Retention Techniques in Gaseous Media 17
VIII. Collection and Retention of Inorganic and Organic Species with
Resilient Polyurethane Foams 22
A. Unloaded Polyurethane Foams 22
1. Collection of Inorganic Species 23
a. Sorption from Aqueous Media 23
i. Acidic Halides 24
ii. Aqueous Nitrate 32
iii. Acidic Thiocyanate 33
iv. Neutral and Alkaline Cyanide 47
v. Acidic Thiourea 49
vi. Other Aqueous Media 49
b. Sorption from Nonaqueous Media 54
2. Collection of Organic Species 55
a. Sorption from Aqueous Media 55
i. Chlorinated Organic Compounds 56
ii. Polynuclear Aromatic Hydrocarbons 60
iii. Other Organic Compounds 65
b. Sorption from Gaseous Media 70
i. Chlorinated Organic Compounds 70
ii. Organophosphorous Compounds 83
iii. Polynuclear Aromatic Hydrocarbons 86
iv. Other Organic Pollutants 88
B. Loaded Polyurethane Foams 92
1. Foams Loaded with Solvent Extractants 92
a. Collection from Aqueous Media 92
b. Collection from Gaseous Media 102
2. Foams Loaded with Hydrophobic Chelating Reagents 102
a. Dithizone Foam 105
b. Diethyldithiocarbamate Foam 110
c. l-Nitroso-2-Naphthol Foam 113
d. Benzoylacetone Foam 113
e. Dimethylglyoxime Foam 113
f. o-Benzildioxime Foam 116
g. 1,2-Ethanedithiol Foam 116
h. Pyridylazo-Naphthol Foam 117
i. Other Reagent Foams 120
3. Reagent Foams in Qualitative and Semiquantitative
Analysis 121
4. Foams Loaded with Liquid Ion Exchangers 128
a. Anion Exchange Foams 128
b. Amberlite® LA-2 Foam 130
c. Aliquat Foam 130
d. Cation Exchange Foams 131
5. Heterogeneous Ion Exchange Foams 132
6. Foams with Anchored Functional Groups 133
IX. Other Analytical Uses of Unloaded and Loaded Resilient Polyurethane
Foams 135
A. Column Redox Reactions 135
B. Isotope- and Redox-Exchange Separations with Polyurethane
Foams 138
1. Isotope-, Redox- and Precipitate-Exchange Separations on
Finely Divided Precipitate Immobilized on Open-Cell
Polyurethane Foams 139
2. Isotope-Exchange Separations on Hydrophobic Organic
Phases Immobilized in Open-Cell Polyurethane
Foams 141
C. Polyurethane Foams for Trapping Volatile Combustion Products
in Organic Microanalysis 148
D. Polyurethane Foams for Trapping Enzyme Inhibitors and the
Immunoadsorption of Cells 155
Chapter 2
Open-Pore Polyurethane (OPP) Sorbents 159
I. Introduction 159
II. OPP Preparation 159
A. Synthesis and Reagents 159
B. OPP Column Preparation 161
III. Physical and Chemical Properties of OPP 162
A. Effects of Synthesis Conditions on OPP Properties 162
B. Compatibility and Other Properties of OPP 173
IV. Analytical Chemistry Applications 173
A. Gas-Solid Chromatography 176
B. Gas-Liquid Chromatography 179
Index 209
1
Chapter 1
POLYURETHANE FOAM SORBENTS
I. QUASI-SPHERICAL SOLID MEMBRANES IN SEPARATIONS

CHEMISTRY
In a great majority of separation and/or preconcentration processes a solid sorbent

is brought into contact with a liquid or a gas phase with the aim of retaining some
solutes (mostly traces of inorganic or organic species) on or in the solid sorbent phase.
The geometrical form of the solid sorbent used is in general granular (irregular grains,
in ideal cases spherical beads). In some cases the sorbent can be planar (sheets or flat
beds, or flat membranes), or even cylindrical (hollow tube or fiber). Investigation and
systematic use in separation and preconcentration processes for sorbents of hollow
solid quasi-spherical membrane geometry began in the early 1970s; the potentialities of
that special geometrical form were accentuated for the first time in a review paper
published in 1975.1
The authors have diligently attempted to collect and present in logical order all the
literature published on polyurethane foam sorbents, the most typical representative of
the above-mentioned quasi-spherical membrane-shaped solid sorbents. The less than
15 years since polyurethane sorbents entered separations chemistry is too short a period
to reveal decisively all potential for such a method. As with most separation tech-
niques, they could be sometimes advantageously used while other times alternate pro-
cedures were more efficient. It is not the purpose of this book to advocate the superi-
ority of polyurethane foam sorbents. Rather, by having the total information available
in one volume, the chemist will have to decide in solving each special separation or
preconcentration problem if polyurethane foam sorbents could provide an advantage
over another procedure or sorbents.
Throughout this book, open-cell type resilient polyurethane foam is viewed as a
regular stack of solid quasi-spherical membranes; that is, because quasi-spherical mem-
brane geometry is considered the most distinctive feature of this special class of poly-
meric sorbents. Irrespective of the mechanism (adsorption, absorption, chelation, dis-
solution, ion exchange, isotope exchange, etc.) of the quasi-spherical membrane
interaction with solute species in a liquid or gaseous phase, the reaction rates at the
liquid-solid (membrane) or gas-solid (membrane) interface will always be more favor-
able than in the case of liquid-solid (bulk) or gas-solid (bulk) contact. From the point
of view of the volume-to-surface ratio, quasi-spherical membrane geometry is the most
advantageous. It is instructive to make a rather rudimentary comparison 2 between a
spherical membrane and equivalent sections of cylindrical and planar membrane sys-
tems (Figure 1). The dimensional parameters of interest in each case are a characteristic
length (diameter) d, the membrane thickness h, and the ratio R of membrane volume
to core volume. These are related to each configuration by:
-d —2 Lh-——1
1
(R + irJ
(R
where the value of n is 1/3 for the spherical, 1/2 for the cylindrical, and unity for the
planar geometry. In Figure 2 this function is plotted for each case. The spherical mem-
brane geometry, of course, results in the largest ratio of surface-to-volume and the
minimum ratio of membrane thickness-to-volume for a given R value.
2 Polyurethane Foam Sorbents in Separation Science
Planar Cylindrical Spherical
FIGURE 1. Equivalent sections of three membrane geometries.
(R +1)
FIGURE 2. Geometrical relationship for three membrane configu-

rations.
Finally we have to mention another very distinctive feature of the polyurethane foam
sorbents, namely its extremely favorable hydrodynamical and/or aerodynamical be-
havior. Columns filled with these sorbents permit the use of liquid and/or gas flow
rates which are much greater than columns filled with granular or bead-shaped sor-
bents.
II. HISTORICAL OVERVIEW

Natural sponge is considered1'3 to be the oldest application of a solid material of
quasi-spherical membrane (foam) geometry in separations chemistry. More than 4 cen-
turies ago, Brunschwig" used a sponge material loaded with olive oil for the purifica-
tion of ethanol in a distillation system. The spherical membrane-shaped sponge mate-
rial can be considered as solid support, olive oil as a stationary (loaded) phase, and
ethanol vapors as a mobile phase. It is worth mentioning that in 1962 Bayer5 tested this
ancient method and found that it operated well.
In 1964, Lai et al.6 described a method for the collection of trace elements from sea
3
water employing natural sponge supporting iron(III) hydroxide precipitate. By towing

the treated sponge through coastal sea water, these researchers were able to enrich
some elements, e.g., silicon, beryllium, gold, and titanium.
In 1965, Bauman et al.7 physically immobilized an enzyme-containing starch gell on
reticulated foamed polyurethane. This foam was employed to monitor water and air
for enzymic-inhibiting atmospheric pollutants.
The work of Van Venrooy8 in 1967 using reticulated polyurethane foam as support
in gas chromatography resulted in a U.S. patent.
In 1970, Bowen9 initiated the use of polyurethane foams for the sorption and recov-
ery of some inorganic and organic components from aqueous solution. He reported
that by using a batch sorption procedure some untreated foamed polyether type poly-
urethanes have good sorption capabilities for a number of metal ions and compounds
from dilute aqueous solutions. On the basis of Bowen's work, the succeeding year
Gesser et al.10 suggested the application of untreated polyurethane foams for the sorp-
tion of trace organic contaminants from water using a batch squeezing technique.
In 1972 Braun and Farag" initiated the application of polyurethane foams for sep-
aration purposes, but in a completely different way. By taking advantage of the spher-
ical-membrane-shaped geometry of the polyurethane foams, they were able to use
foam column operations as a substitute for the traditional granular supports in extrac-
tion chromatographic systems.
These pioneering studies resulted in several unloaded and loaded foamed polyure-
thanes (polyether and polyester type) having versatile applications in separations chem-
istry.
Unloaded foams have been employed for the sorption and separation of inorganic
species from aqueous solutions containing halide, 912 21 nitrate, 9 - 18 ' 22 - 23 thiocyanate,24'39
and cyanide39"40 ions and also in aqueous thiourea41 and other aqueous solutions.42"44
The sorption of some metal chloride complexes in nonaqueous media has also been
reported.45 In addition, the application of untreated polyurethane foams for the sepa-
ration and recovery of various chlorinated organic compounds,10-46*54 polynuclear ar-
omatic hydrocarbons (PAH)55 5S and other organic compounds from aqueous solu-
tions has also been described.59"64 Furthermore, several untreated foams have been
successfully used for the collection and retention of various chlorinated organic insec-
ticides,65 89 organophosphorus compounds, 71 - 72 - 87 - 88 PAH, 9091 and other organic pol-
lutants from gaseous media. 1 - 83 - 9295
Furthermore, loaded polyurethane foams have found wide application for different
separation purposes. Polyurethane foams supporting solvent extractants, chelate com-
pounds, liquid ion exchangers, anchored extracting groups, and powdered ion exchan-
gers have been employed in batch and column operations for the separation of various
inorganic and organic species in aqueous solutions. Specially treated polyurethane
foams have been used for isotope exchange separations and redox reactions. Also, the
application of different treated and untreated foams for the quantitative trapping of
some volatile decomposition products, produced during the combustion of organic
compounds in elemental microanalysis, has been shown. Moreover, suitably treated
polyurethane foams have been prepared and successfully used for the separation of
enzyme inhibitors and immunoadsorption of cells.
Parallel with the polyurethane foams, rigid open pore polyurethane (OPP) micro-
sphere sorbents have been prepared and evaluated for gas-solid and gas-liquid partition
chromatographic separations. Also, the application of these OPP microspheres for the
separation of some metal chelates, alcohols, aromatics, and other compounds has been
described.
As would be seen later, unloaded and reagent loaded polyurethane foams proved to
be suitable for the separation, preconcentration, and collection of a broad spectrum of
inorganic and organic species in aqueous, nonaqueous, and gaseous media. Polyure-
thane foams were found to be quite effective for separation in static (batch) and dy-
namic (column flow) systems. Owing to their quasi-spherical membrane structure, po-
lyurethane foams and open pore microspheres allow very reasonable flow rates when
used in dynamic operations. These favorable flow characteristics which permit high
flow rates suggested application of polyurethanes in the preconcentration of various
trace components from large volumes of water in a relatively short time. The same
properties permitted application of polyurethane foam sorbents in high volume air
samplers. Additionally, easy handling of same facilitated rapid, effective, and inexpen-
sive separations. Furthermore, the resilient character of polyurethane foams allowed
their use in batch squeezing and pulsated column operations. Obviously, this unique
possibility could not be matched by any other known solid sorbent.
Figure 3 shows the cumulative growth curve of publications related to polyurethane
foam sorbents. As seen, there is a steadily growing interest in the topic. 96 9S
III. FOAMED POLYURETHANE POLYMERS

Polyurethane foams, used for almost 40 years, offer a wide variety of products suit-
able for various applications. Several chemical and physical phenomena contribute
largely to the properties of the polymer. Flexible and rigid polyurethane foams of
open- and closed-cell structures with a wide range of properties have been prepared.
Flexible open-cell foams find wide application in furniture upholstery, pillows, mat-
tresses, and other cushioning applications. 99 Rigid closed-cell foams having good in-
sulation properties are widely used in the household refrigeration industry and have
recently been applied in the building and shipping industries. Figure 4 shows the
growth rate curve of the world polyurethane foam consumption during the period 1963
to 1980 with some data extrapolated up to 1990.
IV. FUNDAMENTAL KNOWLEDGE OF FOAMED POLYURETHANES
A. Foam Definition
Polyurethane foams can be defined 100 as plastic materials in which a proportion of
solid phase is replaced by gas in the form of numerous small bubbles (cells). The gas
may be in a continuous phase to give an open-cell material or it may be discontinuous
to give noncommunicating cells. Low density foams are dispersions of relatively large
volumes of gas in relatively small volumes of solids having, for example, a density less
than 0.1 g cm"3. Medium foams are classified101 as having a density of 0.1 to 0.4 g cm~ 3 .
High density foams, therefore, have a density higher than 0.4 g cm"3, i.e., contain small
volumes of gas in the matrix.
B. Foam Geometry
From the geometrical point of view, if the gas bubbles occupy a volume smaller than
76%, they may be spherical. If they occupy a volume larger than 76%, they will be
distorted into quasi-spherical polyhedra. 102 Figure 5 shows a typical polyurethane foam
in which the bubbles (cells) occupy about 97% of the volume. The polyhedral structure
is clearly visible, and the polyhedra on the average are quasi-spherical pentagonal do-
decahedra.
The polymer is distributed between the walls of the bubbles and the lines where
bubbles intersect. The bubbles are called quasi-spherical cells, the lines of intersections
are called strands, and the walls are the factual membranes. In open-cell flexible poly-
urethane foam, at least two windows (from the total) in each cell must be ruptured for
5
FIGURE 3. Growth curve of publications dealing with po-

lyurethane foam sorbents.
FIGURE 4. Growth curve of world polyurethane foam consump-

tion.
Polyurethane Foam Sorbents in Separation Science
^ *;.<i^Jflw^JM«^HP'.,.,
FIGURE 5. Scanning electron micrographs of a typical polyurethane foam struc-

ture. Top-20X; Bottom-lOOX.
7
fluids to pass freely through the foam. It is necessary for each window to be shared by
two cells, and each strand to be shared by three cells.
C. Cell Structure
The cell structure (i.e., presence or absence of windows in the cell or the number of
windows per cell) is a function of the process by which the foam is made. It was
noted100 that both rigid and flexible foams may be obtained with open- and closed-
cells. The structure made up of windowless cells (containing only strands) is called
reticulated foam. 102
It was reported100 that generally flexible polyurethane foams tend to have open-cell
structures while rigid foams tend to have closed-cells. However, there are many excep-
tions and, as the type of cell structure is largely determined by the method of expan-
sion, some materials which can be made by more than one method can exist in both
open- and closed-cell forms. Furthermore, methods are available by which closed-cell
structure can be converted into the open-cell form by rupture of the windows. Ruptur-
ing may be caused mechanically by applying pressure, or chemically by hydrolysis or
oxidation.
D. General Methods of Foam Preparation

With the highly developed technology for making cellular plastics today," methods
exist by which practically every plastic material may be made in the cellular form. The
general principle for preparing cellular plastics is the dispersion of the gas phase in a
liquid to obtain liquid foam which will then be solidified to a solid cellular plastic. The
main methods for uniform dispersion of the gas bubbles are chemical, physical, or
mechanical.
/. Chemical Methods
a. Thermal Decomposition of a Chemical Blowing Agent
This method involves the incorporation of a chemical blowing agent into the plastic
polymer in the liquid state. The blowing agent is usually an organic material which
decomposes under the action of heat to yield a gas. Heating the mixture of the polymer
and the blowing agent to a certain temperature causes a decomposition of the latter.
Subsequent expansion of the polymer occurs which under controlled conditions gives
rise to a foamed plastic.103
Generally, the chemical blowing agent must be chosen in such a manner that the
residue remaining in the polymer be nontoxic and not cause polymer breakdown. Sev-
eral chemical blowing agents are commercially available today. The most widely used
is p-toluenesulfonyl semicarbazide.104 This material, which decomposes at 235°C to
give mainly nitrogen and carbon dioxide, is useful for expanding plastics such as high-
density polyethylene, polypropylene, rigid polyvinyl chloride, etc.
b. Blowing by In Situ Chemical Reaction

In this process gas formation is achieved by the reaction between two species, one of
which can or cannot be a part of the polymer, or both from the polymer alone.
A good example for gas production from a reaction between polymer and nonpoly-
mer fragment is found in polyurethane foam formation (described in detail in a suc-
ceeding section).
Cellular phenolic resins can be prepared by mixing the liquid resin with a simple
inorganic carbonate or bicarbonate which when treated with mineral acids (for hard-
ening) produces carbon dioxide. This is considered to be a good example for the gen-
eration of the blowing agent by in situ chemical reaction between two species, neither
of which is part of the polymer. In some systems and under certain conditions, volatile
materials may be split off as fragments from the polymer which act as blowing agents
representing the last category. For example, a-chloro acrylic esters may be polymerized
at room temperature but split off a volatile alkyl chloride when heated to 150 to
180°C.100
2. Physical Methods
a. Low Pressure Release of Dissolved Gas
This technique employs the dissolution of gas in the liquid polymer under high pres-
sure. Upon releasing pressure, the expansion of gas from the supersaturated polymer
causes the formation of foamed plastic. Expanded ebonite, polystyrene, and polyvinyl
chloride have been prepared by this method. 100
b. Blowing by Vapor from a Volatile Liquid

In this method a liquid blowing agent is incorporated into the polymer under atmos-
pheric conditions. On heating the mixture, the liquid blowing agent will be converted
into vapor which causes expansion of the polymer and formation of a cellular material.
In some cases, exothermic heat of the polymer cross-linking reaction may be applied
for volatilization of the organic blowing agent. The preparation of polyurethane foams
using chlorofluorocarbons (e.g., CFC13) is probably the best known example.103 Plas-
tics, in which external heat is used to volatilize the organic blowing agent (e.g., ethyl-
methyl ketone, methylene chloride, pentane, acetone, ethanol, etc.) include polysty-
rene, polyvinyl chloride, and cellulose acetate.
c. Temporary Filler
This system is used to make cellular material from polymers which are difficult to
expand. Particles of solid material are fixed with the polymer and processed to give a
filled solid plastic. The filler is subsequently removed by leaching with a suitable sol-
vent or by sublimation to leave the plastic material in a cellular form. A good illustra-
tion is the preparation of cellular polytetrafluoroethylene, 100 which results from mixing
and sintering polymer powder with naphthalene. Naphthalene is then sublimed away
leaving a porous form of polytetrafluoroethylene.
3. Mechanical Methods
a. Mechanical Entrainment of Gas
This is probably the oldest means of forming cellular plastics. Air beaten into the
polymer produces a stable liquid foam, which is then cured either chemically or by
heating. Urea-formaldehyde and polyvinyl chloride have been prepared in this way.100
b. The Use of Microspheres

A wide variety of cellular plastics may be made by mixing microspheres with the
liquid polymer which on solidification gives rise to a cellular product without direct
polymer/gas interaction. Microspheres are small hollow spheres with extremely thin
walls which can be made of phenol-formaldehyde, urea-formaldehyde, glass, etc.
E. Polyurethane Foam Synthesis

Polyurethane foams are the most widely used cellular plastics in separations chem-
istry. For that reason, the fundamental chemistry of polyurethane foam synthesis will
be considered here in some detail.
Prepared in soft, flexible, or rigid forms, 105 these foam materials have been fabri-
cated from a variety of polyesters and polyethers. The two important reactions in the
preparation of urethane foams are those between isocyanate and hydroxyl compounds
(polyester or polyether polyols) and those between isocyanate and water. The former
reaction for the formation of a urethane group can be considered as a chain-propagat-
ing reaction:
R-N=C=O + R'-OH -> R-NH-C-0-R' (1)
urethane
The isocyanate group is considered to exist in the following resonance forms: 9
R_N-C=0 •«• R-N=C=0 <-> R-N-C-0: (2)
Electron-withdrawing substituents on the isocyanate molecule should move negative

charges away from the isocyanate carbon, making it more positive and thus facilitating
attack by an electron-donating group such as hydroxyl. The resonance forms may ex-
plain the observed relative high reactivity of aromatic isocyanates owing to the elec-
tron-withdrawing influence of the aromatic rings.
The second reaction, water-isocyanate is responsible for foam formation by the lib-
eration of carbon dioxide as an in situ blowing agent. The first step of this reaction is
formation of unstable carbamic acid which decomposes to form carbon dioxide and
amine. The latter may react with an additional isocyanate to produce substituted urea
R_N=C=O + H 2 0 •[R-NH-C-OH]-" R-NH2 + C02

carbamic acid
0
II
R_N=C=0 + RNH, R-N-C-N-R (3)
I
H H
substituted urea
Alternatively, carbamic acid may react with another isocyanate molecule to produce
carbamic acid anhydride which decomposes to substituted urea and carbon dioxide:
0 0 0
[R_NH-C-OH]+ R-N=C=0 ->[R-NH-C-0-C-NHR] (4)

carbamic acid anhydride
R_NH-CO-NHR + CO, < 1
The main reactions which lead to branching and cross-linking are the isocyanate-ure-
thane reaction producing allophanate linkages (Equation 5) and the isocyanate-urea

reaction which produces biuret (Equation 6):
O 0 0
R _N=C=0 + R-NH-C-OR' R -NH-C-N-C-0-i-R'

J (5)
I
R
allophanate
R_N=C=O + R-NH-C-NHR' R-j_N-CO-NH R' (6)

i I
I CO
II
JNH
R
biuret
Polyols, many of which are commercially available under various trade names, rep-
resent the largest single component in foam preparation. In general, polyols in the
molecular weight range of 400 to 6000 are employed.101-106 Propylene oxide adduct of
glycerol having greater than 90% secondary hydroxyl terminal groups and 3000 mol
wt. is an example of the most widely used polyol (polyether) for the production of
polyether polyurethane foam. The second largest component of the foam formulation
is the isocyanate compound. The most widely used isocyanate is toluene diisocyanate.
The toluene diisocyanates usually employed are the 80/20 and 65/35 mixtures of the 4
and 6 isomers.
In industrial preparation, catalysts are employed to increase the reaction rate and to
establish the proper balance between the chain extension and the foaming reaction.
The catalysts most commonly used105 are tertiary amines and organometallic com-
pounds, e.g., organotin compounds. The tin catalyst promotes the isocyanate-hydroxyl
reaction primarily, while the tertiary amine catalysts favor the isocyanate-water reac-
tion. 106 The properties of the foam can be controlled by proper choice of the catalyst
system. Also, the addition of silicones was generally recommended" to prevent gas
boiling during foam formation and to obtain fine distribution of the gas throughout
the polymer matrix. The quantities of silicones and catalysts are controlled so that most
of the gas is captured in individual cells. However, a small quantity is allowed to break
through to open the cells. This opening is necessary to obtain flexible (resilient) foams.
In making rigid foams, a different kind of simultaneous processing is usually utilized."
Most of the polyurethane foams used in the different chemical separation methods
are of open-cell type and commercially available. They are supplied by several manu-
facturers, e.g., Greiner (Austria), Eurofoam (Belgium), Dunlopillo (England), Chem-
ical Works (Hungary), Canlab, Goodrich, and Monsanto (Canada), diSPo, Union
Carbide, Olimpic, and Read Plastics (U.S.), and others. The foam material (polyether
or polyester type) can be obtained in different shapes, e.g., thin or thick sheets, small
cubes, cylindrical pieces, etc.
For the purpose of studying the visible and infrared absorption spectra of some
absorbed species on the foam material, Hamon et al. 27 prepared a thin film of poly-
urethane. They prepared this film by transferring 0.2 ml aliquots of foam solution to
sodium chloride plates. The polyurethane solution was made by dissolving 0.1 g of a
11
polyether polyurethane foam in 5 mi of m-cresol by refluxing at 203°C. The solvent
was then removed by heating under vacuum and the free —NH 2 or -OH groups thus
obtained were reacted for 18 hr with 0.1 g of phenyl isocyanate in 100 mi of hexane.
Thereafter the plates bearing films were soaked in fresh hexane for 2 days to remove
any excess of the reactant and subsequently dried under vacuum to remove the solvent.
V. PHYSICAL AND CHEMICAL PROPERTIES OF POLYURETHANE

FOAMS
Generally, the physical properties of polyurethane foams depend on the method by

which they are prepared. For example, the windows may or may not be ruptured in the
final stage of expansion, depending on the relative rate of molecular growth (gelation)
and gas reaction, giving rise to flexible (open-cell) or rigid (closed-cell) foams. In po-
lyurethane foam preparation, the variety in choice of simple molecules is great and
consequently, the properties of the product are wide. Choice of the polyol has a major
effect on the foam properties, especially on its rigidity and flexibility.105 The cross-link
density of the urethane polymer determines whether the foam will be flexible (low
cross-link density) or rigid (high cross-link density). Flexible foams are prepared from
polyols of moderately high molecular weight and low degree of branchng, while rigid
foams are prepared from highly branched resins of low molecular weight.
The chemical properties of polyurethane foams are also a function of the prepara-
tion process. For example, solvent resistance of polyurethane structure increases at
higher cross-link densities, appears to be unaffected by the type of aromatic diisocyan-
ate, and is reduced with the use of a large excess of isocyanate.103 It was also reported"
that aliphatic and cycloaliphatic isocyanates can produce a polymer with an outstand-
ing resistance to sunlight, as aliphatics are normally less photosensitive than their aro-
matic counterparts.
The mechanical properties of polyurethane foams are highly dependent on the pro-
portion of the allophanate linkage which increases with reaction time and temperature
for toluene diisocyanate-based urethanes."
Several investigations have been carried out to determine the relative proportion of
allophanate, urea, urethane, and biuret linkages and also the amount of the unreacted
(free) NCO group using infrared spectroscopy107 1U and nuclear magnetic reasonance
methods. 112 ' 113 Foams prepared from the reaction of toluene diisocyanate with polyol
are generally found to have lower free NCO groups than those prepared from diphen-
ylmethane diisocyanate.
Bowen9 examined the chemical resistance of some batches of commercial polyure-
thane foams having different densities and claimed that they are rather stable and inert.
The foam batches tested degraded when heated between 180 and 220°C, and slowly
turned brown in ultraviolet light. They were dissolved by concentrated sulfuric acid,
destoyed by concentrated nitric acid, and reduced alkaline potassium permanganate.
They were mostly unaltered, apart from reversible swelling, by water, hydrochloric
acid up to 6 M, sulfuric acid up to 2 M, glacial acetic acid, 2 M ammonia, and 2 M
sodium hydroxide solutions, as well as by solvents such as light petroleum, benzene,
carbon tetrachloride, chloroform, diethyl ether, diisopropyl ether, acetone, isobutyl
methyl ketone, ethyl acetate, isopentyl acetate, and alcohols. It was also noted that
polyurethane foams can be dissolved in hot arsenic(III) chloride solution.
Braun et al.31 measured the inorganic trace impurities in different batches of poly-
ether and polyester polyurethane foams by neutron activation analysis. The foam sam-
ples were packed, as supplied, into polyethylene capsules and irradiated for 5 or 10
min in the fast rabitt system of a nuclear reactor at a neutron flux of 3.1013 n.cm"J.s"'.
Irradiation for longer times (e.g., 1 hr or more) causes a degradation of the foam
Table 1
TRACE ELEMENTS IN POLYURETHANE FOAM
(ppm)
Ether-type Ester-type
Element (1)
(1) (2)
(2) (3)
(3) (4)
(4) (1)
Tin 850 1110

1110 710 1090
1090 25
Chlorine 110 108 178 96 148
Sodium 39 32 73 43 103
Magnesium 19 14 20 11
Aluminum 3.1 2.5 2.5 1.3 0.7
Iodine 4.3 1.8 3.1 2.5 8.9
Bromine 2.3 2.8 3.4 1.7 12.6
Manganese 0.36
0.36 0.34
0.34 0.34
0.34 0.34
0.34 0.13
Vanadium 0.09
0.09 0.05
0.05 0.04
0.04 0.04
0.04 0.05
Indium 0.02 0.04 0.01 0.04
Arsenic ND ND ND 4.95
Antimony ND ND ND 0.46
Potassium ND ND ND 26
Note: Each result is an average of three determinations; the relative

standard deviation is 2 to 10%. ND = not determined.
From Braun, T., Abbas, M. N., Elek, A., and Bakos, L., J. Ra-
dioanal. Chem., 67, 359, 1981. With permission.
skeleton. The impurities measured in the polyurethane foam samples are shown in
Table 1. As is clear from these results, tin represents the main impurity in the polyether
type foam, while it is by far lower in the polyester foam. This high tin content results
from the use of organotin compounds as catalysts during the polymerization of the
polyether type polyurethane foam. Small amounts of chlorine, sodium, magnesium,
iodine, and bromine are also present. However, washing the foam material before
irradiation with 1 M nitric acid solution was found to decrease the amounts of alkali
metals, halogens, manganese, and vanadium, but does not affect the amount of tin
(Table 2). It was indicated that the amount of heavy metal impurities in polyurethane
foams are generally negligible or even absent. The impurities present are comparable
with or lower than those present in other organic sorbents, e.g., activated carbon," 4 115
chelating filters," 6 chelating resins,"7 or ion exchange resins.116-"8
On the other hand, Bidleman and Olney66 determined the organic extractable com-
pounds in a polyester polyurethane foam (diSPO plugs). They refluxed the foam ma-
terial for 2 hr with 150 mi of petroleum ether followed by another 2 hr extraction in a
Soxhlet extractor (30 c) with 175 ml of the same solvent. The extracts were then in-
jected into a gas chromatographic column after their appropriate concentration to
small volumes. As is evident from Figure 6, two major gas chromatographic peaks
were observed. These peaks were removed by passing the extracts through an alumina
column prior to the gas chromatograph. In using a deactivated silicic acid column for
cleaning up the extracts, the peaks were not detected in the petroleum ether eluate but
measured in the dichloromethane eluate.66 This thorough washing of foam materials
before use was shown to be a very important step, especially when employing such
substances for the collection of organic compounds from aqueous or gaseous media.
Surface areas for different polyether type polyurethane foams were measured.9 "'
The procedure involved 3 hr shaking of 50 mg portions of the foam with 5 g aliquot
portions of solution containing carboxy-14C stearic acid in n-heptane, which is itself
13
Table 2
TRACE ELEMENTS IN
POLYURETHANE FOAM
AFTER WASHING (ppm)
Element Ether-type Ester-type
Tin 1096 23
Chlorine 43 93
Sodium 8 7
Magnesium 8 —
Aluminum 0.7 —
Iodine 1.9 8.7
Bromine 1 8
Manganese 0.1 0.08
Vanadium 0.01 ND
Indium 0.02 —
Arsenic 4.5 —
Antimony 0.48 —
Potassium 8 ND
Note: Each result is an average of three de-

terminations; the relative standard
deviation is 2 to 10%. ND = not de-
termined.
From Braun, T., Abbas, M. N., Elek, A.,

and Bakos, L., J. Radioanal. Chem., 67,
359, 1981. With permission.
absorbed to a negligible extent by the foam material. The bulk densities of the foams
examined ranged between 0.017 to 0.304 g cm~ 3 and their surface areas were found to
be 0.007 to 0.035 m 2 g"1. There was no correlation between the surface area and the
bulk density of the foams examined.
The surface areas of some batches of polyether17 and polyester21 polyurethane foams
were also measured by the BET method, using Krypton gas, and found to be 0.08 m 2
g to 0.081 m 2 g~', respectively. Unfortunately the densities of the foams tested were not
specified.
VI. ANALYTICAL METHODS FOR THE CHARACTERIZATION OF

POLYURETHANE FOAMS
In this section, information is given which will permit identification and characteri-
zation by rapid and simple means of the most usual types of polyurethane foams used
as sorbents in separations chemistry. For more details on the analysis of other com-
ponents and instrumental procedures, the reader is directed to the relevant original
literature. 106
A. Differentiation of Polyurethane Foams from Other Plastic Foams

p-Dimethylaminobenzaldehyde is, in general, used to determine the composition of
a number of different foams. The color of the product after reagent addition deter-
mines the foam type. Urea, melamine, isocyanate, and urethane foams are differen-
tiated in this manner. The reagent develops a yellow color with NCO groups. When
urea foams are hydrolyzed with mineral acids, a positive test is obtained; with unhy-
drolyzed urea foams the test is negative. With isocyanate and polyurethane foams,
which contain —NCO groups, the test is positive without prior treatment. A positive
test is obtained even after these foams are extended with polyols. In glacial acetic acid
the yellow color that forms immediately with the isocyanate foam provides a specific
test for identification. Such probes are conducted by dissolving the foam in 5 to 10 mi
of glacial acetic acid with or without heating. A suitable solvent may be used first for
dissolving those foams not soluble in glacial acetic. m-Cresol, dimethylsulfoxide, or
dimethylacetamide are solvents which will often effect solution. Approximately 0.1 g
of p-dimethylamino benzaldehyde reagent is added and a bright yellow color develops
in a few minutes at room temperature if either isocyanate or urethane groups are pres-
ent.
A spot test permits polyurethane foams prepared from polyethers and those pre-
pared from polyesters to be differentiated. 106 Such determination is based on the fol-
lowing reactions where R and R' are di- or polyfunctional:
0 0
II II
R-C-OR' + H 2 NOH • HC1 + 2KOH -» R-C-NHOK + KC1 + 2H 2 0 + R'OH (7)
0 0
II II
R-C-NHOK + HC1 -> R-C-NHOH + KC1 (8)
O
II ^°---
R-C-NHOH+ 1/3 Fe 3+ -»• R-C " Fe/3 + H + (9)
X
N-0
I
H
The hydroxamic acid from the polyester reacts with the ferric ion to form a complex
which is water-soluble and violet or purple in color for most hydroxamic acids.
B. Qualitative Spot Reaction for Polyester- or Polyether-Based Polyurethane Foam

Reagents —
1. 2 M solution of KOH in methanol plus phenolphthalein to a dark pink color.

2. Saturated solution of NH 2 OH • HC1 in methanol.
3. 1 M hydrochloric acid solution.
4. 1 to 3% solution of FeCl3 in water.
Procedure — Approximately 50 mg of small pieces of foam are treated with a few

drops of reagent 1 and then a few drops of reagent 2 are added. The resulting mixture
must be alkaline as indicated by the phenolphthalein. For some foams it is desirable to
heat the mixture for 20 to 40 sec in order to increase the reactivity. After 30 to 60 sec
reaction time, the mixture is acidified with reagent 3 after which one drop of reagent 4
is added. If esters are present, a characteristic violet color will appear immediately.
Esters present as solvents, plasticizers, etc., interfere.
VII. EXPERIMENTAL TECHNIQUES IN THE ANALYTICAL USE OF

POLYURETHANE FOAM SORBENTS
A. Preparation of Resilient Polyurethane Foam Sorbents for Analytical Use

As a general rule, polyurethane foams must be suitably cut, washed, and dried be-
15
fore using for separation purposes. The foam materials generally employed are in the
form of small cubes (5 mm edge) or in a cylindrical (plug) form. In the latter case the
foam is cut such that each cylindrical rod has a little larger diameter than the column
employed. The diameters of the foam cylinders range between 1.0 and 8.3 cm and their
lengths vary from 1.0 to 12.0 cm. The cylindrical plugs can be cut from commercially
available foam sheets (having different thicknesses) by thin-wall stainless steel tubing
mounted in a drill press.65 Some workers 81 - 82 compressed the foam sheet between two
plywood boards, the upper board containing a number of holes of different diameter.
The plugs were then cut with a pre-cleaned hole saw mounted on a drill press. Other
workers instead soaked the foam material in liquid air or liquid nitrogen and used a
cork-borer for cutting the freezed foam into cylinders of the required diameter. Com-
mercially available foam plugs were also employed.10 45
Foam cubes or cylinders are usually washed with 1 M hydrochloric or nitric acid
followed by distilled water (until the washings are acid-free) and then with acetone or
other volatile organic solvents. However, the foam materials used for the collection
and separation of organic pesticides in aqueous or gaseous media are usually washed
with pesticide grade hexane and/or acetone or any other suitable organic solvent. Most
of the investigators recommend the extraction of the foam material in a Soxhlet ex-
tractor instead of simple washing to eliminate any organic material remaining in the
foam after the synthesis process. Once the washing step is completed, foam is either
air-dried, dried under vacuum, or dried in an oven at 80°C. The cleaned, dried sorbent
foams are then stored in stoppered flasks, aluminum foils, or nylon foil bags until
used.
B. Collection and Retention Techniques in Aqueous Media
1. Batch Methods
Batch methods can be classified into batch shaking and batch squeezing methods. In
the former, the sorption equilibrium is established by shaking a certain amount of the
foam cubes with a known volume or weight of the sample solution to the optimal time.
Stoppered flasks or tubes are used for this purpose. 9 In the case of batch squeezing,
the equilibrium is established by squeezing a foam cube (20 to 40 mm edge) in the
sample solution for a suitable time. 9 Some researchers21 placed a piece or pieces of
foam in a beaker with the desired amount of the solution and used the base of a
measuring cylinder to compress the foam periodically. Others 42 employed the cell
shown in Figure 7 for squeezing a piece of foam.
An automatic squeezing apparatus was also employed. 17 60 This consists of an eccen-
tric cam turned by a motor at 8.5 rpm which depresses and releases the plunger of the
cell once per revolution, i.e., squeezes and releases the foam piece placed in the vessel
beneath the plunger. Alternatively, also employed was a large multiple automatic
squeezer consisting of an eccentric cam (91 cm long, 14 cm diameter), turned by a
heavy-duty motor, which compresses and releases as many as 10 glass plungers (5 cm
stroke, 24 strokes/min). 21
2. Column Methods
Columns of various dimensions have been used in chromatographic foam separa-
tions and also in collection and retention processes on the foam. A vacuum method
for foam column packing has been developed120 and widely employed. In this method
the (loaded or unloaded) foam cubes or cylinders are packed in a column by applying
gentle pressure with a glass rod to reduce the foam volume to about one-third of its
original volume. Air bubbles are expelled during packing by connecting tap 1 (Figure
8) to a suction pump and closing tap 2. The flat-bottomed connection of tap 1 prevents
20
Minutes
FIGURE 6. Chromatograms of petroleum ether extracts of foam

plug blanks, (a) No cleanup, 5 ml, 10 \ii injection, (b) After alumina
cleanup, 5 ml, 10 \il injection, (c) After alumina cleanup, 1 ml, 10 nt
injection. (From Bidleman, T. F. and Olney, C. E., Bull. Environ.
Contam. Tox., 11, 442, 1971. With permission.)
the foam sorbent from upward movement during suction. After about 10 min of evac-
uation, distilled water is allowed to fill the column gradually through tap 2. Then tap
1 and the column top are replaced with a separatory funnel as a reservoir.
Other workers 60 packed the foam material (in cylindrical form) in a glass column
filled with acetone, in such a manner that the foam plugs were merely touching each
other; i.e., not compressed. Acetone was then flushed out with a suitable volume of
distilled water and water was leveled at the top of the foam column.
3. Pulsating Column Methods

Another type of device employed in various separation and preconcentration proc-
esses with polyurethane foam sorbents is the pulsating column.60" This column is sim-
ply a glass or plastic medical syringe (of adequate capacity) packed with loaded or
unloaded foam cubes or a cylindrical foam plug. Owing to the resilient character of
the open-cell polyurethane foam, the column can be easily compressed and released by
moving the plunger of the syringe. Forced pulsation of the foam syringe, with its tip in
17
FIGURE 7. Cell used in foam squeezing. From

Khan, A. S., Baldwin, W. G., and Chow, A., Can.
3. Chem.,59, 1490, 1981. With permission.)
a solution, brings the liquid, containing the substance to be sorbed, into repeated con-
tact with the foam sorbent. Figure 9 shows a schematic diagram of the manual pulsated
column method. 606
The pulsated column operation in a closed arrangement can be automated using a
motor to release and compress the plunger of the syringe cybernetically (Figure 10).
C. Collection and Retention Techniques in Gaseous Media

Polyurethane foams of polyether and polyester type have been employed in air mon-
itoring sampling systems in place of the traditional granular sorbents. For example, a
5.5 x 7.6 cm foam plug was used to substitute the coated glass beads in the lower
compartment of the SURC (Syracuse University Research Corporation) high volume
air sampler (Figure II). 7 1 As a general rule, the foam plugs were held under slight
compression in the (5 cm internal diameter * 7.6 cm) lower chamber of the glass sam-
pling module. This system allows air flow rates up to 250 I mirr1. A new sampling
head was recently suggested to modify this system. 87 The head consists of a milled
aluminum housing that holds a glass sampling cartridge and accomodates a 10-cm filter
for collection of airborne paniculate matter. The module is attached to the inlet of the
high volume sampling system through a trapped and threaded opening in the base of
Suction
120cm
FIGURE 8. Foam chromatographic column in

packing step. (From Braun, T. and Farag, A. B.,
Anal. Chim. Acta, 62, 476, 1972. With permission.)
the cartridge receptacle. A combination of polyurethane foam and granular sorbents

was also suggested as a dual sorbent for this process.
A simple air sampling assembly was also designed to determine chemical profiles at
12 heights in the field. 75 The polyurethane foam plugs were located in light-shielded
glass filter tubes that were aluminum spray painted. The assembly consists of a mast,
a Plexiglas surge tank, tubing and a modified commercial shop vacuum cleaner. The
mast was constructed from 2.54 x 1.27 cm x 2 m channel aluminum with appropriate
size holes drilled each 5 cm throughout the lower one meter, and each 10 cm through-
out the top meter. The sampling probes, 12 x 160 mm glass filter tubes, are positioned
at selected heights on the mast. This system allows air flow rates up to 83 t min'1.
A different high-volume sampling process is shown in Figure 12." Solid particles are
collected on a 142 mm diameter glass fiber filter. The volatile compounds are trapped
by two cylindrical plugs of polyurethane foam (5 cm thick and 11 cm diameter) located
behind the filter in a drainline system of 10 cm diameter. A perforated plate supports
the filter, but no support is necessary for keeping the foam plugs in place. Air flow
rate achieved was 433 I min"1.
19
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(e)
(-«8.7cm»-|
FIGURE 13. High-volume sampling apparatus for polynu-

clear aromatic hydrocarbons in the ambient air. (a) Glass fiber
filter; (b) stainless steel screen; (c) Teflon5" gasket; (d,) first po-
lyurethane foam plug; (d 2 ) second polyurethane foam plug; (e)
stainless steel cylinder. (From Oehme, M. and Stray, H., Z.
Anal. C/iem.,311, 665, 1982. With permission.)
A more or less similar sampling apparatus (Figure 13) was also reported, 89 but the
allowed air flow rate was higher (750 to 800 i min' 1 ).
A high volume gas sampler was employed to determine the retention efficiencies of
polyurethane sorbents using a gas chromatographic method. 81 This apparatus consists
of 14 1 cm thick polyurethane foam plugs packed loosely in a 7 cm diameter x 2.5 cm
long aluminum barrel (Figure 14). A 15th plug was spiked with about 40 ^g of mixed
polychlorinated biphenyl isomers in hexane, the solvent allowed to evaporate, and the
spiked plug placed at the front of the sampling train. A layer of polyurethane foam
prefilter was placed at the front of the sampler to minimize any contamination from
the laboratory atmosphere. Air was drawn through the foam column using a vacuum
pump at a flow rate of 150 to 810 I min"1.
A low volume sampling apparatus was suggested'0 for the recovery tests of polynu-
clear aromatic hydrocarbons (PAH). It consists of a glass fiber filter and two poly-
urethane foam plugs connected in series as shown in Figure 15. PAH (25 /ug of each)
PPF Prefllters
Screen Spiked
Support Plug
To Air Pump
1-cm Plugs
FIGURE 14. Apparatus for studying polychlorinated biphenyl elu-

tion through polyurethane foam sorbent. (From Simon, C. G. and
Bidleman, T. F., Anal. C/iera.,51, 1110, 1979. With permission.)
Air-
FIGURE 15. Low-volume air sampling train for recovery tests of polynuclear aro-
matic hydrocarbons, (a) Activated charcoal column (air purification column); (b) po-
lyurethane foam sorbent column (air purification column); (c) polyurethane foam sor-
bent column (glass tube: inside diameter 2 cm) 25 îg of each PAH was put on the glass
fiber-(GF). (d) GF; (e) stainless steel screen; (f) activated charcoal; (g) polyurethane
foam sorbent. (From Yamasaki, H., Kuwata, K., and Miyamato, M., BunsekiKagaku,
27, 317, 1978. With permission.)
were introduced on the glass fiber filter and air was passed through the tubes at 41 1
min"1.
Recently, a battery powered low-volume air sampling system utilizing polyurethane
foam as a trapping medium was evaluated.88 This portable sampler (Figure 16) pro-
vides air flow rates up to 4 i min"1 using a Dupont® P-4000 constant flow sampling
pump. The sampling cartridge (A) was constructed from a simple 20 mm (internal
diameter) x 10 cm borosilicate glass tube packed with a 22 mm diameter x 7.6 cm long
cylindrical polyurethane foam plug. Alternatively, two 3.8 cm long plugs separated by
a stainless steel wire may be used.
VIII. COLLECTION AND RETENTION OF INORGANIC AND

ORGANIC SPECIES WITH RESILIENT POLYURETHANE FOAMS
A. Unloaded Polyurethane Foams

The use of untreated polyurethane foams for the extraction, recovery, and precon-
centration of various inorganic and organic species in aqueous and nonaqueous media
and also in gaseous mixtures has received considerable attention during the last decade.
The nonselective sorption character of untreated polyurethane foams could be ren-
dered more selective by careful control of the experimental conditions. Several inves-
tigations have been conducted to clarify the sorption mechanism on polyurethane
foams. The present section summarizes the results obtained for the separation of var-
ious species on unloaded polyurethane foams sorbents.
23
Sampling Cartridge 'A'
Flow Range Valve

115V Adaptor/
Charger Plug Flow Rate Adjustment
LED Indicator Lights

(Timing, Flow, Battery) Drive Belt
Off-On Switch
Timing Switches
Sampling Cartridge B'
Paniculate Filter
FIGURE 16. Battery-powered air sampling pump and cartridge.

(From Lewis, R. G. and MacLeod, K. E., Anal. Chem.,54,310, 1982.
With permission.)
1. Collection of Inorganic Species
a. Sorption From Aqueous Media

The use of resilient polyether type polyurethane foams in the sorption of a number
of substances from aqueous solutions was first demonstrated by Bowen9 in 1970. Since
Bowen's pioneering work in this direction, many additional studies of the extraction
and separation of various inorganic species from aqueous solution have been carried
out.
Bowen9 reported that there are two classes of substances which are strongly extracted
from aqueous solution by the foam. These are substances which exist in aqueous so-
lution as free molecules with high polarizability (e.g., iodine, aromatic compounds,
metal dithizonates) and univalent anions with high polarizability (e.g., AuCl;, T1C1;, and
Fed;;). The sorption capacity of various species as determined from their isotherms was
found to be far too large (0.5 to 1.8 mol kg"1) to be attributed to surface adsorption
phenomena, which led to the conclusion that true absorption into the bulk of the pol-
ymer must be occurring. This was further confirmed by microscopical examination of
cross sections of foam membranes after iodine had been sorbed. The iodine color was
found to be uniform throughout the sections and was not confined to its surface.
Moreover, Bowen9 observed that the substances sorbed by polyether-based polyure-
thanes are those which can be extracted from aqueous solution by liquid diethyl ether.
He also noted that some weak-base anion exchange sites might be expected, because of
the presence of amino cross-linkages in the polyether and polyester type foams.
The isotherms of some elements have been measured,9 their distribution ratios and
Table 3
DISTRIBUTION RATIOS AND SORPTION CAPACITIES FOR
FOAM EXTRACTIONS
Absorption
Distribution capacities Formula of
Substance Solvent ratios (mol kg"1) complex
Iodine Water 700—3500 0.67—1.36 h

Chloroform Water 260—420 0.17—0.25 CHC13
Benzene Water 60—140 0.45—1.79 C6H6
Phenol Water 45—410 >0.032 C 6 H S OH
Mercury(II) 0.2 MHC1 30—125 >0.060 ND
Gold(III) 0.2 MHC1 45—3900 0.33—1.27 Aucir
Gold(III) 0.2 MHBr 140—570° 0.71 — 1.07 AuBrr
Gold(III) 0.2 MH1 250—590' 0.76—1.68 AuI 4 -
Iron(III) 6 MHC1 40—1400 0.38—0.77 FeCl4-
Rhenium(III) 6 MHC1 340- >0.043 ND
Thallium(III) 6 MHC1 170—3700 0.29—0.46 T1C14-
Antimony(V) 6 MHC1 75—500 0.25—0.59 Sb2Cl50,"-
Molybdenum(VI) 6 MHC1 27—41° 0.10—0.42 ND
Uranium(VI) Sat. 25—100 5*0.16 ND
A1(N03)3
Note: ND = not determined.
Only one foam tested.
From Bowen, H. J. M., J. Chem. Soc. A, 1082, 1970. With permission.
sorption capacities summarized in Table 3. In most cases the foams become saturated
with sorbant more or less rapidly, so that the distribution ratio falls off as saturation
is approached. In these instances the most favorable distribution ratios were found for
the more dilute solutions.
The sorption isotherms for iodine, gold(III), and iron(III) were measured at two
different temperatures. The sorption of iodine (Figure 17) and gold (III) was better at
low than at high temperatures; while in the case of iron (III) (Figure 18) the reverse
was true. The curves of Figure 17 show that the sorption isotherm of iodine is a straight
line, i.e., the distribution ratio is constant over the iodine concentration range studied.
In some cases attempts were made to investigate the nature of the sorbed species on
the foam using chemical analyses and diffuse reflectance spectra of foams after sorp-
tion. 9 The spectra of sorbed gold (III) halides and iron (III) chloride showed qualitative
resemblance to the spectra of the same substances in acid solutions. However, the
sorbed iodine spectrum had a single broad peak between 397 and 562 nm and differs
from the spectrum of iodine in water. Also attempted has been elution of some species
sorbed on the foam using dilute alkali or ammonia and in some instances acetone or
carbon tetrachloride. 12
i. Acidic Halides
Using a batch procedure, Bowen 912 examined the sorption of mercury (II) and gold
(III) from 0.2 M hydrochloric acid solutions by polyurethane foams. The retention of
gold (III) has also been investigated from 0.2 Mhydrobromic and hydroiodic acid. The
extraction of iron (III), rhenium (III), thallium (III), antimony (V), and molybdenum
(VI) has been tested in 6 M hydrochloric acid solutions (Table 3). Generally, the
amount of metal ion sorbed by the foam was measured by comparing some property
(e.g., UV absorption or radioactivity) of equal aliquot portions of solution before and
25
400
O>
en 51° C
1= 200
re
o
0.1
I2: solution/g kg
FIGURE 17. Uptake of iodine from water by foam at 22 and 51 °C.

(From Bowen, H. J. M., J. Chem. Soc., A, 1082, 1970. With permis-
sion.)
after sorption. Since the original concentration in the solution was known, the final
concentration and the absolute amount sorbed could readily be calculated.
Schiller and Cook13 examined the separation of gold(III) chloride from natural
waters with resilient polyurethane foam sorbent and compared their results with those
obtained by coprecipitation with iron(III) hydroxide, lead sulfide, or aluminum hy-
droxide and also by separation with Dowex® 1-X8 ion exchange resin. All experiments
were carried out in batch systems and the gold collected on the foam was determined
by a neutron activation analysis procedure. Lead sulfide and polyurethane foam were
found to be the most efficient collectors. Furthermore, no interfering gamma peaks
were detected using these carriers. This method facilitates the nondestructive determi-
nation of gold at ppb levels after being quantitatively collected on the foam sorbent.
In a dynamic extraction system, Sukiman14 was able to collect gold(III) chloride in
acidic aqueous solution using foam columns of 20 mm diameter and 100 mm length.
The columns were packed with 0.5 g of unloaded foam cubes by squeezing several
times with water. Three different polyether foam samples were examined. Gold (III)
at trace levels (0.02 to 25 ppm) was recovered from acidic aqueous solution by perco-
lating the solution through the foam column at relatively fast flow rates (30 to 40 ml
min' 1 )- Acetone was then employed for the recovery of gold from the foam column at
3 mi min"1 (Table 4). It was also mentioned that 0.3 thiourea in 1 M hydrochloric acid
solution can be used for elution of sorbed gold at 50°C, but acetone elution was pre-
ferred. Gold concentrations were measured radiometrically, by counting the activity of
0)
0.1 0.2
1
Fe: Solution/g kg
FIGURE 18. Uptake of iron(III) from 6 Mhydrochloric acid by foam at 22 and 51°C.
(From Bowen, H. J. M., /. Chem. Soc.,A, 1082, 1970. With permission.)
Table 4
THE UPTAKE AND RECOVERY OF GOLD FROM DISTILLED WATER AND
NATURAL WATER BY UNTREATED POLYURETHANE FOAM SOLVENT
(300 ml OF SOLUTION WAS EMPLOYED AND GOLD WAS MEASURED
RADIOMETRICALLY)
Acidified distilled water Acidified natural water0

Foam sample
(polyurethane Gold Gold recovered* i Gold recovered
type) (ppm) i Gold absorbed* with acetone % Gold absorbed with acetone
10/74 0.02 93.0 96.9 89.5 100.2

20.0 94.8 97.5
11/74 0.02 99.1 94.1 92.8 102.5
20.0 100.0 98.7
12/74 0.02 94.2 105.5 87.2 88.0
20.0 100.0 100.0
• Collected from Whiteknights Lake, U.K.

* Each figure is an average of three replicate experiments.
From Sukiman, S., Radiochem. Radioanal. Lett., 18, 129, 1974. With permission.
an aliquot of the effluent or eluate solution, or spectrophotometrically as gold chloride

after evaporating the solution to dryness followed by treatment of the residue with
aqua regia and concentrated hydrochloric acid. Polyurethane foam columns were also
employed14 for the collection of gold from natural waters (Table 4).
Recently, Te-Shang Lo et al.15 described a method for the separation of gold from
ore using polyurethane foam sorbent in the batch mode. They first sintered the ore at
600°C to remove sulfur, carbon, and other organic materials, followed by the disso-
27
100-
6 8 10 12
Base
Molarity
FIGURE 19. Effect of acid and base concentrations on the recovery efficiency for
gallium from a foam plug. (From Gesser, H. D., Bock, E., Baldwin, W. G., Chow, A.,
McBride, D. W., and Lipruski, W., Sep. Sci., 11, 315, 1976. With permission.)
lution of the ore in 1:1 aqua regia. The solution was diluted (1:3) and foam cubes (0.5
g) were then shaken with the solution for 30 min. Gold was recovered from the foam
with hot thiourea solution and determined by an atomic absorption method.
Gesser et al.16 have shown that open-cell polyurethane foam of polyether type can
be used as a solid substitute for diethyl ether in extraction systems. They investigated
the extraction and recovery of gallium from acidic chloride solutions. The effect of
hydrochloric acid concentration on the extraction efficiency is more or less similar to
that found in diethyl ether extractions. It was proved that open-cell foam is by far
more efficient than closed-cell rigid foam. It was mentioned that silicone rubber sponge
does not extract gallium under similar experimental conditions. Water or a weakly
basic solution was found to be suitable in eluting gallium from the foam column.
Figure 19 shows the effect of acid and base concentrations on the recovery of gallium
from the column.
The effect of temperature and flow rate on the extraction and recovery of gallium
also has been investigated. As expected, the efficiencies are generally increased by de-
creasing the flow rate. After a detailed experimental study, Gesser et al.16 concluded
that foam column efficiency can be increased either by passing the solution through
several foam plugs or by passing the same solution through the same foam plug several
times. Under optimal experimental conditions, it was possible to sorb gallium in the
foam to the extent of 10% by weight. This relatively high sorption capacity was linked
to the dissolution of gallium chloride complex in the foam material rather than to
adsorption on the foam surface. That is, the foam material acts as a polymeric solid
extractant for gallium. It is worth mentioning that this foam sorption method was
applied for the separation of gallium and iron from aluminum in acidic chloride solu-
tions. Iron(III) and gallium(III) are sorbed from 7.5 M hydrochloric acid and eluted
from the column by water or dilute ammonia. Gallium and iron were determined in
the eluate by atomic absorption spectrometry. It was reported that the extraction effi-
200
20 30 40 50 60
Time (min.)
FIGURE 20. Time dependence for (a) filled circles — the de-
sorption into 150 mt distilled water of gallium from loaded
(25.06 mg Ga) polyurethane foam; (b) other symbols — the
extraction of gallium of (150 ml, 200 ppm Ga) by polyurethane
foam at various HC1 concentrations. (From Gesser, H. D. and
Horsfall, G. A., J. Chim. Phys., 74, 1072, 1977. With permis-
sion.)
ciency of the polyurethane foam is 65 mg g ' for gallium(III) and 44 mg g'1 for iron(III)
with no interference from greater than 1000-fold amounts of aluminum.
In a further detailed study, 17 described were the thermodynamic properties of open-
cell polyurethane foam as a solid polymeric extractor for gallium from acidic chloride
media. A batch squeezing automatic technique was employed and gallium was deter-
mined in solution by atomic absorption spectrometry. The rate at which equilibrium is
established is shown in Figure 20, where the extraction of 200 ppm gallium in 150 ml
aliquots solution having various concentrations of hydrochloric acid was determined
as a function of time. As is evident from the curves, the rate of sorption of gallium
was elevated by increasing the hydrochloric acid concentration. This increase in hydro-
chloric acid concentration also raised the equilibrium extraction efficiency of gallium
(Figure 21). The results were found to be similar to those obtained in the extraction of
gallium by ether. 121 The extraction efficiency for gallium at 0.1 and 1.0 Mhydrochloric
acid containing various concentrations of lithium chloride was also examined (Figure
29
22). The effect of concentrations of acid, chloride, and gallium ions on the extraction
efficiency and the capacity of the foam has also been investigated. 17
The diffusion of gallium through thin polyurethane film sealed into a diffusion ap-
paratus was examined." The diffusion was found to be consistent with the solubility
of the HGaCl 4 complex in polyurethane. The "active transport" of gallium through
polyurethane membrane was explained by the hydrolysis of the complex after it had
passed through the membrane. On the premise of this study, Gesser et al.17 suggested
two alternative mechanisms for the sorption of gallium by polyurethane foam. One is
based on the close resemblance between foam sorption and liquid extraction with ether.
That is, gallium(III) forms a tetrachloro-complex in aqueous solution and the latter is
dissolved in polyurethane foam. In other words, the foam material behaves as a poly-
meric sorbent for the gallium chloride complex. The other mechanism results from
protonation of the ether sites in the polymer when coming into contact with acids in
aqueous solution. That is, the protonated sites act as anion exchangers in the extraction
of GaCU species:
H
I
H + + (-CH2-OCH2-)foam -> (_CH 2 -0-CH 2 -) foam (10)
+
H H
!
GaCU + (-CH2-0-CH2-)foam - (_CH 2 -O-CH 2 -) foam (11)
+ I
GaCl4
However, the results obtained by Gesser and co-workers17'18 do not permit distinc-
tion between the two proposed mechanisms. Some of the experimental results favor
one of the mechanisms while others could be better explained as a consequence of the
second mechanism.
In a further study, Gesser et al.18 investigated the transport of metal complexes, such
as HMX 4 of gallium and iron across thin polyurethane films to determine the mecha-
nism, but they reached a conclusion similar to that stated above.
The equilibria involved in systems employing a polyurethane foam material as com-
pared to systems using a liquid extractant in the removal of M3* from acidic aqueous
solutions was investigated further. 16 -' 9 For this purpose, the extraction of iron(III) by
open-cell polyurethane foam was studied as a function of acid, chloride, and iron
concentrations in the aqueous phase by an automatic batch squeezing technique. Iron
in the equilibrium aqueous phase was determined by spectrophotometry as the iron-
thiocyanate complex. The results obtained are generally explained on the basis of the
presence of the mixed extraction of FeCl3 and HFeCl4. They also show a dependence
of the metal distribution coefficient on iron(III) concentration in the aqueous phase
and give an indication for that dissociation of the extracted HFeCL, species in the foam.
It was concluded that flexible polyurethane foams can be considered as a solid poly-
meric extractant. 19
Further work on the extraction of iron (III) from acidic chloride solution by organic
solvents (ethers) and by foam under comparable conditions as above has been carried
out. It is worth noting that the electron paramagnetic resonance spectra of sorbed iron
studied19 were found to be identical to those obtained122 in liquid-liquid extraction of
iron from acidic chloride media.
Using a manual batch technique, Bowen9 reported that antimony(V) could be ex-
tracted with polyether polyurethane foams from 6 M HC1 solution with distribution
100 r-f
5 6 7
HCI (M)
FIGURE 21. Effect of hydrochloric acid concentration on

the sorption efficiency of gallium by polyurethane foam (150
mi, 200 ppm Ga, 60 min equilibration time). (From Gesser, H.
D. and Horsfall, G. A., J. Chim. Phys.,74, 1072, 1977. With
permission.)
ratios of 75 to 500 and foam capacities of 0.25 to 0.59 mol kg"1. More recently, the
extraction of antimony(III) and (V) from aqueous hydrochloric acid solution by poly-
ether (open-cell) polyurethane foam has been investigated20 using an automatic batch
squeezing device. The sorbed antimony was determined indirectly by measuring the
radioactivity of the aqueous solution before and after extraction. In some experiments
direct measurements of the radioactivity on the foam were carried out. The maximum
extraction of both antimony(III) and (V) was obtained from 7 M hydrochloric acid
solutions. The distribution coefficients of antimony(III) and (V) were only 416 ± 13
and 500 ± 17, respectively. At higher or lower acid concentrations the distribution
coefficients were significantly decreased. However, in the presence of 7 MLiCl and 0.7
Macid solution the extraction of both antimony(III) and (V) is more or less quantita-
tive (Table 5) with quite high distribution coefficients using concentrations ranging
between 0.01 and 100 ppm. However, at 1000 ppm antimony concentration the extrac-
tion decreased by 50%. The capacities of the two polyurethane foams tested were
found to be 8.5 and 4.5% (Sb: foam, w/w). 20
Quantitative elution of antimony from the foam was possible using acetone. It was
31
100
3
LiCI (N)
FIGURE 22. Effect of lithium chloride concentration on the

sorption efficiency of gallium for different (1.0 M circles and
0.10 M squares) HC1 concentrations (150 ml, 200 ppm Ga).
(From Gesser, H. D. and Horsfall, G. A., J. Chim. Phys., 74,
1072, 1977. With permission.)
suggested that the foam acts as a polymeric solvent extractant for HSb(III)Cl4 and
HSb(V)Cl6 species.20
The extraction behavior of tin(II) and tin(IV) from acidic chloride media with poly-
ether and polyester foams has been examined21 using batch squeezing and column sys-
tems. The polyester foam was found to extract tin(II) and tin(IV) from ^ 6 M hydro-
chloric acid solutions. Complete extraction of tin(IV) was achieved in column
experiments using a flow rate of 0.1 mi min~' (column diameter > 2.1 cm). However,
the polyester foam material has a poor stability at this acid concentration and conse-
quently, polyether polyurethane foam is preferable. The effect of the different halic
acids and halide ions on the extraction efficiency of tin(IV) was investigated in a batch
squeezing system. Tin(IV) concentration in the aqueous solution was measured either
radiometrically using tin-119m tracer or by atomic absorption spectrometry. In a few
cases, the amount of tin retained on the foam was determined directly by measuring
the radioactivity of the foam itself. The extraction efficiency of tin(IV) on polyether
foam is generally better than on polyester. Figure 23 shows the effect of hydrochloric
acid and lithium chloride concentrations on the extraction of tin(IV) by the polyether
foam. In this batch experiment the chloride ion concentration was held constant at 10
M and the hydrogen ion concentration increased. As is evident from the figure the
Table 5
EFFECT OF LITHIUM CHLORIDE CONCENTRATION ON
PERCENT EXTRACTION AND DISTRIBUTION COEFFICIENT
(D) OF ANTIMONY (100 ppm) FROM 150 ml OF 0.7 MHC1
SOLUTION BY POLYURETHANE FOAMS (0.5 g)
Regular polyurethane Acid-resistant polyurethane

Sb (III) Sb (III) Sb (V)
LiCl
(M) % Extn. D % Extn. D % Extn. D
4 2 6 1 3 1 3
5 — _ 1 0 33 30 129
6 — — 57 398 58 414
7 93 4,360 95.3 6,150 97.2 10,414
8 — — 88.0 2,200 98.0 14,700
9 — — 72 111 99.2 37,200
10 21 95 57 398 99.2 37,200
From Lo, V. S. K. and Chow, A., Anal. Chim. Acta, 106, 161, 1979. With permission.
extraction decreases drastically at high hydrogen ion concentration. The extraction of

tin(IV) from 3 M solutions of hydrofluoric, hydrochloric, hydrobromic, and hy-
droiodic acid was also examined and found to be 0, 32, 18, and 32%, respectively. The
size of the anion has no consistent effect on the extraction process.
The effect of metal halides on the extraction of tin(IV) by the polyether foam was
also examined (Table 6).21 The efficiency of extraction increases according to the in-
crease in cation size (from Li* -» K*) or the size of the anion (from Cl~ -*• Br"). It was
also realized that the sorption of tin(IV) from HCl-LiCl solution is better than from
HC1 alone. Up to 98 ± 2% of tin(IV) could be extracted from 50 ml 10 M lithium
chloride in 0.12 Mhydrochloric acid by 6 hr of squeezing. The sorbed tin is recovered
from the foam material by another 6 hr squeezing in 0.1 Mhydrochloric acid solution
or acetone.
The extraction of 100 ppm of tin (IV) in the presence of up to 1000 ppm of Bi3*,
Cu 2+ , Fe2+, Sb3*, Sb5+, and Zn2* was also studied by Lo and Chow. 21 Only Fe3+ at 100
ppm concentration level interfered owing to the competitive sorption of Fe3+ and Sn4*
on the foam under the experimental conditions tested. The capacity of two polyether
polyurethane foams for tin was found to be 62 and 81 ± 9 mg/g dry foam. Obviously
these relatively high capacities are due to absorption rather than adsorption processes.
Explanations for the extraction processes involved were reported, but the exact mech-
anism of the absorption of tin(IV) was not verified.
ii. Aqueous Nitrate

In his first publication Bowen9 reported that uranium(IV) could be absorbed from
saturated aqueous aluminum nitrate solution by polyether polyurethane foams. The
uranium distribution ratios are between 23 and 100 and the sorption capacity is /v 0.16
mol kg~' foam. The diffusion of uranyl nitrate from aqueous solution containing alu-
minum nitrate through a thin polyurethane membrane has also been investigated.18
In addition, a close comparison was made between the extraction of uranyl nitrate
from aqueous nitrate solutions by open-cell polyether polyurethane foam 2 2 " and die-
thyl ether. 123 Equilibration of the aqueous solution and the foam material was made
by an automatic squeezing device.22 The rate of extraction of uranium from 11 M
ammonium nitrate solution at 25°C is shown in Figure 24. Water was used for the
recovery of uranium from the foam material.
33
LITHIUM CONCENTRATION, M
8 7 6 5 4 3 2 1
100
1 2 3 4 5 6 7 8 9 1 0
HYDROGEN ION CONCENTRATION, M
FIGURE 23. Effect of hydrochloric acid and lithium chloride

concentration on the sorption of tin(IV) by acid-resistant
foam. Tin(IV) concentration = 100 ppm, volume = 150 mi and
squeezing time = 6 hr. (From Lo, V. S. K. and Chow, A.,
Talanta, 28, 157, 1981. With permission.)
The effect of nitrate ion concentration on the extraction of uranyl nitrate into the
foam material (Figure 25) was examined in the presence of different cations, e.g.,
NH 4 + , Ca2+, and Al3*, and a comparison was made with the results repeated by the
same systems using diethyl ether as extractant. Polyurethane foam was found to be 10
to 100 times more effective than the liquid solvent. The effect of temperature and pH
of the aqueous solution was examined and it was concluded that polyurethane foams
have thermodynamic extraction parameters similar to organic solvents. The capacity
of the foam was found to be 160 mg U g~'. However, it was indicated22 that higher
capacities could be achieved at lower temperatures.
iii. Acidic Thiocyanate

The extraction and separation of iron(III), 9 2 4 2 S cobalt(II), 24 28 rhodium(III), 29 iri-
dium(IV), 29 mercury(II), 30 31 zinc(II),30 indium(III), 30 31 and palladium(II) 32 " in acidic
Table 6
EFFECT OF METAL
HALIDES ON THE
EXTRACTION OF TIN
(IV) BY REGULAR
POLYURETHANE
FOAM-
Metal hal- Sn extracted, %

ide
LiCl 14 ±2
NaCl 25 + 2
KC1 34 ± 2
LiBr 33 ± 2
NaBr 38 ± 2
KBr 40 ±4
Lil 28 ± 2
Nal 37 ± 2
KI 39 ±4
Volume of solution 50 ml,

squeezing time 2 hr, tin(IV)
concentration tracer only;
concentration of metal hal-
ide 3 M.
From Lo, V. S. K. and Chow,

A., Talanta, 28, 157, 1981.
With permission.
aqueous thiocyanate solutions using unloaded polyether and/or polyester polyurethane

foams have been described. Bowen9 has mentioned that iron(III) could be sorbed by
polyether polyurethane foam from this medium. Braun et al.24 reported that cobalt(II)
in aqueous thiocyanate solution is significantly retained by polyether polyurethane
foam. The first detailed study on the separation and preconcentration of iron(III) and
cobalt(II) in aqueous thiocyanate medium is that published in 1978 by Braun and
Farag.25 The rate of extraction of cobalt and iron in acidic (0.1 N HC1 or H2SO4)
aqueous thiocyanate (0.5 M) solution was examined in batch experiments. The concen-
tration of iron and cobalt was measured radiometrically and extraction rates of both
metal ions were found to be quite high, but the rate of extraction of cobalt was slightly
higher than that of iron(III) (Figure 26). In light of these results, polyether polyure-
thane foam was suggested for the collection of these metal ions using columns operated
at relatively high flow rates. More or less complete extraction of 2 ^g cobalt or iron is
obtained from acidic thiocyanate solutions into the foam columns at flow rates as high
as 40 ml min'1 (column diameter, 25 mm). Quantitative collections of iron and cobalt
at concentrations between 0.2 and 200 ^g were also successfully obtained at 20 mi
min"1 flow rates (Table 7).
The high capacity measured for the foam material for thiocyanate complexes was
considered as further proof that polyurethane foam acts as a solid polymeric extrac-
tant. That is, the thiocyanate complexes are sorbed in the foam material instead of
being adsorbed on its surface.
Polyether polyurethane foam columns were also successfully used for the preconcen-
tration of 1 ^g of cobalt or iron in 1.0 I volumes of aqueous thiocyanate solutions at
flow rates of 30 mjf min"'. 25
35
500r
40 80 120 160 200

TIME (min)
FIGURE 24. The sorption of UOjtNOj)* from (a) 150 mi of 11 M

NH 4 NO 3 500 ppm U by a 2 g polyurethane at 25°C as a function of
time. The recovery of the sorbed UOj(NO3)2 into (b) 150 ml of H2O
at 25°C. (From Gesser, H. D. and Gupta, B. M., Proc. I. S. E. C.
Conf., Grenoble, 1980. With permission.)
25
10
25
O)
o
-6 -5 -4 -3 -2 -1
Log (UO*
FIGURE 25. Uranium distribution coefficient vs. aqueous uranyl concentration at

various temperatures and nitrate concentrations. (From Gesser, H. D. and Gupta, B.
M., Proc. I. S. E. C. Conf., Grenoble, 1980. With permission.)
100
FIGURE 26. Rate of sorption of cobalt and iron from 0.5 Macidic thiocyanate so-
lution, (a) Cobalt, (b) Iron. (From Braun, T. and Farag, A. B., Anal. Chim. Acta,9S,
Table 7
COLLECTION OF VARIOUS
CONCENTRATIONS OF COBALT OR
IRON FROM 0.2 MOR 0.5 M
THIOCYANATE SOLUTIONS,
RESPECTIVELY, ON UNLOADED
POLYETHER FOAM COLUMNS AT FLOW
RATES OF 20 Ml MIN-
Average
metal ion
Amount extracted
of metal on foam* Relative accuracy Std.
ion (fig) (x, %) of the mean (%) dev.(s)
0.2 99.7' -0.3 0.23

99.4' -0.6 0.30
2.0 99.7* -0.3 0.24
99.5' -0.5 0.30
20.0 99.5" -0.5 0.22
99.4" -0.6 0.33
200.0 99.5" -0.5 0.21
99.3' -0.7 0.38
Average of 5 determinations.
' Cobalt.
Iron.
From Braun, T. and Farag, A. B., Anal. Chim. Acta, 98,

37
Table 8
EFFECT OF SQUEEZING TIME
AND SOLUTION VOLUME ON
EXTRACTION OF COBALT
Extraction (%)"
Time 100 150

(min) 50ml 75 ml ml ml
10 97.8 91.7 74.3 61.2

20 99.7 98.7 83.8 72.1
30 99.7 99.0 93.3 86.0
40 96.0 91.3
50 96.9 93.6
60 97.1 94.3
Volume of 1.0 ppm cobalt solution in 3

MNH 4 C1-IM NH 4 SCN extracted with 44
± 3 mg of polyurethane foam.
From Chow, A., Yamashita, G. T. and Ha-

mon, R. F., Talanta, 28, 437, 1981. With
permission.
The extraction of cobalt-thiocyanate complex in the presence of a relatively high

ionic strength (5 M NH4C1) has also been examined by Chow et al.26 using a batch
squeezing extraction technique. The extracted cobalt was measured directly on the
foam by X-ray fluorescence spectrometry. In some experiments the cobalt that re-
mained in solution was measured radiometrically or by atomic absorption spectrom-
etry. The effect of the volume of the aqueous solution on the extraction efficiency of
cobalt in 3 MNH4C1-1 Mthiocyanate solution was investigated using 10 to 60 min of
continual squeezing (Table 8). Cobalt is more readily extracted from smaller volumes,
however; in larger solution volumes, longer squeezing times or thicker foam discs are
required. Also, thick foam discs are recommended for the preconcentration of cobalt
in aqueous thiocyanate media.
Quantitative extraction of cobalt by polyurethane foam in 3 MNH 4 C1 1 MNH 4 CNS
solution has been achieved in the presence of (1 ^g ml)'1 copper, iron, lead, zinc, or
nickel.26 Nickel and lead are not extracted at all by the foam under the experimental
conditions tested. However, iron, zinc, and copper are coextracted with cobalt to dif-
ferent extents, but they do not interfere in the subsequent determination of cobalt by
the X-ray fluorescence method.
Positive results have also been reported26 for the extraction of cobalt in a column
operation using foam discs with the same diameter as the column (25 mm), and 0.64
cm thick. The retention of cobalt in concentrations between 0.25 and 2.0 îg mt~l is
quantitative at flow rates of about 1 ml min"1.
The possibility of using polyether polyurethane foam for the preconcentration and
separation of rhodium(III) and iridium(IV) from aqueous thiocyanate solution has
been tested.29 Rhodium and iridium were determined in solution using atomic absorp-
tion spectrometry and radiometric methods, respectively. A multiple automatic squeez-
ing device was used in the concentration step. The extraction efficiencies were investi-
gated as a function of hydrochloric acid and thiocyanate concentrations and solution
temperature. Figure 27 shows the effect of acid concentration on the distribution coef-
ficient of rhodium. The optimal acid concentration is 2 M which is better added after
5 I
(a)
(b)
1 1 1 1 1
0.2 0.4 0.6 0.8 1.0
I I I I
HCI
FIGURE 27. The effect of hydrochloric acid on the sorption of rhodium. Initial rhod-
ium concentration 16.67 jjg ml'1; volume of solution 145 ml; weight of foam 0.1 g: (O)
0.15 M thiocyanate, acid added before heating: (•) 0.004 M thiocyanate, acid added
after heating. (From Al-Bazi, S. J. and Chow, A., Anal. Chem., 53, 1073, 1981. With
permission.)
heating the solution to 90°C for 4 hr to ensure the formation of the Rh(SCN)3; complex.
In the case of iridium, however, the distribution coefficient is quite independent of the
acid concentration. It was observed that the formation of the extractable species of
both rhodium and iridium is slow at room temperature and thus heating the solution
to 90°C is necessary. The extraction of iridium decreases at thiocyanate concentration
below 0.02 M, but the extraction of iridium increases (Figure 28). On the basis of these
results 0.002 M thiocyanate concentration was chosen in the separation of iridium and
rhodium using 3 hr of batch squeezing. Finally, it was reported that the extraction of
iridium and rhodium depends on different interrelated parameters, i.e., on the amount
of the thiocyanate complex formed rather than on the distribution of the complex
between the foam and the aqueous phase. Attempts to improve the extraction of rhod-
ium by increasing the amount of foam were unsuccessful. Although this separation
method is not entirely convenient, because of the difficulty of the separation, in com-
paring the results with those obtained by other separation techniques the foam method
can be considered competitive.
Braun et al.30-31 examined the sorption of zinc(II), mercury(II), indium(III), and
gold(III) from aqueous thiocyanate solution with polyether and polyester polyurethane
foams. Special attention was given to the extraction properties of the polyester foam
as it contains less trace metal impurities than the ether type. This is of special impor-
tance when the neutron activation analysis method is used for trace metal determina-
tion after its preconcentration on foam.31
Both the polyether and polyester foams were found30'31 to extract the thiocyanate
complexes of zinc, mercury, gold, and indium from aqueous solution. Figure 29 shows
the effect of thiocyanate concentration on the sorption of zinc and indium using a
batch technique. The mercury thiocyanate complex is also extracted by both types of
foam.
39
o
o
(b)
0.02 0.04 0.06

(SCIST)
FIGURE 28. The effect of thiocyanate on the separation of rhodium

and iridium (acid added after heating the solution), (a) Sorption of
rhodium; initial rhodium concentration 16.67 pg ml'', volume of so-
lution 145 ml; weight of foam 0.1 g, hydrochloric acid concentration
2 M; (b) sorption of iridium, initial iridium concentration 15 ng ml"',
volume of solution; 100 mt, weight of foam 0.05 g, hydrochloric acid
concentration 2 M. (From Al-Bazi, S. J. and Chow, A., Anal. Chem.,
The foam extraction of zinc from 0.2 M thiocyanate solution is almost quantitative
over the pH range 0 to 6, but the distribution ratios were improved as the pH increased
from 0 to 6.30 In the case of mercury, the sorption is almost quantitative up to pH 6,
but the polyester foam is less efficient. For indium, the extraction is quantitative in the
pH range 2 to 8, the distribution ratios being higher at lower pH values. In batch
experiments 1 min contact time was found to be sufficient for complete sorption of
zinc and indium on the polyether foam. Various concentrations of zinc and mercury
were successfully extracted with the polyether foam (Table 9).
Zinc(II), indium(III), and mercury(II) were quantitatively collected on the foam col-
umn from very dilute aqueous solutions using flow rates of 100, 87, and 28 mi min"1,
respectively.30 Nitric acid (1 M) was employed to elute zinc at 2 m,f min'1 flow rate.
However, mercury and indium were completely eluted with a 1 M potassium thiocya-
nate solution in 80% acetone at a flow rate of 15 mi min"1. It was noted that acetone
alone can be employed for the elution of mercury from the foam column but at a flow
rate of 1 mi min"1.
Conditions for the extraction of the thiocyanate complex of palladium by polyether
polyurethane foams have been reported32-33 and sorption mechanisms were suggested.
In a multiple automatic batch squeezing system, the extraction of palladium thiocya-
nate was first studied as a function of contact time. Palladium concentration in the
aqueous solution was measured by atomic absorption spectrometry. The percentage of
palladium extracted increased sharply with extraction time up to 15 min and then more
slowly up to 1 hr, after which it remained almost constant. It was reported that a rapid
increase in the extraction of palladium occurred as the thiocyanate concentration in-
creased up to 0.001 M. At higher thiocyanate concentrations the extraction decreased.
The same behavior was also observed in the presence of 2 M potassium chloride under
identical conditions (Table 10).
The effect of hydrochloric acid concentration and the pH of the aqueous solution
Polyether
100i
(a)
n r _
80 - / if '" 'V %
— Polyester —'
/
— 60
UJ
40 -
20 —
I I I
0
0.2 0.4 0.6 0.8 1.C
1 KSCN] (M)
(b) i— Polyether
100 1
80 f \— Polyester
5 60 £- —
40 -
20
1 1 1 1
0 0.2 0.4 0.6 0.8 1.C
[KSCN] (M)
FIGURE 29. Effect of thiocyanate concentration on percent

sorption on unloaded polyether (O) and polyester (•) type
foams for (a) 10.5 ^ Zn2* mt~' at pH 2.5, (b) 1.8 fig In3* ml-
at pH 2. (From Braun, T. and Abbas, M. N., Anal. Chim.
Acta, 134, 321, 1982. With permission.)
Table 9
EFFECT OF METAL ION CONCENTRATION ON THE EXTRACTION
EFFICIENCIES FOR ZINC AND MERCURY ON UNLOADED POLYETHER-
TYPE FOAM FROM 0.2 MTHIOCYANATE SOLUTION AT pH 2 TO 3
Zinc Std. dev. Confidence Mercury Std. dev. Confidence

jJg ml- s° limit* % E s° limit*
0.50 99.2 0.35 0.6 0.01 99.2 0.2 0.3
10.00 98.8 0.3 0.4 0.10 99.9 0.1 0.2
50.00 96.3 0.5 0.8 1.00 99.3 0.2 0.3
" n = 5.
* (ts/n)'/2 for t = 95.
From Braun, T. and Abbas, M. N., Anal. Chim. Acta, 134, 321, 1982. With permission.
on the extraction efficiency of palladium by the foam material has also been investi-
gated.32 Extraction increased rapidly with hydrochloric acid up to 0.08 M. At higher
pH values extraction decreased considerably. However, sorption of the palladium com-
plex was quite quantitative and independent of pH in the presence of 2 M potassium
41
Table 10
EFFECT OF
THIOCYANATE ON
PALLADIUM
EXTRACTION AND
DISTRIBUTION RATIO
IN THE PRESENCE OF
POTASSIUM
CHLORIDE"
(SCN~) M E, % log D
0.002 100.0 6.95

0.004 98.4 5.09
0.006 99.9 6.95
0.008 98.3 5.05
0.012 99.9 6.16
0.02 99.2 5.38
0.06 99.7 5.76
0.1 97.1 4.80
0.5 96.1 4.69
1.0 92.0 4.34
Initial palladium concentration

13.3 fjg ml''; pH = 2.7; potas-
sium chloride concentration 2
M; volume of solution 95 ml;
weight of foam 0.05 g; time for
extraction 20 hr.
From Al-Bazi, S. J. and Chow, A.,

Talanta, 29, 507, 1982. With per-
mission.
chloride in aqueous thiocyanate solution (Figure 30). It is worth noting that the extrac-
tion of palladium is highly minimized by the presence of ammonia in the aqueous
solution. This fact is useful in the recovery of palladium from the foam material.
The ionic strength effect of various chlorides on the extraction of palladium thiocy-
anate by polyurethane foam was investigated32 using lithium, sodium, potassium, and
ammonium chlorides. The effect of the added salt on the extraction is virtually inde-
pendent of the nature of the salt at concentrations above 0.5 M (Figure 31). At lower
salt concentrations a very different behavior was observed. Also, the extraction effi-
ciency increases in the following order of the cation added: Li* < Na* < K+ < NHt, < Rb+
< Cs+. The ion-dipole interaction of ammonium ions with the oxygen sites of polyure-
thane foam was claimed to contribute to the extraction of Pd(SCN)2; the interaction
being higher in the presence of ammonium chloride than potassium chloride at concen-
trations above 0.5 M. However, the extraction of palladium as a function of the ionic
diameter of the added cation passes through a maximum which suggests that there are
other factors involved. On the basis of the above-mentioned results it was
concluded32 33 that polyurethane molecules behave as long acyclic chains and the ex-
traction of the anion complexes occurs through a cation chelation mechanism (de-
scribed below).
Recently, the mechanism of metal ion sorption by polyether polyurethane foam was
critically investigated using the extraction of cobalt(II)27 and palladium(H)33 thiocya-
nate complexes as models. The mechanisms considered were surface adsorption on the
100-
40
FIGURE 30. Effect of pH on palladium sorption in the absence and

presence of potassium chloride. Initial palladium concentration 13.3
^g mi~': thiocyanate concentration 0.006 M volume of solution 95
ml; weight of foam 0.05 g; time for extraction 20 hr: (1) in the absence
of potassium chloride; (b) in the presence of 2 Mpotassium chloride.
(From Ali-Bazi, S. J. and Chow, A., Talanta, 29, 507, 1982. With
permission.)
0.5 1 1.5
Ionic strength
FIGURE 31. Effect of ionic strength on the extraction of palladium;

initial palladium concentration 13.3 pig my1; thiocyanate concentra-
tion 0.006 M. (a) NH- 4 (b) K', (c) Na*; (d) Li*; pH~6, except for
NHi where pH was ^4; volume of solution 95 ml; weight of foam 0.05
g; time for extraction 20 hr. (From Al-Bazi, S. J. and Chow, A.,
Talanta, 29, 507, 1982. With permission.)
foam membranes, ether-like solvent extraction, ligand addition, ligand exchange, an-
ion exchange, and cation chelation mechanisms.27-33 Taking into account the low sur-
face areas measured for several polyether polyurethane foams 9 - 17 - 21 - 119 the surface ad-
sorption mechanism has been rejected by many investigators.' 192024 This is actually
confirmed by the relatively high capacity measured9 (0.5 to 1.8 mol kg"1) for various
43
species on the foam material. Coupled with the observation that several species, such
as I 2 , 9 GaCl;,16-17 Co(NCS)2;,3 3" Fed;,17 UO 2 2 3 1 8 are able to diffuse through intact
polyurethane membranes, confirms that true sorption into the bulk of the polymer
must occur.
The solvent extraction mechanism, which relies on the consideration that polyether
and polyester polyurethane foams can act as solid polymeric extractants,9-16-19 22-25-35
has also been criticized and excluded as a singular mechanism. 27 ' 33 Obviously, the sol-
vent extraction mechanism is based on the assumption that neutral metal complexes
are first formed in the aqueous solution and then extracted via dissolution in the hy-
drophobic foam material. However, this mechanism fails to explain the extraction of
e.g., Co(NCS)2; from aqueous alkaline solution in the presence of sodium chloride.
Under these conditions, the formation of the neutral protonated species H2Co(NCS)4
is not probable. Also, the abrupt drop in the extraction efficiency of polyurethane
foam for cobalt thiocyanate complex in more acidic media cannot be satisfactorily
explained on the basis of this mechanism. An increase in the extraction efficiency
rather than a decrease could be expected with increasing acid concentration. Finally,
the distribution ratios of various species on the foam sorbent were found 9 2 7 3 3 to be
several orders of magnitude higher than those obtained under comparable experimen-
tal conditions for ether extractions. Table 11 shows the distribution ratios reported in
the literature for ether extraction of some metal ions in various media and those ob-
tained for polyether polyurethane foam sorbent.
Ligand addition and ligand exchange mechanisms were also taken into consideration
but later discarded.27-33 Ligand addition (considering polyurethane as a ligand), for
example to Co(NCS)2^ will cause an increase in the coordination number of the metal
which is quite rare. Also, absorption spectra of the extracted cobalt-thiocyanate species
sorbed in polyurethane foam films suggested that the sorbed species is tetrahedral.
Furthermore, the colors obtained27 when some other complexes are extracted by poly-
urethane foam are typical to the tetrahedral species (e.g., Fed;;, Pd(NCS)2;) and seem
to confirm that appreciable complexation of the metal ion in the foam by the ligand
addition mechanism cannot be common.27'33
In the case of ligand exchange it was thought the symmetry of the complex would
change, which would be accompanied by some alteration of the absorption spectra.
This is not the case as the sorbed complexes of several metals were rapidly recovered
from the foam material into various organic solvents (e.g., acetone, methyl isobutyl
ketone and bis 2-(2-methoxyethoxy)ethyl ether). On the basis of these results the ligand
exchange mechanism is considered to be unlikely. 27 - 33
The possibility that polyurethane foam can behave as a weak-base anion exchanger
has also been mentioned by some authors. 9 - 27 " This could occur by the protonation of
some sites in the polymer, such as nitrogen-containing urea or urethane linkages, or
perhaps the ether linkages in polyether-base foams followed by exchange of the anionic
metal complexes on these protonated sites. Obviously, this mechanism could work in
the presence of high concentrations of strong acids, but it should not play a significant
role in the absence of appreciable amounts of acid. For this reason, Hamon et al."
came to the conclusion that if anion exchange does occur, it necessarily takes place at
sites generated by some other mechanisms. Consequently, they proposed a new sorp-
tion mode they call the cation-chelation mechanism. In their view many cations, such
as Na*, K% Ag+, NH}, Pb2*, Ba2*, and H3O% are capable of being multiply complexed
by the polyurethane polymer macromolecules at specific sites. This results in a solid-
phase (or matrix) species which can be regarded as equivalent to an ion-exchange ma-
trix or to a solvated cation in solid solution:
site ^± (M.site)"+ (12)

Table 11
COMPARISON OF COMPLEX METAL ANION SORPTION BY OXYGEN-
CONTAINING ORGANIC SOLVENTS AND POLYETHER-BASED
POLYURETHANE FOAM
Metal
ion Aqueous phase Organic phase
Sb (III) 6 M HC1 Diethyl ether 0.06

6.5—8.5 M HC1 Di-isopropyl ether 0.16
7 M HC1 Polyether foam 416
Sb (V) 6 M HC1 Diethyl ether 4.3
6.5—8.5 M HCI Di-isopropyl ether 199
7 M HCI Polyether foam 500
Sn (IV) 6 M HCI Diethyl ether 0.2
Fe (III) 6 M HCI Diethyl ether 99
7.75—8 M HCI Di-/'sppropyl ether 1,000
9 M HCI /3,/3'-Dichloroethyl ether 99
1 M HCI + 6 M LiCl Polyether foam 10,000
1 M HCI Polyether foam 1,000
Ga(III) 6MHC1 Diethyl ether 32
7 M HCI Di-isopropyl ether >1,000
0.85 M HCI Polyether foam 6,300
Co (II) 0.5 M HCI + 1 M NH 4 SCN Diethyl ether 0.037
0.5 M HCI + 2 M NH 4 SCN Diethyl ether 0.605
0.5 M HCI + 3 M NH4SCN Diethyl ether 1.39
0.5 M HCI + 7 M NH.SCN Diethyl ether 3.03
1 M KSCN + 1 M buffer + 1 M KC1 Polyether foam >106
5 M KSCN + 1 M buffer Polyether foam >106
1 M NaSCN + 1 M buffer + 1 M NaCl Polyether foam >106
2 M NaSCN + 1 M buffer Polyether foam >106
Pd (II) 0.5 M HCI + 1 M NH 4 SCN Diethyl ether 0.02
0.5 M HCI + 0.15 M KSCN Polyether foam 18,200
Distribution ratio in kg'1 for polyurethane foam. From Hamon, R. F., Khan, A. S. and Chow,
A., Talanta, 29, 313, 1982. With permission.
where species within the polymer phase are indicated by bars. The extraction of ion-
association complexes having these cations as counter-ions will greatly be facilitated
owing to the stability of the chelate. However, which anions will accompany the cat-
ions in largest numbers will be determined by a variety of factors, including the indi-
vidual hydrophobic nature and charge of the anions, and perhaps their ability to inter-
act in other ways with the polymer. Anionic metal complexes MeX"1;, particularly those
which are coordinatively saturated with nonhydrophilic ligands, might be expected to
be well extracted. It was reported27'33 that the sorption of the ion-association complex
can be regarded as taking place by a solvent extraction process in which the cation
happens to be more effectively solvated than usual. This results, of course, when little
or no sorption of anions other than MeXm; occurred. The extraction mechanism could
be represented by:
mM p+ + pMeX;;1" + m site ^ m (M.site) p + + pMeX™- (13)

45
On the other hand, if considerable sorption of another ion-association complex con-

taining M p+ and some moderately extracted anion, A", occurs either before or concur-
rently with the sorption of MeX"1;, then the latter may be more conveniently regarded
as sorbed by an anion-exchange process in which it is exchanged for A~ at the positive
sites that result from the chelation of Mp* by the polymer. The extraction mechanism
can be represented by:
M1" + pA 4- site ^ (M.site)1" + pA (14)
(M.site)1" + pA + pMeX;;1 ^ (M.site) p+ + pMeX;;1" + mA~ (15)
Therefore, the cation-chelation mechanism resembles both solvent extraction and ion-
exchange depending to some extent on solution conditions.
Hamon et al.27 confirmed their cation-chelation mechanism by comparing the results
obtained for the sorption of some species with polyurethane foam sorbent and those
reported with macrocyclic ("crown") ethers. They noted increased sorption of
Co(NCS)24 by polyether polyurethanes containing increased proportions of polyethylene
oxide relative to polypropylene oxide. This was explained on the basis of previous
work 124 126 on crown ethers. That is, polyethylene oxide has a strong cation complexing
ability giving rise to a helical pattern of inwardly directed oxygen atoms with the che-
lated cation. Moreover, the authors interpreted the superiority of the sorption efficien-
cies of polyether polyurethane foams over those of the polyester by the fact that the
latter has an inherent inability to become helically oriented about the central axis owing
to the geometry and limited flexibility of the ester bond. 27
Further compelling evidence in support of strong polyether involvement in the ex-
traction of ion pairs was reported. 27 Measurement of the infrared spectrum showed a
shift of about 30 cm"1 in the ether vibrational modes near 1100 cm"1 when cobalt(II)
was sorbed by the foam from aqueous sodium thiocyanate solution. This change is
indicative of metal-polyether interactions. Moreover, the strong infrared absorption at
2055 cm"1 indicates that the thiocyanate is bonded to cobalt through the nitrogen atom.
Additional evidence for the existence of strong polyether-metal ion interactions comes
from the observation that polyurethane foams which are nearly saturated with co-
balt(II) thiocyanate exhibit a marked increase in the polymer glass transition tempera-
ture (i.e., they fail to return to their original shape when compressed and lose much of
their flexibility, to the point of becoming brittle).
Furthermore, it was reported that some selectivity of the polyether chain is demon-
strated for particular cations.27 In the extraction of Co(NCS)24, Zn(NCS) 2 4 , picrate, and
8-anilino-l-naphthaline-sulfonate (ANS~) anions, the order of extractability follows
the series Li* < Na* < Cs* < Rb* < K* ^ NH*. < Ag* ^ Tl* < Ba2* < Pb2*. This order of
cation performance was found to be nearly identical to that of 18-crown-6 deriva-
tives127 and also noncyclic polyethers.128 The proposed helical structure of M2Co(NCS)4
sorbed on polyurethane foam is shown in Figure 32.
Al-Bazi et al.33 suggested two mechanisms for the sorption of palladium(II) thiocy-
anate complex by polyether type polyurethane foam. At low thiocyanate and chloride
concentration, palladium is most likely sorbed as the neutral species Pd(NCS)2 by a
ligand addition mechanism. At high thiocyanate concentration, Pd(NCS)2; is formed
and sorbed on the foam by the previously described cation chelation mechanism.
In a recent publication, Moody et al.36 reported on the extraction of Co2*, Fe3*, Zn2*,
Cd2*, and Mn2* from potassium thiocyanate solution by polyether polyurethane foam-
sorbent. They measured the metal-to-thiocyanate and potassium-to-metal ratios asso-
ciated with the foam phase at equilibrium (Table 12). They then compared these values
FIGURE 32. Helical structure (not to scale) of sorbed M2Co(NCS)4-polyether com-

plex suggested by the cation chelation mechanism. The poly(ethylene oxide) chains have
been extended beyond a length typical of polyurethane foam (~20 to 25 -CH 2 CH 2 O-
units) to clarify the geometry. (From Hamon, R. F., Khan, A. S., and Chow, A.,
Talanta,29, 313, 1982. With permission.)
Table 12
THIOCYANATE-METAL AND POTASSIUM-METAL
STOICHIOMETRICS ON D2 POLYETHER POLYURETHANE FOAM FOR
VARIOUS THIOCYANATE LEVELS IN SOLUTION
Taken: 0.5 g of foam + 10 mg M"* per 100 cm3 of solution. Thiocyanate data based on elemental
nitrogen determination (allowance made for foam nitrogen). Potassium data based on potassium
determination (allowance made for KSCN sorption on foam).
CoCl2 FeCl3 Zn(N03)2 CdCl2
[KSCN] in
solution NCS:Co K:Co NCS:Fe K:Fe NCS:Zn K:Zn NCS:Cd K:Cd
0.1 2.4 1.6 2.2 0.5 2.6 1.4 3.8 0.2

0.4 2.1 1.5 2.5 0.6 2.6 1.1 7.9 3.9
0.6 2.9 1.7 3.6 0.6 2.3 1.3 5.4 3.1
1.0 3.7 1.7 2.4 1.6 3.2 1.8 4.5 3.9
2.0 2.9 2.2 2.9 2.1 3.2 2.1 4.4 3.2
From Moody, G. J., Thomas, J. D. R., and Yarmo, M. A., Anal. Proc., 20, 132, 1983. With per-
mission.
with those predicted from the calculated stability constants for the participating com-
plexes using the ECCLES computer program. 129 In the case of zinc (100 ppm) the
predicted species likely to be present in 0.1 M thiocyanate are Zn(NCS)2; and
Zn(NCS)!. These were considered to be most important in equilibrium interaction with
polyurethane foam, for the thiocyanate-to-zinc ratio of 2 to 6 falls somewhat below
that for the predicted complexes. The ratio of potassium-to-zinc was consistent with
the expectations from the predicted complexes. However, for the cobalt system it was
difficult to draw conclusions from the potassium-to-cobalt ratios of Table 12. Here the
ECCLES program predicts the presence of Co(NCS)a, Co(OH)2; and Co(NCS)* in equal
amounts for approximately 90% of all species present in solution. The investigators36
47
finally indicated that the loading of the complexes seems to be related to their ability
to form thiocyanate complexes which presumably sorb via the cation-chelation mech-
anism.
Khan and Chow44 investigated the sorption mechanism of the phosphomolybdate
anion by polyether-based polyurethane foam and indicated that the cation-chelation
mechanism cannot account for the sorption by polyether foam. More recently, sorp-
tion of gold from acidic thiocyanate solution was examined.37 The effect of several
variables on sorption was studied and optimum conditions ascertained. The percentage
extraction of gold (III) in thiocyanate solution was found to decrease by the addition
of salts such as NaCl, KC1, and LiCl. The drop in extractability was found to increase
by increasing the salt concentration, suggesting that the cation-chelation mechanism
cannot account for the extraction of the gold-thiocyanate complex. Furthermore, it
was reported38 that Fe(NCS)3L3 (where L represents the line pair and two associated
atoms in the polyurethane) is the species sorbed from solutions containing iron and
thiocyanate in molar ratio 1:3. Again, this cannot be explained by the cation-chelation
mechanism.
The work of Hamon et al.27 and Al-Bazi et al.33 represents a remarkable attempt to
determine the most probable sorption mechanism on unloaded polyether polyurethane
foam. However, additional work is necessary to prove the exact sorption mechanism
of various inorganic and organic species on unloaded polyurethane foam.
iv. Neutral and Alkaline Cyanide

The efficiency of gold(III) from collected mineral waste waters, containing about
800 mg sodium cyanide, 0.8 mg silver, together with traces of gold per kg barren, has
been tested in batch experiments on polyether polyurethane foam sorbent.39
Tracers were dissolved in the barren solution at concentrations of 0.2 mg Ag kg"1
and 0.02 mg Au kg"1 to give convenient counting rates. The foam sorption was com-
pared with the conventional coprecipitation with iron or lead sulfides prepared by var-
ious techniques. Polyurethane foam was found to have good gold-sorbing ability in a
cyanide medium (Table 13).
The possibility of using untreated polyurethane foams for the collection and recov-
ery of gold from an alkaline cyanide solution has also been examined.40 Polyether and
polyester foams were tested for this purpose, however, the polyester foam is completely
dissolved in strong alkaline media. The sorption isotherms of gold from ammonium
hydroxide solution (10 vol %) containing potassium cyanide (1 vol %) have been meas-
ured in batch experiments using two polyether foams of different manufactures (Aus-
trian and Hungarian) (Figure 33). Gold in aqueous solution was determined radiometr-
ically. The sorption capacities of both foams, as could be predicted from their sorption
isotherms, are relatively high. However, the Austrian foam showed a higher absorption
capacity (Figure 33).
Further experiments have been carried out using Austrian foam in column opera-
tions. Aliquots (100 ml) of ammonium hydroxide solution (10 vol <7o) containing 0.1 g
gold and 1 g potassium cyanide were allowed to percolate through a short foam column
(packed with 5 g dry foam) at a flow rate of 10 to 20 mi min"1 (column diameter, 25
mm). Under these conditions 90 to 95% of gold was retained by the foam column. To
obtain more or less complete collection of gold, the application of two foam columns
was recommended. The first column was packed with 5 g foam while the second was
packed only with 2 g foam; the effluent from the first passed directly through the
second.
Furthermore, the application of a pulsated column method for the collection of gold
from the alkaline cyanide media has also been examined.40 Two glass syringes (200 ml
capacity) packed with 5 and 2 g foams were employed. Quantitative sorption of gold
Table 13
PERCENTAGE RECOVERY OF
PRECIOUS METALS FROM
BARREN SOLUTION
Method Ag Au
Using FeS precipitate 97.7 49.7

Using PbS precipitate 99.7 4.1
Freshly precipitated PbS 37.3 1.9
Column of ground gal- 9.2 5.3
ena
Polyurethane foam Not tested 38.0
From Bowen, H. J. M., Radiochem. Radioanal.

Lett., 1, 71, 1971. With permission.
0.1 0.2 0.3 0.4 0.5
g Au L ' Solution
FIGURE 33. Sorption isotherms of gold from alkaline cyanide solution on polyether
Polyurethane foam, (a) Austrian foam, (b) Hungarian foam. (From Braun, T. and
Farag, A. B., Anal. Chim. Acta, 153, 319, 1983. With permission.)
was achieved by pressing and releasing the glass plunger of the 5 g foam syringe with
its tip in the alkaline gold-cyanide solution. The second fresh foam syringe was then
applied to the same gold solution. Ten pulses were recommended with each column.
In both normal and pulsated columns, gold sorbed on the foam material is success-
fully recovered either by direct dissolution of the foam (after squeezing) in aqua regia
or by burning the foam before acid dissolution. The latter procedure is preferred and
gold is obtained in the metallic form by precipitation with hydroquinone. The re-
covered gold was analyzed gravimetrically and titrimetrically and both methods
showed recovery of gold was quantitative. 40
A further advantage of the proposed foam sorption method is its possible use for an
industrial alkaline gold-cyanide waste solution. More than 95% of gold was recovered
from the waste solution using either the normal or pulsated foam column method.40
49
Table 14
THE RECOVERY OF GOLD FROM ACIDIC SOLUTIONS OF
THIOUREA WITH DIFFERENT POLYURETHANE FOAMS
AND ACTIVE CARBON
Sample % Absorption of gold

no. Type of foam on sorbent
1 Polyurethane foam, polyether, more than 93.2

95% open cell (H.I., Hungarian)
2 Polyurethane foam, polyether, more than 91.3
95% open cell (H.2., Hungarian)
3 Polyurethane foam, polyether, about 100% 89.0
open cell (W8100, W. German)
4 Poiyurethane foam, polyether, about 100% 85.2
5 Polyurethane foam, polyether, about 100% 77.2
6 Active carbon 95.0
Note: Cell dimensions of sample 1 > sample 2; and sample 3 > sample 4 > sample
5.
From Braun, T. and Farag, A. B., Anal. Chim. Acts, 66, 419, 1973. With permis-
sion.
v. Acidic Thiourea
It was reported that unloaded polyurethane foams have good ability to retain gold-
thiourea complex from acidic aqueous solutions. 41 The sorption capacity of the gold
complex on various polyether and polyester polyurethane foams has been tested. Ali-
quots (10 mjf) of gold complex (5.10~6 JV1) were shaken with 0.1 g of each foam sample
in stoppered flasks for 90 min. After equilibration the activity of the aqueous solution
was measured and the concentration of gold determined. The results (Table 14) showed
that the uptake of gold-thiourea complex by the different foams depends to some ex-
tent on cell dimension; the uptake decreases as the cell size decreases.
Although the uptake of the gold complex by 10 g of foam material is approximately
equal to the uptake of 0.2 g of active carbon under identical experimental conditions130,
the application of the inexpensive foam material seems quite advantageous.41 Figure
34 shows the effect of foam charge on the recovery of gold from acidic thiourea solu-
tion; gold-free solution can be obtained by using a foam charge of about 30 g I"1.
Furthermore, the retention rates of the gold-thiourea complex on the different foam
samples were determined and compared with those obtained on active carbon. The
half-lives of sorption of the gold-complex on all foams tested ranged between 1.3 and
2.0 min which is comparable to that obtained with active carbon (0.6 min). 41 It was
also mentioned that the palladium-thiourea complex is sorbed on unloaded polyether
polyurethane foams and the complex retained firmly on the foam. 41
vi. Other Aqueous Media

Khan et al.42 examined the sorption of alkali metal picrates in the presence of dicy-
clohexyl 18-crown-6 (DCHC-6) on polyether polyurethane foam. Crown ethers are
known to form stable complexes with alkali metal ions.131 Complexation occurs mainly
from electrostatic ion-dipole attraction between the metal ion and the oxygen atoms in
crown ethers.132 The stability and stoichiometry of the cation-crown ether complexes
depend mainly on the ratio of the ionic size of the cation to the cavity size of the crown
ether. 133 If the ionic diameter of the cation is such that it just fits into the cavity, a
40
FIGURE 34. Effect of foam charge (unloaded polyether polyure-

thane) on the sorption of gold from acidic thiourea solution. [Au] =
5 x 10-' M. [Thiourea] = 3%. [NaClO 4 ] = 1%. [HC1O4] = 0.1 M. (O)
Gold in soln, (O) gold on foam. (From Braun, T. and Farag, A. B.,
Anal. Chim. Acta,66, 419, 1973. With permission.)
stable complex is formed. However, if the cation is too small or relatively large, either
incomplete complexation or formation of 2:1 (or 3:2) and 1:2 (or 2:3) (metal-to-ligand)
complexes, respectively, may result.
Khan et al.42 suggested that the overall sorption equilibrium between an aqueous
solution containing a metal ion (M*), picrate ion (A"), a crown ether (CE), and the
polyurethane foam could be represented by the following equation:
M(+aq CE(aq) A uq) ^ MCEA(0 (16)
where MCEA represents the ion pair between the metalcrown cation MCE* and picrate
anion A". The labels "aq" and "f" denote the aqueous and foam phases, respectively.
A formula for calculating the distribution coefficient for the ion pair MCEA has been
derived. 42 The overall equilibrium was calculated taking into consideration the distri-
bution of free crown ether, picric acid, and the ion pair (MCEA) between the two
phases. Also, the dissociation of picric acid in both phases, reaction of metal ion with
the crown ether, association of the complexed cation with picrate ion, and dissociation
of the ion pair and the metal ion-crown ether complex have also been considered.
The dependence of sorption behavior of the alkali metal cations (Na% K + , Rb + , and
Cs*), in aqueous solution containing DCHC-6 and picric acid, on the total initial con-
centration of picric acid (Ar) or crown ether (Cr) has been measured.42 The sorption
efficiency of the metal ions was found to increase with increasing concentration of
picric acid or crown ether. Figure 35 shows the effect of picric acid concentration.
However, the sorption is independent of the concentration of metal and hydrogen ions
(pH in the range 2.5 to 8). It was also indicated that the values of the distribution ratios
of alkali metal complexes increase in the order Na* < Cs+ < Pb+ < K + . Worth mention-
51
600-
4 8 12 16
3 1
A T /10 mol L'
FIGURE 35. The effect of varying the initial concentration of picric

acid, A r , on the distribution ratio, D, for the distribution of various
alkali metal cations between polyurethane foam and aqueous solu-
tion. Total metal ion concentration 1 * 10"" mol I'1: total crown ether
(c) concentation 4 x io~3 mol t~'; weight of foam 0.2 g; volume of
solution 40 ml: K* (O), Rb~ (D), Cs' (A), and Na~ (•). (From Khan,
A. S., Baldwin, W. G., and Chow, A., Anal. Chim. Acta, 146, 201,
1983. With permission.)
ing is that all these results are in agreement with those expected from the theoretically
suggested equations. Furthermore, similar results have been reported for the solvent
extraction of ion pairs of Na + , K*, and Ca2* complexes of DCHC-6 with picrate and
other anions.135
On the basis of the above-mentioned results, Khan et al." came to the conclusion
that the sorption of alkali metals from an aqueous solution by polyurethane foam in
the presence of crown ether and picric acid can be considered as ion-pair extraction of
MCEA by an organic solvent of moderate dielectric constant.
Recently, the sorption of silver(I), thallium(I), barium(II), and lead(II) ions from
aqueous solution containing picric acid has been investigated.43 In the absence of picric
acid, no detectable sorption was observed. However, in the presence of other bulkier
anions, e.g., 8-anilino-l-naphthalene sulfonic acid, the sorption of thallium(I) was
even better than that obtained from aqueous picric acid up to a certain concentration
(Figures 36 and 37). Formation of an ion-pair complex between the metal ion and the
picrate ion was suggested. Sorption of the ion pairs by polyurethane foam was found
to be independent of metal ion concentration.
FIGURE 36. Effect of varing the initial concentration of picric acid on the sorption
of monovalent cations: (•) Ag*, (O) IT. Conditions; 0.4 g of foam, 100 ml of solution,
1 x 1Q-4 Min cations. (From Khan, A. S., Baldwin, W. G., and Chow, A., Anal. Chim.
FIGURE 37. Sorption of divalent cations: (O) Ba2*; (•) Pb as a

function of initial concentration of picric acid. Conditions as in Figure
36. (From Khan, A. S., Baldwin, W. G., and Chow, A., Anal. Chim.
53
6.01 1 I I i T
O,
5.0
o> 4.0
o
3.0
2.4 -
-77- I
1.0 1.5 2.0 2.5 3.0
PH
FIGURE 38. Effect of pH on the sorption of phosphomolyb-

date. Conditions: 70 ± 5 mg of foam. 150 ml of solution 4 x
10~3 MPO3;. 1 x 1Q-3 MMoO 2 ;. pH adjusted with HC1. LiCl
added to maintain 0.5 M ionic strength. (From Khan, A. S.
and Chow, A., Talanta, 30, 173, 1983. With permission.)
The distribution coefficient of silver ion was determined as a function of silver ion
concentration at several different initial picrate ion concentrations.43 The D values
remain constant up to 7 x 10~4 Minitial concentration of silver ion, then start to decline
with a slope of approximately 0.4. This drop was attributed to the continuous decrease
in the metal ion to picrate ratio. The authors43 came to the conclusion that this sorption
system cannot be easily explained by a simple ion-pair mechanism but rather by the
previously described cation-chelation mechanism.
On the other hand, it was reported that heteropolymolybdates of phosphorus, sili-
con, arsenic, and germanium, both in the reduced and nonreduced forms, are effec-
tively sorbed by polyether polyurethane foam. 44 No detectable sorption is observed for
the hetero-atom species in the absence of molybdate. The sorption of phosphate ion
from aqueous solution containing molybdate by polyurethane foam has been examined
in some detail.44 The distribution ratio of phosphomolybdate increases as the pH in-
creases, reaches a maximum at pH 1.2, remains constant up to pH 2.5, and then de-
creases steadily (Figure 38). The sorption of phosphomolybdate by the foam was found
to depend on the molybdate concentration in the aqueous solution, reaching a maxi-
mum at about 25-fold excess of molybdate-to-phosphate. However, above 750-fold
3.0
-t"
0.5 1.0 1.5 2.0
(Alkali—Metal Chloride) (M)
FIGURE 39. Effect of varying initial concentra-

tion of alkali-metal chlorides on the sorption of
phosphomolybdate. Conditions: 70 ± 5 mg of foam.
150 ml solution. 4 x 1Q--' MPO3;. 6 x 10'3 MMoO2;.
pH = 2.0 ± 0.1, (O) LiCl. (D) NaCl. (A) KC1. (From
Khan, A. S. and Chow, A., Talanta, 30, 173, 1983.
With permission.)
excess of molybdate the distribution ratio decreases. This was attributed to the proba-
ble competitive sorption of /sopolymolybdate species into the polyether foam at high
molybdate concentrations.
The effect of alkali-metal chlorides on the sorption of phosphomolybdate has been
examined in order to evaluate the possible sorption mechanism.4'1 In the presence of
lithium chloride the distribution ratio remains constant up to a certain concentration
(depending on the initial concentration of lithium chloride); then the D decreases.
However, in the presence of sodium or potassium chloride the distribution ratio ini-
tially decreases rapidly, then slowly with increasing alkali metal concentration (Figure
39). Obviously, these results show that the cation-chelation mechanism cannot explain
this system.
b. Sorption from Nonaqueous Media

The feasibility of using untreated polyurethane foams for the sorption of some in-
organic species from nonaqueous solvents has been investigated by Moore and Chow.45
They used this system for the extraction of iridium(IV) and platinum(IV) in the form
of their hexachloro-complexes in order to prevent the possible decomposition of the
complexes in aqueous media.
The sorption efficiency of hexachloroiridate(IV) from ethyl acetate solution was
found higher than from acetone. The iridium-complex was extracted from ethanol or
propanol, but its solutions in these solvents were unstable.
55
240
00 40 80 120 160 200 240 280 320

Time (hr)
FIGURE 40. Effect of water on the sorption of Na 2 IrCl 6 from acetone solution. So-
lution, 50 ml; foam, 0.08 g; flr(IV)], 10 Mg ml; temperature, 25.0 ± 0.05°C; manual
squeezing. (From Moore, R. A. and Chow, A., Talanta, 27, 315, 1980. With permis-
sion.)
The distribution coefficient from acetone was determined as a function of contact

time and showed that equilibrium is reached in about 20 hr. The D remained essentially
independent of Ir(IV) concentration and had a value of 225 over the concentration
range 8.56 x 10"6 to 5.06 x 10~5 Mlr(IV), but became smaller at high concentrations.
The efficiency of extraction decreased with increasing the proportion of water (Fig-
ure 40). This was linked to the reduction of the Ir(IV) complex to the corresponding
Ir(III) compound which is not sorbable. The presence of trichloroacetic acid (0.7 M)
in the aqueous solution favors the sorption of the Ir(IV) complex (more than doubled
the sorption efficiency), but acetic acid is not as effective.
The sorption behavior of hexachloroiridate(IV) from ethyl acetate and acetone sug-
gested that the sorption cannot be explained by a simple solvent extraction mechanism.
Iridium has been recovered from the foam material by reduction to the nonextractable
Ir(III) species with sodium thiocyanate, sodium oxalate, hydroxylamine hydrochloride,
or hydrazine hydrochloride in acidic solutions.
The sorption of hexachloroplatinate from acetone, ethanol, propan-2-ol, and ethyl
acetate was also tested; however, the highest efficiency was obtained from ethyl acetate
solution. The sorption equilibrium is reached in about 24 hr. The value of the D was
4.8 x 103 and essentially independent of Pt(IV) concentration in the range 1.21 x \Q~S
to 2.42 x IQ-5 M.
2. Collection of Organic Species

A whole series of organic compounds, e.g., chlorinated hydrocarbons, polynuclear
aromatic hydrocarbons (PAHs) organophosphorus and other organic compounds, are
recognized as dangerous pollutants of air and water. Since these organic compounds
are present in air and water at parts per trillion (10~9 g m~3) and parts per billion (10~9
g mJ~') levels, respectively, efficient collection methods are inevitably required to pro-
vide enough material for a reliable analytical determination. Polyurethane foams have
been tested in recent years as efficient collectors for a wide range of organic pollutants
from aqueous and gaseous media.
a. Sorption from Aqueous Media

Gesser et al.'° initiated the application of unloaded polyurethane foam (polyether
type) for the sorption and recovery of organic contaminants from water. Since then
several investigations have been published describing the application of untreated
foams as collectors in separating and concentrating chlorinated organic com-
pounds, 1046 54 polynuclear aromatic hydrocarbons, 55 58 and other organic com-
pounds. 59 - 64
In this connection, it is important to note that the untreated polyurethane foams
(polyethers or polyesters) are used as collectors for the concentration of organic com-
pounds from fairly large volumes of polluted water. Generally the water is passed
through a chromatographic column containing several foam plugs, at flow rates rang-
ing between 10 and 270 mi min'1 (column diameters are in the range 20 to 76 mm).
The collected organic compounds are then recovered from the foam either by simple
elution or Soxhlet extraction with different combinations of hexane and acetone. After
the appropriate volume reduction of the leachate using a rotary evaporator, the re-
covered compounds are generally identified and determined by gas chromatography.
It is worth noting that unloaded polyurethane foam is not specific to a certain group
of organic compounds.
Consequently, the leachate produced from the recovery of a complex mixture would
require some separation prior to its injection into the gas chromatograph. The nonse-
lective character of polyurethane foams towards organic materials is not a serious dis-
advantage as identical behavior has also been reported with other sorbents. 138139
i. Chlorinated Organic Compounds

The chlorinated organic pollutants present in the environment, as published by the
U.S. Environmental Protection Agency, in their descending importance are: Chlor-
dane, toxaphene, Aldrin, a-BHC, BHC, y-BHC (lindane), d-BHC, 4,4'-DDD, 4,4'-
DDE, 4,4'-DDT, Dieldrin, Endosulfan I, Endosulfan II, Endosulfan sulfate, Endrin,
Endrinaldehyde, Heptachlor, Heptachlor epoxide. It is to be noted that polychlori-
nated biphenyls are complex mixtures containing about 209 possible chloroisomers; as
an example, 54 isomers have been identified in Aroclor® 1242.M0
Polyurethane foams were found to sorb many polychlorinated biphenyls from
water. 10 Concentrations ranging between 2 and 20 ^g i'1 have been collected success-
fully by percolating the aqueous solution through polyurethane foam plugs designed
as culture tube stoppers (22 mm diameter and 38 mm long). It was reported that 95%
of the polychlorinated biphenyls (PCBs) are retained by the first foam plug and only a
few percent retained by the second plug at a flow rate as high as 250 m^ min"1 (column
diameter 20 mm). After squeezing water from the foam column, the PCBs are eluted
from the foam column with acetone and n-hexane. The application of a separatory
funnel was advised for the separation of water which may be coextracted with hexane
prior to the use of anhydrous sodium sulfate. The dried elutant was then concentrated
on a rotary evaporator and analyzed by a gas chromatographic method.
Furthermore, two polyester polyurethane foam plugs (34 x 44 mm) packed in glass
columns (22 mm diameter) were successfully used for the collection of Aroclor 1254 in
3 I of distilled water (spiked with 10 (^g of this PCB compound) by percolating the
aqueous solution through the foam column at a flow rate of 250 to 275 m/ min"1.46
Recoveries (~ 45%) are observed on applying this method for the collection of the
same compound from lake water. This was attributed to the presence of small particles
which adsorb some amounts of the Aroclor and pass without hindrance through the
foam column. This conclusion was confirmed by carrying out the same procedure after
prefiltering the lake water through a 0.45 n membrane and measuring Aroclor on the
foam and in the effluent solution. Good recoveries were obtained for the collection of
Aroclor spiked in the prefiltered lake water (Table 15).
In another investigation,47 polyurethane foam plugs have been examined for the
57
Table 15
SORPTION EFFICIENCY OF
POLYURETHANE FOAM FOR
AROCLOR® 1254 IN FILTERED VS.
UNFILTERED LAKEWATER
Recovered (jig)
Spiked ~~~~~~~~^~"~~~~
Water type (yg) Foam Effluent Total
Filtered lake 10 8.8 0.4 9.2

Unfiltered lake 10 6.9 1.1 8.0
Distilled 10 9.1 0.2 9.3
From Bedford, J. W., Bull. Environ. Contain. Toxicol.,

12, 622, 1974. With permission.
quantitative extraction of PCBs, dieldrin, and some DDTs from industrial and agri-
cultural waters. The average recoveries of all spiked materials were generally > 90%.
The concentration levels measured by the foam sorption method are in good agreement
with those obtained by a solvent extraction method.
In a separate study, 48 polyurethane foam was employed for the retention and deter-
mination of PCB, DDT, and Clordane in Bermuda and Sargasso Sea surface water.
A detailed examination of the different factors affecting the extraction and recovery
of various organochlorine insecticides has also been carried out by Musty and Nick-
less,49 who investigated six different foam samples having different surface areas and
densities. The sorption efficiency of methylene blue by the foam material was taken as
a criterion to the relative extraction efficiency of organic insecticides from aqueous
solution. The higher the amount of methylene blue sorbed, the higher the efficiency of
the foam material for recovering insecticides from water. Polyurethane foams sorbing
approximately 250 m mol of methylene blue per kg of foam in 24 hr were recom-
mended for use in the extraction of chlorinated insecticides and PCBs. The effect of
flow rate on the collection efficiency of a polyurethane foam column (packed with two
foam plugs each 2.2 x 4 cm) is shown in Table 16. Quantitative recoveries of 13 insec-
ticides from water were obtained using flow rates of 10 to 100 ml min~', whereas at
higher flow rates (e.g., 250 mt min"1) the sorption was less efficient. 49 - 50 As usual,
acetone and n-hexane were used to elute the insecticides from the foam column.
The recoveries of the different insecticides by the foam material were found to be
pH dependent. Complete recoveries were generally obtained at pHs ranging between 6
and 9. At pH 5, however, slightly decreased recoveries were observed (Table 17). The
authors accentuated the superiority of polyurethane foam for the sorption of chlori-
nated insecticides over the conventional activated carbon. In the latter case the re-
covered material is often different from the original one owing to the catalytic effects
exhibited by the carbon. Obviously, these effects are not present in the case of poly-
urethane foam as shown from the quantitative recoveries obtained. Moreover, the
foam material showed a very high capacity for these pesticides, and the concentration
of chloride ions (up to 25 g (.'') did not significantly affect the performance of the
foam columns which is considered to be of importance for application of the proposed
foam method in the analyses of saline waters.50 A useful study was made for the sorp-
tion efficiency of polyurethane foam in comparison with other methods including Car-
bowax® -undecane, Amberlite® XAD-4, and solvent extraction for the extraction and
determination of organochlorine insecticides and PCB from water samples.51 Lindane
and o-BHC were detected in River Leaden sample (Table 18), while the presence of
Table 16
THE EFFECT OF WATER FLOW RATE ON INSECTICIDE RECOVERY
FOR FOAM UNCOATED AND COATED WITH DC-200
Recovery (%)
Uncoated Coated with DC-200
10 30 250 10 30 250
Concentration ml ml ml mt mt mi
Insecticide (ppb) min~' min~' min"1 min"1 min"1 min"1
o-BHC 1 101 95 49 83 86 66
Lindane 1 101 91 40 77 77 61
/3-BHC 1 101 86 44 91 83 61
Aldrin 1 99 73 46 77 67 54
p,p'-DDE 2 106 77 68 81 81 77
Dieldrin 1 106 77 58 88 82 76
Endrin 10 100 94 54 106 91 64
o,p'-DDT 10 113 84 43 106 57 56
p,p'-DDD 2 102 89 57 81 80 52
p,p'-DDT 10 114 100 26 62 30
Note: Two plugs, 2.2 cm diameter and 4 cm long, were used.
From Musty, P. R. and Nickless, G., J. Chromatogr., 100, 83, 1974. With permission.
Table 17
THE EFFECT OF pH OF DOPED WATER ON
RECOVERY WHEN USING UNCOATED FOAM;
WATER FLOW RATE 10 mi MIN'1
Recovery (%)
Concentration
Insecticide (PPb) pH 5 pH 6 pH 7 pH 8 pH 9
a-BHC 1 75 117 102 101 112

Lindane 1 75 114 103 101 112
/3-BHC 1 75 110 103 101 116
Aldrin 1 81 94 96 99 109
p,p'-DDE 2 96 115 119 106 117
Dieldrin 1 97 116 117 106 117
Endrin 10 94 108 107 100 110
o,p'-DDT 10 85 114 108 113 109
p,p'-DDD 2 117 119 119 102 118
p,p'-DDT 10 60 117 96 114 98
Note: Two plugs, 2.2 cm diameter and 4 cm long, were used.

Source: Musty, P. R. and Nickless, G., /. Chromatogr., 100, 83, 1974.
With permission.
Lindane, a-BHC, and Aroclor® 1260 was proved in a broad oak sample (Table 19).
As a result of this investigation the application of a combined sorbent, made of 100 g
Chromosorb® W, 50 g of n-undecane and 5 g Carbowax® 4000 monostearate, was
recommended and claimed to be better than polyurethane foam.51
In a more recent investigation,53 54 different combinations of charcoal and polyure-
thane foam (40% charcoal and 60% foam wt/vol.) were evaluated for the separation
59
Table 18
CONCENTRATION OF ORGANOCHLORINES IN RIVER
LEADON SAMPLE
Concentration
Procedure Organochlorine (ng r-)
Amberlite® XAD-4 Lindane 21

a-BHC 5
Porous polyurethane foam Lindane 16
a-BHC 4
Chromosorb® -undecane-Carbowax® Lindane 15
a-BHC 5
Solvent extraction Lindane 15
a-BHC 3
From Musty, P. R. and Nickless, G., J. Chromatogr., 120, 369, 1976. With
permission.
Table 19
CONCENTRATION OF ORGANOCHLORINES IN
BROAD OAK SAMPLE
Concentration
Procedure Organochlorine (ng/-)
Amberlite® XAD-4 Aroclor® 1260 81

Lindane 30
a-BHC 3
Porous polyurethane foam Aroclor® 1260 88
Lindane 40
a-BHC 3
Chromosorb® -undecan-Carbowax ® Aroclor® 1260 13
Lindane 20
a-BHC 5
Solvent extraction Aroclor® 1260 675
Lindane 55
a-BHC 8
Sediment Aroclor® 1260 174.6°
Lindane 5.0'
a-BHC 1.0-
Concentrations in sediment are in jjg kg~'.
From Musty, P. R. and Nickless, G., J. Chromatogr., 120, 369, 1976. With
permission.
of mirex, photomirex, and Aroclor® 1254. Microcolumns containing 0.2 g charcoal-

foam mixture were employed for the sorption of these chlorinated hydrocarbons.
Mirex and photomirex were eluted first from the column with 10 ml cyclohexane and
Aroclor® 1254 with 10 ml of benzene. Fourteen different charcoals were examined
and the Norit® C-170 charcoal- foam mixture was found to be the best." The average
recoveries obtained for photomirex and Aroclor® were 99.1% and 96.8%, respec-
tively. The same procedure proved useful for the determination of mirex, photomirex,
and PCBs in lake sediments. In this case the sediment sample was extracted with ace-
tone-hexane (1:1) in an ultrasonic apparatus, the extracts were cleaned on Florisil®
column and then separated on the charcoal-foam column as described above.
Table 20
RECOVERY OF BENZO(A)PYRENE (BaP) FROM SPIKED WATER
Continuous flow system'
Static conditions" (^g % Recov-

BaP sorbed from dis- % Recov- ery from
tilled water per g, ery from distilled
Foam plug Plug characteristics foam) tap water water
A.diSPo plugs Polyester, white; 50 x 150 62 89

38 mm; density, 24
kgnr 3
B, Identi plugs Polyether, white; 45 * 135 65 91
45 mm, density, 25
kgnr 3
C, p l u g s out Polyester, green; 45 x 187 66 96
from UU34 45 mm, density, 24
sheets kgnr 3
° BaP concn, 200/jg t ~ ' .

b
Water temperature, 23°C; volume 4 I; BaP cone, 0.1 ppb; flow rate, 150 ml min"1 (± 10 ml);
column diameter, 25 mm.
From Saxena, J., Kozuchowski, J., and Basu, D. K., Environ. Sci. Technol., 11, 682, 1977. With
permission.
ii. Polynuclear Aromatic Hydrocarbons

Polynuclear aromatic hydrocarbons have serious carcinogenic activity,"" and are
widely dispersed and have long persistence in the environment. 55 56 Owing to the very
low concentrations of these compounds in drinking water, a suitable preconcentration
procedure is required to meet the detection limit of most analytical methods. The sor-
bent must be capable of rapid and efficient collection of these compounds, and must
be insoluble in relatively high volumes of water, and unaffected by the passage of the
aqueous solution at high flow rates.
Saxena et al.56 claim polyurethane foams fulfill all these requirements. It was re-
ported that the chemical nature of the foam (polyether or polyester) and its density do
not have significant effects on the sorption of benzo(a)pyrene, which is considered a
major representative of carcinogenic PAHs in water. Some results obtained in batch
and flow systems are summarized in Table 20. Static experiments were conducted with
a foam plug in contact with radiolabeled 14C-benzo(a)pyrene (BaP) (20 to 500 ng I"1)
for 4 hr. Column experiments were carried out using one foam plug and percolating
the aqueous solution (4 1,0.1 ppb) at a flow rate of 150 mi min"1 (column diameter,
25 mm). The amount of BaP retained by the foam was determined by measuring the
14
C-activity in the initial and final solutions. The concentration of radioactive BaP in
spiked water and effluent solution was determined by extracting a known aliquot with
benzene and counting the 14C-activity in the solvent phase. The BaP sorbed on the
foam plugs was eluted with 20 ml acetone followed by 75 ml of benzene.
It was noticed that the diameter of the column holding the plugs has a distinct effect
on the recovery of BaP from tap water. The recovery decreased by about 20% with an
increase in column diameter from 20 to 50 mm. The sorption efficiency of polyure-
thane foam was found to be independent on the flow rate (130 to 520 mi min"1).56
However, the retention efficiency steadily increased with the increase of the pH of the
solution (pH 3 to 10). On the other hand a dramatic effect on the recovery of BaP
from spiked tap water was observed when the water temperature varied. In the case of
tap water, the retention increased with the increase of temperature up to 40°C, then
61
100
(a)
90
cc
LU
> 80
70
60
50 I I _L I I
10 20 30 40 50 60 70 80
TEMPERATURE OF WATER PASSED THROUGH FOAM fC)
FIGURE 41. Effect of water temperature on the recovery of benzo(a)pyrene; water

volume, 4 t; BaP concentration, 0.1 ppb; flow rate, 250 ± 10 ml min" 1 (a) filtered tap
water; (b) distilled water; (c) tap water (unfiltered). (From Saxena, J., Kozuchowski,
J., and Basu, D. K., Environ. Sci. Technol., 11, 682, 1977. With permission.)
decreased in the region of 40 to 50°C and finally increased beyond 50°C reaching a
plateau at 60°C (Figure 41). The initial increase in the retention efficiency was linked
to the presence of suspended particles in water; such an increase was less pronounced
when tap-water was Millipore-filtered prior to spiking and also was not observed when
distilled water was used (Figure 41). The increase in the retention efficiency by heating
the water was attributed to the desorption of BaP from suspended particles into water
as well as to a possible change in the foam itself. The recovery of BaP from distilled
water is generally higher than that from tap water at all temperatures examined.
For sampling 20 S. of water, it was recommended to use two foam columns (each
packed with two foam plugs) and to heat the water to 60 to 65 °C before its passage
through the foam columns at 250 ml min' 1 . 56 The BaP sorbed foam was found to be
quite stable and its recovery quantitative even after storing the plugs for seven days (at
4°C). Some losses of BaP were observed when the foam plugs were stored at room
temperature.
The possibility of using polyether polyurethane foam plugs for the recovery of other
PAHs from finished and raw waters has also been examined. 5 7 A mixture of
benzo(a)pyrene, fluoranthene (FL), benzo(j)fluoranthene (BjF), benzo(k)fluoranthene
(BkF), indeno(l,2,3-cd)pyrene (IP), and benzo(ghi)perylene (BPR) has been tested.
The retention efficiencies of the individual polynuclear aromatic hydrocarbons on the
foam were generally not less than 88 and 72% from finished and raw waters, respec-
tively. In all experiments the spiked water was heated to 62 ± 2°C prior to its percola-
tion through the foam column at 250 ± 10 mjf min"1 flow rate.
The retention of PAHs on the foam plugs from large volumes of water has also been
investigated with both raw (30 I) and finished (60 i) waters. Water was spiked with a
PAH's mixture containing 500 ng t~l of fluoranthene and 100 ng i'' from each of the
other compounds and passed through foam columns maintaining optimum retention
conditions.57 Foam columns were changed after every 20 t of finished water and every
10 i of raw water. The foam plugs were eluted with acetone and cyclohexane. The
Table 21
FOAM RETENTION EFFICIENCIES FOR PAH FROM
TREATED WATER
Cone in
aqueous phase Amt retained by foam Retention
Compound (ng /"') from 1 I of water (ng) (%)
Fluoranthene 278.6 260.4 93.5

Benzo(j)fluoranthene 48.3 47.4 98.1
Benzo(k)fluoranthene 51.7 50.6 97.9
Benzo(a)pyrene 36.4 33.6 92.3
Indeno(l,2,3-cd)pyrene 25.5 23.9 93.7
Benzo(ghi)perylene 22.6 19.8 87.6
Note: Water source: laboratory tap water; water volume: 60 I; cone of fluoran-
thene: 500 ppt; all others: 100 ppt; detection method: TLC-fluorometric.
From Basu, D. K. and Saxena, J., Environ. Sci. Techno!., 12, 791, 1978. With
permission.
Table 22
FOAM RETENTION EFFICIENCIES FOR PAH FROM RAW
WATER
Cone in
aqueous phase Amt retained by foam Retention
Compound (ng f~') from 1 I of water (ng) (%)
Fluoranthene 289.1 343.7 118.9

Benzo(j)fluoranthene 77.6 94.0 121.1
Benzo(k)fluoranthene 66.1 55.6 84.1
Benzo(a)pyrene 74.5 59.7 80.1
Indeno(l,2,3-cd)pyrene 85.2 61.2 71.8
Benzo(ghi)perylene 23.9 28.3 118.4
Note: Water source: Onondaga Lake; water volume: 30 I cone of fluoranthene:

500 ppt; all others: 100 ppt; detection method: TLC-fluorometric
From Basu, D. K. and Saxena, J., Environ. Sci. Technol., 12, 791, 1978. With
permission.
results of these investigations are summarized in Tables 21 and 22. In addition, the
recovery of PAH from unspiked finished water using 60 i of water was tried.57
The application of a direct gas chromatographic method for measuring the amount
of PAH in the eluate (after the preconcentration step on the foam column) was not
possible because of the presence of several contaminants, which are also concentrated
on the foam and eluted with acetone and cyclohexane. Some other impurities from the
foam itself could also be leached during the elution process. For these reasons a
cleanup step for the eluate was found to be necessary before the gas chromatographic
step.57 A cleanup procedure based on a solvent partitioning method was recommended
to eliminate some impurities.141 However, to remove all impurities, an additional
cleanup step involving a short Florisil® column was suggested (Figure 42).
The gas-liquid chromatographic conditions used failed to separate the isomers
benzo(j)fluoranthene and benzo(k) fluorancene and therefore combined values have
been given for them.57 The technique described detected as low as 0.1 ng I'1 of each
individual PAH.
63
B(j)F+B(k)F Standard Mixture
BaP BPR
IP/v
Solvent Partitioned Concentrate

After Column Chromatography on
Florisil.Elutlon Volume 125 ml.
Uncleaned
vJU
I
12 16 20 24 28 32 36
Time (min.)
FIGURE 42. Purification efficiency of cleanup

procedure. (From Basu, D. K. and Saxena, J., En-
viron. Sci. Technol., 12, 791, 1978. With permis-
sion.)
The same investigators58 suggested the application of polyurethane foam sorbents to

monitor the previously mentioned PAHs in some selected treated waters and their re-
spective raw water suppliers in the eastern U.S. A pumping system allowed water from
the sample source to be injected through a thermostated (62 ± 2°C) water circulator to
the foam columns at a controlled rate of 250 ± 10 m^ min"1. Foam plugs were held in
two 25 mm diameter Chromoflex columns connected in series. Used were the same
retention, elution, cleanup, and quantification procedures described previously with
PAHs.57 In some experiments, the efficiency of PAH elution and purification proce-
dure was evaluated by the addition of a known amount of "lC-benzo(a)pyrene as an
internal standard to the foam plugs prior to initiating any sample workup.
The results obtained for the analyses of 10 treated and 4 raw water samples for PAH
are shown in Table 23.58 Although both TLC-spectrofluorometric and GLC-FID meth-
ods were employed58 in PAH analysis, the latter method failed in most cases to detect
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65
FIGURE 43. Effect of pH upon the sorption of laurylbenzene sul-

fonate-dye complex on polyurethane foam, (a) Crystal violet, at 588
nm; (b) methylene blue, at 656 nm; Laurylbenzene sulfonate: 5 ppm;
solvent: methanol, 20 ml; reference: reagent blank. (From Tanaka,
T., Hiiro, K., and Kawahara, A., Bunseki Kagaku (Japan Analyst),
PAH. TLC-spectrofluorometry, however, is capable of detecting PAH at sub-ng t~

levels and provides excellent resolution.
iii. Other Organic Compounds

The sorption and separation of other organic compounds in water with polyurethane
foam sorbents has also been described in batch and column modes.59 " Tanaka et al.59
reported that polyether polyurethane foam is able to extract alkylbenzene sulfonate
from aqueous solution containing either crystal violet or methylene blue. The color
intensity of the foam with sorbed alkylbenzene sulfonate-crystal violet (or methylene
blue) complex was found to be proportional to the alkylbenzene sulfonate concentra-
tion. Subsequently, these investigators employed standard series methods for color
comparison and determined the alkylbenzene sulfonate visually. Alternatively, the
sorbed complex was eluted from the foam material with methanol and determined
spectrophotometrically at 588 or 656 nm for crystal violet or methylene blue dyes,
respectively. The researchers indicated that polyester polyurethane, polyvinyl chloride,
polystyrene, and polyethylene foams are not suitable for the proposed system. Figure
43 shows the effect of pH on the sorption of laurylbenzene sulfonate-dye complex by
polyether polyurethane foam. The optimal pH-values are 2.5 and 4.6 in the presence
of crystal violet and methylene blue dyes, respectively.
Batch and flow operations have been employed for the proposed test. In the former
mode one polyurethane foam sorbent cube (2 cm edge) was soaked for 5 min in 100
mt of the aqueous solution, adjusted to the optimum pH value. In the column experi-
ments the aqueous solution was allowed to percolate through the foam sorbent column
(packed with 0.19 g foam) at 20 to 30 mjf miir1 flow rate (column diameter 8 mm).
The limit of detection of the flow method was generally lower than that of the batch
method and the application of crystal violet dye allowed better sensitivity than with
Table 24
DETERMINATION OF ALKYLBENZENE SULFONATE
IN RIVER WATER
ABS found (ppm)

Sample taken" ABS added
(mjf) (ppm) Visual method Spectrophotometry
20 — 5 5.7
40 — 5 5.5
20 5 10 11.0
20 10 15 13.8
Small river water in Ikeda city, pH = 7; ABS content: 6.4 ppm by Meth-
ylene blue method.
From Tanaka, T., Hiiro, K., and Kawahara, A., Bunseki Kagaku (Japan
Analyst), 22, 523, 1973. With permission.
Table 25
RECOVERY OF A SERIES OF
PHTHALATE ESTERS UNDER FLOW
CONDITIONS
Recovery (%)
Phthalate Type A" Type B'
Dimethyl phthalate (DMP) 20 ± 5 S±l

Diethyl phthalate (DEP) 84 ± 8 80
Di-n-butyl phthalate (DnBP) 102 ± 4 101 ± 1
Di/sobutyl phthalate (DiBP) 93 ± 2 99 ± 2
Diamyl phthalate (DAP)' 85 80
Di-n-hexyl phthalate (DnHxP) 34 ± 2 33 ± 2
Di-n-heptyl phthalate (DnHpP) 23 ± 2 25 ± 2
Di-2-ethylhexyl phthalate (DEHP) — —
Dioctyl phthalate (DOP) — —
Diisodecyl phthalate (DiDP) — —
Butyl benzyl phthalate (BBP) 70 ± 3 86 ± 3
Note: For each test, 100 ml of water spiked with 0.1 pig of
each phthalate was run on a column of five foam
plugs at 10 mt min~'
Foam density 0.030 g m<~'.

* Foam density 0.019 g mi"1.
One run only.
From Gough, K. M. and Gesser, H. D., /. Chromatogr.,

methylene blue. The test was employed for the detection of alkylbenzene sulfonate in
river water (Table 24).
Gough and Gesser60 described a method for the collection and recovery of phthalate
ester (usually eroded from synthetic polymer tubing) from water with polyurethane
foam sorbents. They tested batches of polyurethane foams having different densities.
A series of column tests on phthalates, with side chains varying in length from one to
ten carbons, was run with batches A and B (Table 25). Each of the five foam plugs (50
67
O DMP
a DEP
o
o
<n
CC
Foam Number
(a)
FIGURE 44. Profiles of phthalate esters on foam (density 0.019 g
mt~') column of five plugs, numbered 1 to 5 from top to bottom. In
each test, 100 ml of water containing 0.1 mg of the phthalate was
passed at a flow rate of 10 ml min~' down the column, followed by
100 mi clean water. Each point represents the percentage of the initial
spike found on the foam, (a) DMP and DEP; (b) DnBP, DAP and
DnHxP; (c) DiBP, BBP, DHpP, DEHP, DOP, and DiDP. (See Table
25 for abbreviations.) (From Gough, K. M. and Gesser, H. D., J.
Chromatogr., 115, 383, 1975. With permission.)
x 38 mm) employed in the column was extracted into a 10 ml volumetric flask to

determine the phthalates down the length of the column (Figure 44). It was observed
that phthalates with longer side chains are not significantly sorbed by the foam column
using a single run at 10 ml min"1 (column diameter, 15 mm). This was attributed to
the probable slow sorption rates of these pthalates on the foam.
Polyurethane foam plugs (8.3 cm diameter x 5 cm long) were employed as an alter-
nate to active carbon for the determination of trace organic contaminants in water."
The foam material was placed in a standard carbon adsorption metering apparatus and
used to monitor organic matter in drinking water. A certain volume of water (1 to 2 I)
was allowed to pass through the foam column at 83 to 167 ml min"1 (column diameter,
7.6 cm). It was noted that even higher flow rates could be used. The foam plugs were
then extracted with hexane in a Soxhlet extractor. After evaporating the hexane solu-
tion to the appropriate volume, the collected organic materials were measured by gas
chromatography. No interfering components were observed in the blank experiments
using the same solvent and foam. Figure 45 shows typical results obtained where a
comparison was made of raw (1425 I) and treated water spiked with a mixture of
polychlorinated biphenyls (1790 I). The levels of impurities present in the examined
water were found to be in the range 0.005 to 0.010 ppb and the water treatment process
did not significantly remove or reduce the organic contaminants from the raw river
water. The slight difference in the contents of water contaminants before and after
treatment was attributed to chlorination of the organic components or their removal
or introduction in the treatment process. According to this investigation, the applica-
tion of polyurethane foam for monitoring organic compounds in water is quite supe-
rior to active carbon because the carbon surface acts as a catalyst for several chemical
changes of the adsorbed substances which makes the identification of the recovered
organic compounds quite difficult.
Foam N u m b e r
FIGURE 44b
3 4
Foam Number
FIGURE 44c
69
Time
FIGURE 45. A comparison of three chromato-

grams: (a) river water extracted by polyurethane
foam and concentrated to 5 ml of hexane; (b)
treated municipal drinking water extracted by polyu-
rethane foam and concentrated to 5 ml of hexane;
(c) 2 ^g mi" 1 polychlorinated biphenyls in hexane.
Each sample was 5 pi. (From Gesser, H. D., Spar-
ling, A. B., Chow, A., and Turner, C. W., /. Am.
Water Works Assoc., 65, 220, 1973. With permis-
sion.)
A further application of polyether polyurethane foam sorbents is their use for the
collection of phenol in nonaqueous media.63 The uptake of phenolics from /i-heptane
was examined in batch experiments by comparing the infrared band at 1600 cm"1 of
the solution before and after shaking. The sorption of phenol and mixed cresols by
polyurethane foam and three other sorbents was measured and compared. No phenol
could be detected on attapulgite clay and porcelalumina sorbents, and the uptake of
phenolics by polyurethane foam (60 to 85%) was found to be generally higher than
that of activated carbon (45%). Moreover, the flow method using polyurethane foam
sorbents gave better results for the collection of phenolics from n-heptane or methyl-
cyclohexane solutions. The break through capacity of the foam was found to be 0.8 to
0.9 g/g foam employing a flow rate of 5 to 10 ml min"1. For the clay sorbent, however,
it was 0.038 to 0.045 g/g sorbent under the same experimental conditions. In static and
dynamic experiments, the sorbed phenolics could be recovered from the sorbent by
acetone elution and the sorbent could thus be reused.
Another useful application of polyurethane foam sorbents is the collection of oil
from surface waters.64 This method depends mainly on the physical sorption of oil on
the surfaces of the foam material using a simple apparatus designed specially for this
purpose and carried by boats which move over water at speeds of 0.5 to 3 mph. It was
possible to collect surface oil on the foam and recover it by squeezing. Thereafter the
foam can be reused.
b. Sorption from Gaseous Media

Each year several million pounds of different pesticides are applied to agricultural
and forest lands, mainly by aeration. During application, a significant fraction re-
mains in the air as vapor, paniculate matter, or aerosols.142 Also some of the material
that does reach the ground can later be fed back into the air as air absorbate on fine
particles by volatilization, and wind or mechanical agricultural operations.65 Atmos-
pheric transport of various organic compounds is the major factor in the dispersal of
these compounds through the biosphere. High volume air sampling techniques are usu-
ally required to provide enough material for a reliable analytical determination because
most organic pollutants are present in ambient air at part per trillion (10~9 g m~ 3 ) levels.
The use of polyurethane foam sorbents for this purpose appears to offer many advan-
tages: they are inexpensive, easy to clean, convenient to handle in the field, and present
low resistance to air flow, i.e., allow the passage of high volumes of air in a relatively
short time. Polyurethane foam sorbents have been evaluated for use in high volume air
samples to collect chlorinated organic compounds, 65 89 organophosphorus pesti-
cides, 7 1 7 2 8 7 8 S polynuclear aromatic hydrocarbons, 90 " 1 and some other organic pollu-
tants. 92 - 95
i. Chlorinated Organic Compounds

Interest in the measurement of chlorinated pesticides and polychlorinated biphenyls
in air has existed for several years. A number of sampling methods have been devel-
oped and applied to the collection of such compounds from the ambient atmosphere,
near agricultural, industrial, and other areas. The common approaches to sampling
airborne pesticides are columns packed with solid sorbents, impingers, and gas bub-
blers.143 145 Most of these methods were developed for use in low volume air samplers
where the concentrations of insecticides in the atmosphere are relatively high. That is,
5 to 50 m3 samples are usually enough for the detection of chlorinated pesticides. How-
ever, for ambient (uncontaminated) air, sufficiently large samples must be taken to
permit detection at ultratrace levels (pg m"3 to ng m'3). In order to reduce the time
required for sampling uncontaminated air, it is necessary to use sorbents with high
efficiency and suitable aerodynamical properties for use in high-volume sampler sys-
tems.
On the basis of the promising results obtained by Gesser et al.10 in the fast collection
and retention of polychlorinated biphenyls in sea water by polyurethane foam sor-
bents, Bidleman and Olney66 evaluated foam sorbents, packed in a suitable air sampler,
for the collection of polychlorinated biphenyls in ambient air. Obviously, the open cell
foam presents little resistance to air passage and therefore is compatible with high-
volume sampling equipment. 66 A Gelman Hurricane air sampler (Model 16003) was
employed for this purpose. Two foam plugs, each of 10 cm diameter and 5 cm thick,
were inserted into the aluminum cylinder (8.8 cm diameter) of the sampler. The cylin-
der was attached to the rear of a stainless steel filter holder containing a Gelman glass
fiber A (GFA) filter to ensure that only vapors were sampled and the filtering appara-
tus was connected to a pump.
As a general rule for studying the collection and retention efficiencies of polyure-
thane foam sorbents in gaseous media, the individual compounds or mixtures to be
tested are vaporized in the intake of the air sampler under study. Usually, the test
compounds were introduced from wool-coated felt filters or glass beads mounted over
the intake faces.71 In some investigations, the intake air was prefiltered through a rel-
atively thick polyurethane foam plug to ensure the removal of any interfering contam-
71
Table 26
COLLECTION OF POLYCHLORINATED BIPHENYLS (PCB) VAPORS ON
POLYURETHANE FOAM PLUGS
% On GFA
PCB in air (ng nr3) % On first PUF plug6 filter
Flow rate Volume air
(I min'1) (m3) Tri- Tetra- Penta- Tri- Tetra- Penta- Tri- Tetra- Penta-
480 987 — 5.6 1.2 — 99 96 — 0.7 4

500 683 2.3 2.4 0.86 99 99 98 0.4 0.6 2
620 865 — 2.4 0.47 — 99 97 — 0.5 2
680 958 — 0.4 0.14 — 98 96 — 1.0 3
760 550 1.7 — 99 — 0.3 —
—
— —
Calculated from volume of air sampled and quantity of PCB trapped.
1
1 % or less of total PCB was found on the second plug in all cases.
From Bidleman, T. F. and Olney, C. E., Bull. Environ. Contam. Toxicol., 11, 442, 1971. With per-
mission.
Table 27
COLLECTION OF PCB VAPORS IN
GREENBURG-SMITH IMPINGER
PCB in air
(ng nr3) % In impinger'
Flow rate Volume air
(jf min-1) (m3) Tetra- Penta- Tetra- Penta-
17 17.3 543 148 79 83

28 18.4 322 76 75 79
28 32.8 33 11 79 82
• Remainder trapped on polyurethane foam.
From Bidleman, T. F. and Olney, C. E., Bull. Environ. Contam.

Toxicol., 11, 442, 1971. With permission.
inants. Also, some investigators used a glass fiber filter to remove paniculate matter
present in ambient air. On the other hand, several researchers preferred to introduce
the tested compounds directly to the foam column by injecting a suitable amount of
their solution in an organic volatile solvent into the first foam sorbent plug.71
Bidleman and Olney66 examined, for example, the collection efficiency of polychlor-
inated biphenyls on a polyurethane foam sorbent by employing glass beads coated with
the compound of interest to serve as a known source of atmospheric PCB. The beads
were placed a few inches to several feet from the collection device, thus regulating the
levels in the air being sampled. After completing the sampling step, the foam plugs
were extracted with petroleum ether in Soxhlet extractors and the insecticides deter-
mined in the concentrated extracts by gas chromatography. It should be mentioned
that a cleanup step of the extracts is recommended on an alumina column to remove
peaks appearing in the blank foam itself.
A comparative study was made for the collection of PCB isomers on both polyure-
thane foam sorbent and a Greenburg-Smith impinger containing ethylene glycol.66 The
results presented in Tables 26 and 27 show the superiority of the foam sorbent for the
sorption of PCB isomers even when fast flow rates were used.
Polyurethane foam sorbent-containing air samplers were successfully employed for
the collection of PCB in open-ocean atmosphere.66 The GC patterns matched Aro-
clor® 1248 and the concentrations in the air were calculated as both Aroclor© 1248
and 1254. Generally, most of the PCBs were found on the first foam plug.
In a recent investigation, Lewis et al. 71 employed a standard high-volume air sam-
pler146 as modified by SURC (Syracuse University Research Corporation 147 ) (Figure
11). The coated glass beads situated in the lower compartment of the SURC sampler
were substituted with a 5.5 x 7.6 cm cylindrical polyether polyurethane foam sorbent
plug (density 0.021 g cm"3). The foam plugs were held under a slight compression in
the 5 cm (i.d.) x 7.6 cm lower chamber of the glass sampling module. It was indicated
that the foam plug is at least as efficient a sorbent as the cottonseed oil for most
pesticides tested.71 PCBs and PCNs tested include y-BHC, Aldrin, pp'-DDE, pp'-DDT,
and Mirex.
In order to determine the ability of polyurethane foam to hold the sorbed PCBs and
PCNs, microgram quantities of the test compounds in n-hexane were injected into the
plug and air was passed through it into a second plug at 225 I min'1 (column diameter,
3 cm) for 24 hr. The chlorinated hydrocarbons remaining in the plugs were recovered
with 5% diethyl ether in /i-hexane by separate Soxhlet extractors. A cleanup process
was found to be necessary and carried out on the concentrated extracts before the gas
chromatographic analysis (Figure 46). Except for Aldrin, 88 to 106% of the pesticides
were retained on the fortified foam sorbent plug with only 2 to 6% recovered from the
second plug. The percentage of Aldrin remaining in the upper trap was found to be 61
and in the lower trap 4. This poor retention of Aldrin is linked to its probable oxidation
to dieldrin. The retention of Aroclor® 1242 and Halowax® 1001 was found to be 79
and 57%, respectively.
The collection efficiencies of separate mixtures of organochlorine pesticides were
also determined by volatilization from a wool felt filter into a tandem pair of foam
sorbent plugs. It was indicated that there is little dependency of trapping efficiency on
apparent air concentrations in the subnanogram to nanogram per cubic meter range
(Table 28).70 The retention efficiency was found to be generally increased by decreasing
the volatility of pesticide compounds. Similar conclusions were reported by others. 65 - 72
Two polyester polyurethane foam sorbent plugs placed in a suitable sampling appa-
ratus (Figure 11) were successfully employed for the collection of some chlorinated
insecticides (dieldrin, heptachlor, trans-chlordane, and lindane) in field analysis.75 The
equipment developed allowed the determination of the insecticide concentration levels
at different heights above the ground (within several meters). This permitted the deter-
mination of pesticide concentration profiles. High sorption efficiency and capacity
were reported for the foam sorbent examined.
Some measurements have also been carried out with two commercial mixtures of
PCB and PCN. 71 Using a flow rate of 225 I min"1, collection efficiencies (single plug)
for PCB mixture averaged from 70 to 85%, while the more volatile PCN mixture was
collected less efficiently (44 to 61%). The reduction of air flow to 140 i min"1 was
found to have little effect on the trapping efficiencies.
In another investigation, Erickson et al.76'78 recommended polyurethane foam as an
efficient collector for polychlorinated naphthalenes in ambient air. They used an air
sampler built of a glass fiber filter and two polyurethane foam sorbent plugs in tan-
dem. PCNs collected on the glass filter and the foam plugs were triply extracted with
toluene and the PCN concentrations measured by gas chromatography. The presence
of PCNs was confirmed by mass spectra or by monitoring the chloride isotope ratio.
It was reported that PCNs detected in air near a manufacturing site had an average
concentration of 150 and 1400 ng m"3 during two successive 24-hr sampling periods.
All isomers were found to have good abilities for sorption on polyurethane foams with
the majority (93%) sorbed in the first foam plug. The remainder was found in the
second foam plug and in the glass fiber filter. The percentages of mono-, di-, and
73
O
o.
C/3
LU
DC
QC
UJ
D
ca
O
o
8 10 12 14 16 18 20 22
TIME (minutes)
FIGURE 46. Gas chromatograms of polyurethane foam extracts

after alumina cleanup, (a) upper trap, 24-hr ambient air collection; (b)
lower trap, 24-hr ambient air collection; (c) unused foam plug. Chro-
matographed on 3% OV-1 at 180°C with "Ni ECD. All chromato-
grams made at 102 x 2 attenuation. (From Lewis, R. G., Brown, A.
R., and Jackson, M. D., Anal. Cftem.,49, 1668, 1977. With permis-
sion.)
trichloronaphthalene (relative to the total isomer concentrations) collected from am-

bient air were found to be 27, 31, and 37%, respectively. This foam method was suc-
cessfully employed for the detection and determination of polychlorinated biphenyls
in different air samples.
Simon and Bidleman81 examined in more detail the penetration of PCB in gaseous
mixtures through polyurethane foam sorbent plugs. They suggested a very simple high-
volume gas sampler (Figure 14) made of an aluminum barrel (7 cm diameter x 25 cm
long) packed with 14 polyurethane foam plugs (7.6 cm diameter, 1 cm thick). A 15th
plug was spiked with about 40 ng of mixed PCB isomers in hexane and after evapora-
ting the solvent it was placed at the front of the sampling train as a source of PCB. Air
was drawn through the foam column with the help of a pump at flow rates of 150 to
810 I min"1 and total air volumes of 300 to 1600 m3. The amount of PCB present in
each foam plug was determined by a gas chromatographic method after extracting each
of them in a Soxhlet with petroleum ether and cleaning the extracts by shaking with
7% fuming sulfuric acid. The following PCB isomers were examined: 3,3'-dichlorobi-
Table 28
COLLECTION EFFICIENCIES OF
POLYURETHANE FOAM FOR
CHLORINATED PESTICIDES VS. AIR
CONCENTRATIONS (225 I MIN'1)
Statistical
Calc. air Collection data
cone efficiency
(ng m'3)
a-BHC 0.15 53.2 6 6.4

0.08 38.4 5 14.0
0.03 55.0 6 20.7
Aldrin 1.50 58.5 2 2.1
0.30 35.3 9 24.1
0.06 50.2 5 9.4
p,p'-DDE 3.10 95.7 3 9.0
0.60 96.2 7 16.4
0.30 104.8 7 24.5
0.10 101.0 3 27.6
p,p'-DDT 9.20 114.7 3 12.6
1.84 94.6 8 13.4
0.92 93.6 7 9.0
0.37 83.0 2 21.2
Mirex 9.20 103.7 3 11.6
0.60 100.4 7 7.1
0.30 98.7 6 5.6
0.12 105.4 5 5.7
From Stratton, C. L., Whitlock, S. A., and Allan, J.

M., EPA Rep. 600/4-78-048, U.S. Environmental Pro-
tection Agency, Washington, D.C., 1978. With permis-
sion.
phenyl, 2',3,4-trichlorobiphenyl, 2,4',5-trichlorobiphenyl, 3,3',4,4'-tetrachlorobi-

phenyl, 2,2',5,5'-tetrachlorobiphenyl, 2,2',4,5,5'-pentachlorobiphenyl, 2,2',4,4',6,6'-
hexachlorobiphenyl and Aroclor® 1016.
Individual PCB isomers were found to be eluted through the foam column in distinct
bands and in order of decreasing volatility. The order of eluting the components of the
commercial PCB mixture Aroclor® 1016 through the foam material was found to
parallel their order of elution from a gas chromatographic column (Figure 47).
It was also reported that the penetration of the PCB isomers (positions of their peak
maxima) is linear with total air volume and the elution band widths increase with the
flow rate (Figure 48).8l Finally, it was concluded that the collection efficiency of a
polyurethane foam sorbent trap depends strongly on sample volatility, total air volume
passed through the collector and the thickness of the foam column. Two foam plugs
(each 7.6 cm diameter and 7.6 cm thick) were recommended to retain PCB isomers
with molecular weights as low as dichlorobiphenyl in a 24-hr sampling period (600 m3
of air).
The limitation of this procedure is that it does not adequately reflect field sampling
conditions. Burdick and Bidleman82 made an extension of the above-mentioned pro-
cedure to conditions closer to those in the field by continuous introduction of sample
vapors. They used a similar sampling apparatus with some adjustments made for fron-
tal chromatographic operation. Continous sample introduction took place directly be-
hind the prefilter using a Pasteur pipet packed with glass beads previously coated with
75
10 11 12 13 14
FIGURE 47. Movement of Aroclor® 1016 components through polyurethane foam

sorbent. 760 m3 air, 0.5 m3 min~'. For clarification, the experimental points are not
shown. Inset shows a gas chromatogram of Aroclor® 1016. (From Simon, C. G. and
Bidleman, T. F., Anal. Chem., 51, 1110, 1979. With permission.)
about 50 mg of a single compound of interest. The slight vacuum in the system created
by high volume air flow caused a stream of air to be drawn through the coated bead
column, bleading sample vapors into the mixing chamber. The flow rate through the
lead column was adjusted to 6 to 25 ml miir'.
The frontal movements of hexachlorobenzene (HCB) and two PCB isomers (DCB
and TCB) through the foam material have been measured using the previously de-
scribed system. It was indicated that vapor penetration through the foam column is
dependent on both total air volume and the volatility of PCB compound. The break-
through volume (the point at which the concentration of solute in the column effluent
is half the concentration introduced to the column) was found 82 to be in good agree-
ment with the retention volume obtained in the high-volume elution experiments81 for
the same chlorinated biphenyl isomers. A method was developed for predicting the
movement of the more volatile chlorinated hydrocarbons through polyurethane foam
sorbent and the amount of the foam needed to prevent breakthrough. This can be seen
in Figure 49, where the quantity of the chlorinated compound found on the individual
foam plug was calculated and expressed as cumulative percentage of the total amount
recovered in all 15 plugs. At 500 m3, 90% of the TCB was found within the first 4 cm
of foam sorbent. At 900 m3, however, 7 cm of foam was required to retain 90% of
TCB.
Vannucchi and Berlincioni83 examined the possibility of using a polyurethane foam
sorbent for the sorption of Apirolio® 1431C vapors (a polychlorinated biphenyl die-
lectric fluid containing 42% chlorine). They designed an experiment using conditions
very similar to those present in electrical industry manufacturing capacitors. Polyure-
thane foam packed in a simple sampler consisting of a tube of 2.8 cm internal diameter
and 5 cm length was employed for the collection of Apirolio® vapors. These investi-
gators compared the sorption efficiency of the foam with a Greenburg-Smith impinger
filled with isopropyl alcohol or diethyl glycol using a flow rate of 17 i. min"1 and 1 m3
FIGURE 48. Effect of flow rate on 2,4',5-TCB elution bands. 880

m3 air volume. Flows (m3 min~'); O = 0.22,* = 0.81. (From Simon,
C. G. and Bidleman, T. F., Anal. Chem., 51, 1110, 1979. With per-
mission.)
100 -
15
FIGURE 49. Cumulative percent of TCB retained by polyurethane

foam sorbent at (a) 500, (b) 700, and (c) 900 m3 air. For n cm foam,
cumulative percent = g of TCB on plugs 1 + 2 4- . . . + n/ (total p%
of TCB on all 15 plugs). (From Burdick, N. F. and Bidleman, T. F.,
Anal. Chem.,53, 1926, 1981. With permission.)
77
sample volume. The foam plugs were extracted with petroleum ether in a Soxhlet ex-
tractor (60 discharge cycles) and the extracts were brought to a suitable volume and
analyzed by gas chromatography. The highest recovery was obtained with polyure-
thane foam plugs (99.9%), followed by diethylene glycol (99.45%), and finally by
isopropyl alcohol (98.6%).
Some authors 84 recommended the use of polyurethane foam sorbent for trapping
high molecular weight chlorinated organic compounds in air by a high-volume air flow
system (450 to 500 f min'1) and sample size of 1000 to 2000 m3. For more volatile
organic compounds, Florisil® sorbent was better using low-volume sampling condi-
tions (20 i min" 1 ). With these two systems it was possible to identify about 30 PCB
("fingerprint") isomers in air samples examined which match those in Aroclor® 1242.
Heavier PCBs (Aroclor® 1254) were estimated to be about 10% of the total present in
the samples. The data obtained confirm the presence of selected organic pollutants in
the atmosphere and remote marine regions and provide a baseline against which future
pollutants may be measured.
A comparative study of the collection efficiency and sampling reproducibility of
polyurethane foam and Tenax® sorbents for field sampling of PCB and chlorinated
hydrocarbon pesticides of different volatilities has been carried out.85 In this investi-
gation, air was pulled at 350 to 500 i min"1 through a 10 cm diameter or 20 x 25-cm
glass fiber filter followed by two 7.6 x 7.6-cm polyurethane foam plugs or two 10-g
Tenax® traps (54 cm2 cross-section) using a Ratron® DR-313 brushless pump. Petro-
leum ether was employed for the recovery of pesticides from the sorbents in a Soxhlet
extractor and the extracts were cleaned by alumina chromatography and then separated
on a silicic acid column. Fractions from the columns were shaken with 7% fuming
sulfuric acid and the PCB/DDE fraction was further treated with alcoholic potassium
hydroxide and determined as usual by gas chromatography. Comparisons were made
between the foam and Tenax® sorbents for collecting HCB (hexachlorobenzene),
PCB, chlordane, and toxaphene. The concentration levels of chlorinated hydrocarbon
pesticides determined by the two sampling methods were in good agreement except for
HCB which was very poorly retained by the foam owing to its high volatility.
In another comparative study,86 the retention and collection abilities of airborne
polychlorinated biphenyls by polyurethane foam (plug, 1.3 cm diameter and 3.8 cm
thick), Florisil® (0.3 g, 100 to 200 mesh), and Amberlite® XAD-2 resin (0.4 g, 20 to
50 mesh) were examined. The investigators employed two or three columns (0.9 cm
diameter) packed with each sorbent. The retention efficiencies were determined by the
direct spike of the sorbent with the PCB compound dissolved in a suitable volatile
solvent; after drying, air was allowed to draw through the column. Retention and
collection efficiencies were calculated by dividing the amount of 14C-labeled 2,5,2' ,5'-
tetrachlorobiphenyl (TCB) recovered by the first column by the total amounts of TCB
recovered from all columns used in tandem for each sorbent (Tables 29 and 30). Al-
though the Amberlite® XAD-2 and Florisil® gave higher TCB collection efficiencies
than polyurethane, the authors indicated that the use of larger amounts of foam sor-
bent could produce better collection efficiencies.
Lewis et al.72'87 stated that polyurethane foam can easily trap the less volatile com-
pounds and suggested the use of a combination of foam and a granular sorbent for the
retention of more volatile compounds in air. A comprehensive investigation of the
sorption of various insecticides by the foam alone and by its combination with
Chromo-102, Propak R, XAD-2, Tenax® GC, or Florisil®, has been made. The dual
sorbent trap used is shown in Figure 50. Measurements made with six PCBs are shown
in Table 31. The dichlorobiphenyl and one of the two trichlorobiphenyls tested were
more efficiently collected by the dual trap than by the trap containing polyurethane
foam alone. The chromatograms shown in Figure 51 indicate the preferential vapori-
Table 29
TETRACHLOROBIPHENYL PARTICULATE RETENTION
EFFICIENCIES
Vol. air 1st Col- 2nd Retention

Flow rate sampled umn Column efficiency
Adsorbent (cm3 min"1) (m3) Recovery (%)" (ng) (ng) (%)
XAD-2 7000 10.1 100 301 0 100

6200 8.6 77 223 0 100
6400 8.8 72 215 0 100
Av. 83(92)' Av. 100
Florisil« 6000 8.0 91 272 0 100
5600 7.4 94 282 0 100
4200 11.3 94 272 0 97
3800 18.5 104 300 12 96
3400 16.5 90 255 15 94
Av. 95(99) Av. 97
Polyurethane 7200 8.2 81 202 41 83
7300 9.2 77 161 71 69
7000 8.8 80 213 26 89
Av. 79(79) Av. 80
Coated 7300 9.2 84 182 70 72
polyurethane 6500 8.9 71 96 116 45
6800 9.3 81 140 103 58
Av. 79(79) Av. 58
• TCB spike = 300 ng = 2.22 x 104 dpm.

* Average elution efficiencies from separate recovery experiment run in triplicate.
From Doskey, P. V. and Andren, A. W., Anal. Chim. Acta, 110, 129, 1979. With permission.
Table 30
TETRACHLOROBIPHENYL VAPOR COLLECTION EFFICIENCIES
Flow rate Vol 1st 2nd 3rd Collection

(cm3 air sampled Recovery Column Column Column efficiency
Sorbent min"1) (m3) (%)• (ng) (ng) (ng) (%)
XAD-2 8,500 9.6 95 141 1 0 99

5,700 5.5 113 168 1 0 99
9,400 10.6 71 106 0 0 100
8,500 17.1 113 163 4 2 97
Av. 98(92)' Av. 99
FlorisiF 4,900 16.5 100(99) 149 0 0 100
Polyurethane 15,800 15.9 75(79) 57 45 11 50
° TCB spike = 150 ng = 1.11 x 104 dpm.

* Average elution efficiencies from separate recovery experiment run in triplicate.
From Doskey, P. V. and Andren, A. W., Anal. Chim. Acta, 110, 129, 1979. With permission.
zation of the more volatile PCBs from the fortified felt pad (trace b) and more efficient
trapping of the less volatile PCBs by the polyurethane foam sorbent alone. However,
no differences were observed between the sorbent systems for seven other pesticides
(Table 32). Repetitive use of the sampling cartridges over long periods of time revealed
no problems associated with retention of chemicals or buildup of interfering back-
ground material.
In a more recent publication, Lewis and MacLeod88 used a combination of open-cell
79
FIGURE 50. Dual sorbent vapor trap. (Sampling cartridge) PUF =

polyurethane foam. (From Lewis, R. G. and Jackson, M. D., Anal.
Chem., 54, 592, 1982. With permission.)
polyether polyurethane foam sorbent and Tenax® GC in a single sampling cartridge

to improve the collection of more volatile compounds, such as 1,2,3-tri- and 1,2,3,4-
tetrachlorobenzene. A battery powered, low-volume air sampling system (Figure 16)
was employed. The sampler provided air flows of up to 4 I min"1 which afforded
theoretical detection limits of less than 0.1 pig nr3 for most chemicals tested.
The dual-sorbent trap used in that study consisted of a 0.6-g layer of Tenax® GC
or other granular polymeric sorbent "sandwiched" between two 2.2 cm diameter x 3.8
cm thick polyurethane foam plugs and packed in a 2.0 x 10 cm borosilicate glass tube.
To estimate the collection efficiencies of polyurethane foam alone or in the dual trap
system, the trap was attached to a modified midget impinger vapor generator to which
a weighed quantity of the test compound or mixture in 1 ml hexane was added. Reten-
tion efficiencies were determined by fortifying the polyurethane foam with a known
quantity of chemical or mixture dissolved in 0.5 to 1.0 ml of hexane by slow, dropwise
addition of the solution to the intake face of the plug. After drying, the fortified plug
was placed in the first cartridge of the train and a clean polyurethane foam plug placed
in the second cartridge. Ambient air was then drawn through the train at 3.8 I min"1
for 4 hr. The organic materials retained on the polyurethane foam or polyurethane
foam Tenax® GC combination were recovered with diethyl ether in hexane using a
Soxhlet extractor. After concentrating the extracts, aliquots were analyzed by gas or
high performance liquid chromatography. Collection efficiencies are tabulated in Ta-
bles 33 and 34. The storage stability of the polyurethane foam cartridge after use was
also evaluated.88
In most of the above procedures, the organochlorine insecticides retained on the
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Time/Min.
FIGURE 51. Electron capture gas chromatograms showing

collection of polychlorinated biphenyls on polyurethane foam
at 225 I min"'. (a) Mixture of PCB congeners in n-hexane, (b)
residue remaining on the wool felt pad after 24 hr (at one-half
the attenuation), and (c) residue collected by the foam. (From
Lewis, R. G., MacLeod, K. E., and Jackson, M. D., Paper no.
65, Chemical Congress, Am. Chem. Soc. — Chem. Soc. Jpn.,
Honolulu, Hawaii, April 2-6, 1979. With permission.)
foam sorbent were leached by various solvents; e.g., acetone n-hexane, petroleum
ether, etc., using a simple elution procedure or Soxhlet extractor. The extracts were
usually passed through an alumina or silica gel column for cleaning, and after their
concentration to the appropriate volume, injected directly into a gas chromatograph
using a suitable column. The pesticides were usually identified and quantitated on the
basis of GC peak heights, or areas of the corresponding standards. In some cases the
amounts of pesticides were determined on both the foam sorbent and the glass bead
column used as a feeder source for the pesticide under investigation.
In some other cases, especially with polychlorinated biphenyls which can be present
in many isomeric forms, a derivatization technique was employed.148 By using this
Table 32
HIGH-VOLUME COLLECTION EFFICIENCIES OF PESTICIDES ON FOAM/
GRANULAR SORBENT COMBINATIONS
% Collection" on foam/sorbent combinations after 24 hr, 225 I rain"1
Foam/
Calc. air cone Foam Foam/ Foam/Po- Foam/ Tenax® Foam/
Pesticide (ng nr3) alone Chromo 102 rapak R XAD-2 GC Floi-isi!®
Aldrin 0.3—3.0 28 34 35 33 40
p,p'-DDE 0.6—6.0 89 83 93 135 71 138
p,p'-DDT 1.8—18.0 83 77 89 138 69 119
Mirex 1.8—18.0 93 94 95 132 78 123
Tech. Chlordane 15—150 73 85 74 87 73 97
a-Chlordane 1.5—15.0 114 108 96 102 100 98
y-Chlordane 1.5—15.0 126 104 91 96 93 100
" Average 6 to 12 determinations.
From Lewis, R. G. and Jackson, M. D., Anal. Chem., 54, 592, 1982. With permission.
Table 33
COLLECTION EFFICIENCIES FOR ORGANOCHLORINE
PESTICIDES
Quantity Air Collection efficiency (CE)

introduced volume
Compound G/g) x (%) RSD (%) n
o-Hexachlorocyclohexane 0.005 0.9 115 8 6

y-Hexachlorocyclohexane 0.05—1.0 0.9 91.5 8 5
(Lindane)
Technical chlordane 0.2 0.9 84.0 11 8
p,p'-DDT 0.6, 1.2 0.9 97.5 21 12
p,p'-DDE 0.2, 0.4 0.9 102 11 12
Mirex 0.6, 1.2 0.9 85.9 22 7
2,4-D Esters
Isopropyl 0.5 3.6 92.0 5 12
Butyl 0.5 3.6 82.0 10 11
Isobutyl 0.5 3.6 79.0 20 12
Isooctyl 0.5 3.6 >80"
Not vaporized. Value based on retention efficiency (RE) = 81.0 (RSD = 10%, n
= 6).
From Lewis, R. G. and MacLeod, K. E., Anal. Chem., 54, 310, 1982. With permission.
method all non-fully chlorinated PCB species were converted to a single isomeric spe-
cies, DCB (decachlorobiphenyl) with antimony(V) chloride, e.g.,
Cl Cl
oô
Cl Cl Cl Cl Cl Cl
2,2,5,5', tetrachlorobiphenyl Decachlorobiphenyl (17)
and the gas chromatographic pattern greatly simplified as the many peaks were re-
placed by only one peak for decachlorobiphenyl.74 The detection limit is also enhanced
83
Table 34
COLLECTION EFFICIENCIES FOR SEMIVOLATILE
ORGANOCHLORINE COMPOUNDS AND PCB
Quantity in- Collection efficiency

troduced'
Compound or mixture x (%) RSD (%)
1,2,3-Trichlorobenzene 1.0 6.6' 22

1,2,3,4-Tetrachlorobenzene 1.0 62.3' 33 5
Pentachlorobenzene 1.0 94.0 12 5
Hexachlorobenzene 0.5, 1.0 94.5 8 5
Hexachlorocyclopentadiene 1.0 8.3' 12 5
2,4,5-Trichlorophenol 1.0 108 3 5
Pentachlorophenol 1.0 107 16 5
Aroclor® 1242 0.1 96.0 15 6
Aroclor® 1254 0.1 95.0 7 6
Aroclor® 1260 0.1 109 5 11
• Air volume 0.9 m3

* % CEs were 98, 98, and 97% (n = 2), respectively, for these three com-
pounds by the PUF/Tenax GC "sandwich" trap.
From Lewis, R. G. and MacLeod, K. E., Anal. Chem., 54, 310, 1982. With
permission.
as the electron capture detector is much more sensitive to DCB than to partially chlor-
inated biphenyls. The advantages and disadvantages of this derivatization method have
been discussed in detail in Reference 74.
Although polyurethane foam sorbents have extensively been employed for the reten-
tion of many chlorinated pesticides in air, the type of foam used is rarely specified.
Fortunately, Adams and Caro65 made an excellent comparative investigation on the
sorption of various insecticides in air by polyether and polyester polyurethane foams
under otherwise the same experimental conditions. No significant differences between
the ester and ether forms of foam were observed with respect to the trapping and
extraction of the pesticides examined. The sorption of different organochlorine insec-
ticides in air has been investigated also as a function of temperature; complete recov-
eries were obtained even on using a temperature as high as 52°C (Table 35). The reten-
tion of organochlorine insecticides in aerosols was also tested. Generally collection of
the examined compounds from aerosol with polyurethane foams was inefficient (Table
36).
ii. Organophosphorus Compounds

Polyurethane foam of polyether type has been evaluated for use in a high-volume
air sampler to collect several organophosphorus pesticides,65'71 e.g., Diazinon, methyl
parathion, parathion, and Malathion. The sampler (Figure 11) draws air through a
glass module equipped with a particulate filter and a polyurethane foam trap at flow
rates which could be controlled from 100 to 250 t mhr1. Up to 360 m"3 of air could be
sampled in 24 hr, providing theoretical detection limits of less then 0.1 ng m3 for indi-
vidual compounds. The organophosphorus compounds retained on the foam plug were
recovered with 5% diethyl ether in n-hexane using a Soxhlet extractor. No cleanup was
found to be necessary before injecting the concentrated extracts in the gas chromato-
graph.
It was recognized that acceptable trapping efficiencies (75%) are feasible for these
compounds despite their high vapor pressure.65 71 Polyether and polyester polyurethane
Table 35
ESTER-FORM PUF TRAPPING
EFFICIENCY FOR INSECTICIDES AT 52°C
(31.0 m3 OF AIR PASSED THROUGH THE
SYSTEM)
Residues (% of applied pesticides)
Compound On source On plugs Total
a-BHC 92 92
Aldrin 106 106
p,p'-DDE 99 99
o,p'-DDT 101 101
p,p'-DDD 88 88
p,p'-DDT 104 106
Lindane 95 95
/3-BHC 98 103
Heptachlor epoxide 88 88
Dieldrin 83 83
Endrin 98 101
From Adams, J. D. and Caro, J. H., EPA Research Report

EPA-600/4-80-008, U.S. Environmental Protection
Agency, Washington, D.C., 1980. With permission.
Table 36
THE TRAPPING OF PESTICIDE AEROSOLS BY A 5-
CM ESTER-FORM PUF PLUG (8.5 m3 OF AIR
PASSED THROUGH THE SYSTEM)
In chamber In PUF
Compound In bomb washings trap Total
o-BHC 9.0 24.8 >33.8

Aldrin 17.8 — 39.7 S=57.5
p,p'-DDE 19.8 — 29.4 >49.2
o,p'-DDT 24.6 — 32.0 3*56.6
p,p'-DDD 18.6 — 25.7 3*44.3
p,p'-DDT 45.7 — 43.9 3*89.6
Lindane 12.0 5.4 46.2 63.6
/3-BHC 18.5 3.7 40.0 62.2
Heptachlor epoxide 13.6 10.6 33.8 58.0
Dieldrin 14.3 7.4 28.3 50.0
Endrin 20.7 23.3 43.5 87.5
From Adams, J. D. and Caro, J. H., EPA Research Report EPA-600/4-

80-008, U.S. Environmental Protection Agency, Washington, D.C.,
1980. With permission.
foams show about the same sorption ability towards organophosphorus pesticides. The
foam sorbent retained these compounds efficiently at room temperature as well as at
higher temperatures.
Table 37 shows, for example, the retention efficiency of polyurethane foam at 52°C.
As in the case of organochlorine insecticides, the trapping ability of polyurethane
foams for organophosphorus compounds injected as aerosols is substantially lower
than that of molecular vapors (Table 38).
85
Table 37
ESTER-FORM POLYURETHANE FOAM
PESTICIDE TRAPPING EFFICIENCY AT
52°C°
Methyl parathion 0 95 95
Ronnel 5 102 107
Parathion 0 88 88
,Ethion 0 96 96
Carbophenothion 0 82 82
Diazinon 5 90 95
Malathion 3 90 93
31.0 m3 of air passed through the system.
From Adams, J. D. and Caro, J. H., EPA Research Re-

port EPA-600/4-80-008, U.S. Environmental Protection
Agency, Washington, D.C., 1980. With permission.
Table 38
THE TRAPPING OF ORGANOPHOSPHORUS
PESTICIDE AEROSOLS BY A 5-CM ESTER-FORM
POLYURETHANE FOAM PLUG0
Residues (% applied pesticides)

In chamber InPUF
Methyl parathion 15.2 4.9 27.4 47.5

Ronnel 13.0 4.3 32.9 50.2
Parathion 16.3 4.2 27.3 47.8
Ethion 15.1 1.9 24.8 41.8
Carbophenothion 6.3 1.2 17.2 24.7
Diazinon 8.9 2.8 13.2 24.9
Malathion 1.9 0.6 2.5 5.0
8.5 m 3 of air passed through the system.
From Adams, J. D. and Caro, J. H., EPA Research Report EPA-600/

4-80-008, U.S. Environmental Protection Agency, Washington, D.C.,
The previously described88 low-volume air sampling system utilizing polyurethane

foam as a trapping medium has also been examined for the collection of organophos-
phorus compounds in gaseous mixtures. It was found that this class of compounds is
generally efficiently collected by polyurethane foam sorbents (Table 39).
A comparative study of the collection capabilities of polyurethane foam sorbent
alone and in combination with other granular absorbents in a high-volume air sampling
system for the absorption of organophosphorus pesticides has also been carried
out. 72 87 Polyurethane foam is at least as efficient as the different combinations tested
(Table 40).
Table 39
COLLECTION EFFICIENCIES FOR
ORGANOPHOSPHORUS PESTICIDES
Quantity Collection efficiency

introduced'
Compound <Mg) RSD (%)
Dichlorvos (DDVP) 0.2 72.0 13 2

Ronnel 0.2 106 8 12
Chlorpyrifos 0.2 108 9 12
Diazinon 1.0 84.0 18 18
Methyl parathion 0.6 80.0 19 18
Ethyl parathion 0.3 75.9 15 18
Malathion 0.3 100'
Air volume = 0.9 m3.

' Decomposed in generator; value based on % RE = 101 (RSD = 7%,
n = 4).
From Lewis, R. G. and MacLeod, K. E., Anal. Chem.,54, 310, 1982.

With permission.
Table 40
COLLECTION EFFICIENCIES FOR SEMIVOLATILE
ORGANOPHOSPHORUS COMPOUNDS
% Collected0 after 24 hr at 225 / mhr1
Calculated Foam/ Foam/ Foam/

air cone Foam/ Chromosorb® Foam/ Foam/ Tenax® Florisil®
Pesticide ng m"3 alone 102 Propak R XAD-2 GC PR
Diazinon 3.0—30.0 63 72 59 71 76 72
Methly parathion 1.8—18.0 91 82 72 80 87 83
Ethyl parathion 3.6—36 96 85 72 81 86 83
Malthion 0.9—9.0 97 88 78 89 91 81
• Average 6 to 12 determinations.
From Lewis, R. G. and Jackson, M. D., Anal. Chem.,54, 592, 1982. With permission.
iii. Polynuclear Aromatic Hydrocarbons

Polynuclear aromatic hydrocarbons generally produced by inefficient combustion of
carbonaceous materials149 are known to have a carcinogenic effect. 150 Relatively high
concentrations of PAHs in air have been found in urban and industrialized areas;
however, paniculate PAHs may be transported by air masses over long distances to
nonurban areas.151
Yamasaki et al.90-90" employed polyurethane foam sorbents in a high-volume sam-
pling method for the collection of several PAHs in air. Air was pulled at 750 to 800 1
min"1 for 24 hr through a glass fiber filter (20.3 x 25.4 cm) and then through two
polyurethane foam sorbent plugs (10 cm diameter x 5 Cm thick) (Figure 13). Both the
glass fiber filter and polyurethane foam plugs were separately extracted with cyclohex-
ane in a Soxhlet extractor. The PAHs in each extract were removed with dimethyl
sulfoxide, cleaned by passing through a silica gel column and determined by gas chro-
matography. Table 41 shows the collection of different PAHs in ambient air following
this procedure. As is clear from these results, the trapping efficiencies of glass fiber
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filter for the PAHs examined were less than 5% except for chrysene +
benzo(a)anthracene 4- triphenylene, benzo(a) pyrene + benzo(e)pyrene, o-phenyleno-
pyrene, and benzo(ghi)perylene + anthracene, where the percentages of trapping are
43.4, 94.6, and 100%, respectively. Most of the PAHs tested were efficiently collected
on the first foam plug except for phenanthrene + anthracene.
The same investigators90 made a recovery test for the different PAHs from air using
a glass fiber filter (2 cm diameter) and two polyurethane foam plugs (2.3 cm diameter)
placed into glass tubes (2 cm diameter) in series (Figure 15). Each PAH (25 ^g) was put
on the glass fiber filter and clean air was allowed to pass through the tubes at 41 I
min~' for 24 hr. The PAHs, except phenanthrene, were moved away from the glass
fiber filter and trapped efficiently on the first polyurethane foam plug. Recoveries were
more than 90%, but for phenanthrene it was only 79.2%.
Thrane and Mikalsen91 examined several sorbents for the collection of PAHs in the
gaseous phase; polyurethane foam was found to be the most appropriate. They used a
simple air sampler (Figure 12) made of a glass fiber filter (14.2 cm diameter; for col-
lecting particulate matter) and cylindrical polyurethane foam plugs (11 cm diameter, 5
cm thick). Air was drawn through the sampler at a rate of 417 I min"' employing a
vacuum pump. This system was used for the collection of PAH in real air samples and
the organic pollutants were recovered from the filter and foam plugs with cyclohexane
in a Soxhlet apparatus. It was reported that cleaning of the foam plugs before use is a
very important step to eliminate any interference in the subsequent gas chromato-
graphic analysis." The plugs were squeezed in toluene at 100°C and then extracted
with acetone for 24 hr in a Soxhlet apparatus followed by extraction with cyclohexane
for the same period. Although the cleaning procedure suggested is time consuming, the
plugs once cleaned can be used several times with the same efficiency. Following the
recommended procedure, it was possible to collect a wide range of volatile PAHs on
polyurethane foam plugs. Only a minor part of the volatile PAHs is found in the glass
fiber filter. In some samples an average of 5 to 6% of the total PAHs collected was
found to be retained by the glass filter, 65 to 70% on the first polyurethane foam plug
and 25 to 30% on the second plug. However, it was noted that the distribution of
PAHs between the glass filter and the foam plugs can be influenced by the concentra-
tion and the composition of air pollutants as well as sampling conditions."
iv. Other Organic Pollutants

Polyurethane foams have also been used as a trapping sorbent for some other classes
of organic pollutants, 92 - 93 e.g., phthalate ester plasticizers. Two phthalate esters, di-(2-
ethylhexyl) phthalate and di-n-dibutylphthalate were detected in relatively high concen-
trations in the atmosphere over the North Atlantic Ocean.92 Other researchers93 em-
ployed a combination of a glass fiber filter and polyurethane foam plugs in a high-
volume air sampler for the retention determination of dibutylphthalate, diheptyl-
phthalate and diethylphthalate in atmospheric environments. Air was sampled at 28 i
min"1 for 24 hr through a glass tube containing a glass fiber filter (20 mm diameter)
and two polyurethane foam plugs (23 mm diameter x 50 mm) in series. The filter and
the first foam plug were extracted in a Soxhlet extractor with 5% petroleum ether in n-
hexane and the phthalate ester was then determined by gas chromatography. When 20
j^g of each phthalate ester was put on the filter and 75 m 3 of clean air allowed to pass
through the tube, the phthalate compounds moved away from the filter and were trap-
ped completely on the first polyurethane foam plug. No phthalate esters were detected
in the second foam plug. The average recoveries of dibutylphthalate, dihexylphthalate,
and diethylhexylphthalate were found to be 99.1, 93.3, and 92.9%, respectively.
Employing the previously described low-volume air sampling system it was also pos-
sible to collect some other pesticides. Carbamate pesticides were collected with 62 to
89
Table 42
RETENTION AND COLLECTION EFFICIENCIES FOR CARBAMATES,
UREAS, TRIAZINES, AND PYRETHRINS
Static recovery Retention efficiency Collection efficiency

Fortification
Compound level- (jjg) x (%) RSD (%) n x ( % ) RSD (%) n x(%) RSD (%) n
Carbamates
Propoxur 5 61.4 10 6 77. 6 37 6 96.7 11 6
Carbofuran 15 55.3 12 6 64. 2 46 6 87.2 14 6
Bendiocarb 50 57.3 11 6 69. 8 43 6 62.1 14 6
Mexacarbate 10 62.8 19 6 62. 7 41 6 89.8 14 6
Carbaryl 100 56.6 14 6 63. 6 53 6 b
13 6
Ureas
Monuron 19 87.0 6 6 91. 2 6 5 NV
Diuron 20 84.1 8 6 90 .0 2 5 NV
Linuron 20 86.7 8 6 92 .5 4 5 NV
Terbuthiuron 18 85.0 8 6 88 .8 8 5 NV
Fluometuron 20 91.4 10 6 101 3 5 NV
Chlortoluron 20 86.2 11 6 92 .0 7 5 NV
Triazines
Simazine 10 103 6 5 101 9 6 NV
Atrazine 10 104 7 5 98 .9 7 6 NV
Propazine 10 105 11 5 99.9 14 6 NV
Pyrethrins
Pyrethrin I (9.7)< 90.5 10 6 95..6 22 5 NV
Pyrethrin II (6.1)' 88.6 11 6 69.9 29 5 NV
Allethrin 25 69.2 9 5 58..3 12 6 NV
D- trans-allethrin 25 76.8 9 6 74..4 9 5 NV
Dicrotophos 25 72.0 22 6 71 .7 8 5 NV
Resmethrin 25 76.5 14 6 66.7 14 6 NV
Fenvalerate 25 87.9 3 6 57 .2 20 3 NV
Note: NV = not vaporized.
Air volume 0.9 m3.

* Decomposed in generator.
Estimated on the basis of 20 ^g of pyrethrin with a composition of 48.4% and 30.3% by weight of
pyrethrins I and II, respectively.
From Lewis, R. G. and MacLeod, K. E., Anal. Chem.,54, 310, 1982. With permission.
97% collection efficiencies at concentration levels of 5.6 to 111 pg m"3. The retention
of some pyrethrins was also examined and retention values of 57 to 96% were given
(Table 42). Furthermore, retention measurements have indicated that both ureas (89 to
101%) and triazines (99 to 101%) could be quantitatively trapped on polyurethane
foam if present in air (Table 42). These pesticides were detectable at 1 ^g m"3 or less in
1 m 3 air samples.
The collection of various carbamate compounds, e.g., 2,3,5-Landrin® , Methiocarb,
Mexacarbate, Aminocarb, Carbaryl, Carbofuren, and Propoxur in air by polyurethane
foam has also been tried.65-72 Unlike other organic pollutants, the retention efficiencies
of carbamates in air samples were very low. However, their collection from aerosols
was quite high (Tables 43 and 44). These results suggested that polyurethane foam can
be used as an effective trap for these pesticides when present in airborne aerosols.65
Tests of the derivatization of the carbamate insecticides for analysis by electron-cap-
ture gas chromatography showed that the pentafluoropropionic anhydride proce-
Table 43
ESTER-FORM POLYURETHANE
FOAM TRAPPING EFFICIENCY FOR
PESTICIDES AT 52°C°
Propoxur 82 10 92
Carbaryl 78 0 78
Carbofuran 88 8 96
Aminocarb 68 5 73
Methiocarb 91 3 94
Mexacarbate 62 2 64
31.0 m3 of air passed through system.
From Adams, J. D. and Caro, J. H., EPA Research

Report EPA-600/4-80-008, U.S. Environmental Pro-
tection Agency, Washington, D.C., 1980. With per-
mission.
Table 44
THE TRAPPING OF PESTICIDE AEROSOLS BY
A 5-CM3 ESTER-FORM PUF"

In chamber InPUF
Propoxur 18.0 20.0 25.0 63.0

Carbaryl 17.0 2.4 25.0 44.4
Carbofuran 27.0 19.6 57.0 103.6
Aminocarb — 21.2 87.0 108.2
Methiocarb 14.5 4.4 22.0 40.9
Mexacarbate 34.5 8.0 76.0 118.5
• 8.5 m j of air passed through system.
From Adams, J. D. and Caro, J. H., EPA Research Report EPA-

600/4-80-008, U.S. Environmental Protection Agency, Washing-
ton, D.C., 1980. With permission.
dure152 gave the most satisfactory results. Trifluoracetic anhydride, l-fluoro-2,4-dini-

trobenzene and heptafluorbutyric anhydrides were also tested as derivatization
reagents. The first two gave unacceptable results and the last did not offer any im-
provement over pentafluoropropionic anhydride.
It was also reported that polyester polyurethane foam is an efficient sorbent for
trapping vapors of butyl esters of 2,4-D(2,4-dichlorophenoxyacetic acid) and triallate
in high volume monitoring studies.94 In short-term, low-volume, worker inhalation
exposure studies, the foam sorbent was found to trap butyl esters of 2,4-D, /so-octyl
ester of 2,4-D, bromoxynil octanoate, triallate, and trifluralin. The collected herbicide
vapors were readily recovered from the foam with n-hexane in a Soxhlet extractor and
the extracts analyzed by gas chromatography. The overall efficiencies, for both trap-
ping and extraction, were more than 90%, except for triallate using a single foam plug
(45 mm diameter x 50 mm thick). Two foam plugs were recommended for efficient
91
Table 45
COLLECTION EFFICIENCY FOR 2,4-D BUTYL
ESTER ON 45 x 50 MM POLYURETHANE PLUGS
OVER 24-HR PERIOD
Amount
Amount in U- found in
Air flow Total tube foam plug
rate air vol- (us) (eg) Total
(1
V* ume recovery
min"') (m3) Added left 1 2
0.8 1.2 10 0.23 9.3 0.05 96

10.0 14.4 10 1.54 8.6 0.08 102
20.0 28.8 10 1.02 8.3 0.02 93
25.0 36.0 10 1.76 9.7 0.0 115
1 0.39 0.53 0.0 92
50.0 72.0 10 0.17 9.8 0.02 100
1 0.05 1.0 0.0 105
From Grover, R. and Kerr, L. A., J. Environ. Sci. Health, B16, 59,
Table 46
COLLECTION EFFICIENCY FOR TRIALLATE ON 45 x
50 MM POLYURETHANE PLUGS OVER 24-HR
PERIOD
Amount
found
Amount in U- in foam plug
Air Total air tube (t*g) Total
flow rate volume recovery
(/ min"') Added Left
10 14.4 10 0.18 11.0 0.06 112

100 3.85 95.0 0.19 99
15 21.6 100 0.24 90.0 7.48 98
20 28.8 100 1.58 67.5 27.63 97
25 36.0 1 0.00 0.6 0.40 101
10 0.00 6.0 5.10 111
100 0.64 88.0 16.93 106
From Grover, R. and Kerr, L. A., J. Environ. Sci. Health, B16, 59, 1981.
With permission.
trapping of triallate under high-volume air monitoring conditions. Tables 45 and 46

show, for example, the collection efficiency of 2,4-o butyl ester and triallate by two
foam plugs over a 24 hr period, respectively.
Moreover, an open-cell polyurethane foam prepared from polyol LA-475 and crude
polyisocyanate MDI has been examined as a cigarette filter. 95 A certain volume of
smoke produced from various brands of cigarettes containing tar and nicotine was
drawn slowly through each of five samples of foam (cut to the same size as cellulose
filters, e.g., 1.4 cm long x 0.7 cm diameter) and also through each of five cellulose
plugs removed from the brand cigarettes. The average increase in weight of polyure-
thane foam filters and cellulose filters was 45 and 33%, respectively. Practically, it was
found that the foam filter removes nicotine and other particulate matter from cigarette
smoke and also reduces the moisture and the temperature of the smoke streams. Ad-
dition of aluminum hydroxide or magnesium trisilicate to the foam filter has also been
suggested.
B. Loaded Polyurethane Foams

Polyurethane foams supporting various organic and/or inorganic compounds, en-
zymes, and ion exchangers have been successfully prepared and employed for several
separation and preconcentration purposes. The immobilization of organic reagents in
the foam material is based mainly on the hydrophobic character of polyurethane
foams. Owing to these properties, the foam material swells in contact with hydropho-
bic solvents. That is, hydrophobic solvents and solutes can be physically immobilized
in the foam matrix by swelling. Practically, the foam is immersed in the required sol-
vent for a reasonable time to ensure equilibration, and the excess solvent is then re-
moved by pressing the foam between sheets of filter paper. The foam so obtained
contains about 50 to 80% of solvent, depending, of course, on the type of both the
foam and solvent used. Polyurethane foams supporting solvent extractants and/or liq-
uid ion exchangers are prepared by this procedure. Liquid organic reagents are used
directly or diluted with an appropriate solvent. This procedure is also useful for the
immobilization of chelating agents or iodine solutions dissolved in nonvolatile sol-
vents.
Sometimes organic reagents are immobilized in the foam membranes by dissolving
the solid reagent in a volatile organic solvent; after allowing the foam to swell in it, the
solvent is gradually evaporated from the swollen foam by gentle heating. This proce-
dure was employed for the preparation of some reagent foams and foams supporting
redox reagents. Heterogeneous ion exchange foams are prepared by adding very finely
powdered ion exchangers to the polyol solution before mixing it with the isocyanate
for foam synthesis. The experimental conditions are adjusted so that an even distribu-
tion of the ion exchange powder in the foam membrane will be obtained.
Foams supporting inorganic compounds were also prepared by converting them to
the required cation form and precipitating the latter within the foam matrix as one of
their insoluble salts or by reducing them to the metallic form. The foams thus produced
are suitable for isotope exchange or redox separations, respectively.
Furthermore, foams containing certain functional groups chemically bonded to the
foam matrix are prepared by anchoring these chelating groups directly or indirectly to
the foam matrix.
1. Foams Loaded with Solvent Extractants

a. Collection from Aqueous Media
Braun and Farag11 153 suggested the loading of polyurethane foam with tri-n-butyl
phosphate (TBP) and described the analytical use of the TBP foam in batch and col-
umn operations. Since then several separations and preconcentrations of inor-
ganic,""1 as.-".153-155 and organic 47495660157 species in aqueous media by foam sup-
ported solvent extractants have been described.
A detailed study has been made on the loading properties of different batches of
polyether and polyester polyurethane foams for the organic extractant TBP.41 Poly-
urethane was found to retain TBP much more efficiently than for example granular
Voltalef, which is considered as one of the best granular supports in extraction chro-
matography. Polyether polyurethane foams retain TBP more efficiently than polyester
ones. The uptake of TBP by polyether foams is increased slightly by decreasing cell
dimensions of the foam (Table 47).
Braun and Farag157 made several comparative investigations on TBP-loaded foam
and TBP-loaded Voltalef powder, and demonstrated the practical advantages of using
TBP-loaded foam in many separation systems. The half-life of equilibrium sorption of
93
Table 47
THE TBP-LOADING CAPACITY OF VARIOUS TYPES
OF POLYURETHANE FOAM (IN EACH CASE, 5 G OF
DRY FOAM WAS TAKEN)
Weight of
Sample loaded TBP in loaded
no. Type of foam° foam (g) support (%)
1 Polyurethane foam polyether, 14.9516 66.6

more than 95% open cell (HI)
2 Polyurethane foam, polyether, 15.9490 68.7
more than 95% open cell (H2)
ca. 100% open cell (W8100)
6 Polyurethane foam, polyester, 10.3270 50.7
ca. 100% open cell (PPI-80 n
FR)
° Cell dimensions of sample 1 > sample 2 = sample 3 > sample 4 > sample
5.
From Braun, T. and Farag, A. B., Anal. Chim. Acta, 66, 419, 1973. With
permission.
gold-thiourea complex on different batches of polyether and polyester polyurethane

foams loaded with TBP were found to be, generally, better than those of loaded Vol-
talef. 41 Consequently, the rate of sorption of gold on loaded foam membranes pro-
ceeds faster than with loaded-Voltalef powder.
Polyurethane foam loaded with TBP has been used for the separation of palladium,
bismuth, and nickel in a thiourea-perchloric acid system. The retention behavior of the
three metal ions onto loaded polyurethane foam was examined in batch and column
modes.153
In batch experiments, the rate of retention of palladium-thiourea complex was found
to be quite fast. The half-life time of equilibrium retention as calculated from the curve
of Figure 52 was found to be 0.5 min. The retention isotherm of the palladium-thiourea
complex on the TBP-loaded foam is linear over a wide range of palladium concentra-
tions. Consequently, a symmetrical chromatographic peak could be expected for the
elution of the palladium-complex from TBP-loaded foam columns. This was the situ-
ation as the palladium-thiourea complex, which is retained as a narrow yellow band on
the top of the foam column, was quantitatively eluted with water at a rate of 1ml min"1
(column diameter 15 mm) giving a symmetrical peak (Figure 53). The height equivalent
to a theoretical plate (HETP) was calculated from the elution curve using the following
equation:153
V2 L
N = 8 -^^ = (18)
U
W2 HETP '
where N = number of plates, V m « = volume of eluate at peak maximum, W = width

of peak at 1/e times the maximum solute concentration, and L = length of the foam
I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
0.8 |t"
0.6
\
0.4
\
\
\\
\ \
i \
02
\ N. (g) |l
o \ 11
<J \
-^ 0.1
o
~~ \ "•
_ \
0.08
\
0.06 — \> —
0.04 \
\M
\
\
0.02 \ ~
\
' H
i H
0.01 i i i\ i i i i i i i i i i i i!|
C) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 5' 3(
TIME (minutes)
FIGURE 52. Rate of sorption of the palladium-thiourea complex on

TBP-loaded polyurethane foam at room temperature. Pd2* 1.44-10""
M; NaCKX, 1%: thiourea 3%; HC1O4 0.1 M. (From Braun, T. and
Farag, A. B., Anal. Chim. Acta,6l, 265, 1972. With permission.)
bed and from the breakthrough capacity curve:
V V
N = (19)
(V - V') 2
where V = volume of effluent at the center of the S-shaped breakthrough curve where
the concentration is one-half the initial concentration and V = volume at which the
effluent has the concentration 0.1587 of the initial concentration.
The value of HETP calculated by both methods was found to be the same (1.7 mm
± 7%). It is worth noting that the HETP determined under the same experimental
conditions for TBP supporting Voltalef columns is 2.8 mm. The HETP is increased
(column efficiency decreased) with increasing flow rate in the range of 2 to 13 ml mhr1
(column diameter 15 mm) at all the temperatures tested (25, 35, and 45°C), but this
effect is only pronounced at 25 °C (Figure 54). Consequently, relatively high flow rates
could be applied at 35 or 45°C without any appreciable loss in column performance.
The Vmo, value is not affected by flow rate but decreases with increasing temperature,
yielding sharper peaks.
The breakthrough capacity of the foam was found to be better than that of the
Voltalef column but was dependent to some extent on the foam structure. Also, the
overall capacity of the TBP-loaded foam is about double that of TBP-loaded Voltalef.
Quantitative separations of palladium from various concentrations of nickel and
bismuth in thiourea-perchloric acid systems were possible using TBP-loaded foam col-
umns.153 Nickel does not form a complex with thiourea and consequently is not re-
95
100
H 2 O, ml
FIGURE 53. Chromatogram of the palladium-thi-

ourea complex on TBP-loaded foam at 25°. Bed
height 115 mm; flow rate 1 ml min' 1 . (From Braun,
T. and Farag, A. B., Anal. Chim. Acta, 61, 265,
tained by the foam bed. Bismuth(III)-thiourea complex, which is completely retained

together with palladium on the foam column, can be eluted with 0.5 Mperchloric acid
and lastly the palladium(II) complex can be eluted with water. The water used for
eluent should be presaturated with TBP to maintain the original loading on the foam.
The stepwise elution of nickel, bismuth, and palladium is shown in Figure 55.
More or less similar results were also obtained by another group of researchers35 for
the separation of nickel, bismuth, and palladium in a perchloric acid-thiourea system.
The separation of gold-thiourea complex from dilute aqueous solutions by TBP-
loaded polyurethane foam has also been examined.41 154 Preliminary experiments were
performed in a liquid-liquid extraction system to select the suitable conditions for the
extraction of gold-thiourea complex with TBP. The use of undiluted TBP solution was
recommended for loading the foam material as it gave better results for the extraction
of the gold-thiourea complex. The uptake of the gold complex by TBP-loaded foam
was found to depend on the concentration of the complex in the aqueous solution. The
isotherm shows a good linear relationship over a relatively wide range of gold concen-
trations (Figure 56).
2 3 4 5
FLOW-RATE, ml-cm" 2 -min''
FIGURE 54. Effect of temperature and flow rate on the HETP of the palladium-
thiourea complex. (From Braun, T. and Farag, A. B., Anal. Chim. Acta,6l, 265, 1972.
With permission.)
0.1M HCI04
24 ^Containing: ^
thiourea and
22 1% NaCIO 4
20
18
16
14
12
10
0
20 40 60 80 100 120 140 160 180 200 220
EFFLUENT, ml
FIGURE 55. Separation of nickel, bismuth, and palladium on TBP-loaded foam at

room temperature. Bed height 100 mm; flow rate 2.5 ml min~'. (From Braun, T. and
Farag, A. B., Anal. Chim. Acta, 61, 265, 1972. With permission.)
The elements which can interfere with the analytical and industrial separation of
gold are Zn2*, Co2*, Ni2*, Cu2*, Fe3+, Sb3+, Bi3*, Pd 2+ , and Ag*. These elements were
grouped into three categories: (1) elements which do not interact with thiourea under
the experimental conditions used, e.g., Zn2+, Co2*, and Ni2*; (2) elements which form
thiourea complexes, but are not retained or only partially retained with TBP-loaded
97
10
<
o
o
X
o
CJ
5 10 15
Au-COMPLEX IN AQ PHASE
FIGURE 56. Sorption isotherm of the gold thiourea complex

on TBP-loaded polyurethane foam. (From Braun, T. and
Farag, A. B., Anal. Chim. Acta, 65, 115, 1973. With permis-
sion.)
foam, e.g., Cu 2+ , Fe3+, and Sb3*; and (3) elements which form stable thiourea com-
plexes which are strongly retained by the loaded foam sorbent, e.g., Pd2*, Bi3*, and
Ag+.
Zinc(II), iron(III), and bismuth(III) were selected to be representative of a variety of
elements, and the effect of these elements on the rate of extraction of the gold-thiourea
complex was tested. Generally, the rate of extraction of the gold-complex was quite
fast and not effected considerably by the presence of these elements. The half-lives of
sorption of gold-thiourea complex alone and in the presence of Zn2*, Fe3*, or Bi3* were
found to be 0.4, 0.6, 1.0, and 0.9 min, respectively.
In column experiments using the undiluted TBP solution in loading the foam, the
efficiency of extraction of 10 \t% gold from 100 ml of 0.1 M perchloric acid solution
containing 3 g thiourea and 1 g sodium perchlorate was not affected by the solution
flow rate up to 100 mi min"' (column diameter, 25 mm). On a short foam column (25
mm diameter, 12 cm length and containing 5 g TBP-loaded foam), trace amounts of
gold(III) could be separated from high levels of zinc(II), cobalt(II), nickel(II),
iron(III), antimony(III), copper(II), bismuth(III), and palladium(II) by sorption from
a thiourea-perchloric acid solution (Table 48) at a fast flow rate (50 to 60 ml min"1).
However, the silver-thiourea complex could not be completely removed without af-
fecting the retention of the gold complex.
A comparative batch measurement was made for the sorption capacity of gold-thi-
ourea complex on TBP-loaded and unloaded foams and also active carbon. 41 All
loaded and unloaded foams tested gave more or less similar retentions for gold and the
uptake of the gold-thiourea complex by 10 g foam was approximately equal to that of
0.2 g of active carbon. The half-life sorption of gold-thiourea complex on all foam
Table 48
SEPARATION OF GOLD FROM VARIOUS ELEMENTS
Amount (jjg) Average

Average Au %
Element Au3* inter- No. of Au "In in on the
3
Element Au (mg) fering ion det. effluent foam
— 10 — — 6 1.60 98.40
Zn 2 * 10 1000 1:105 5 2.30 97.70
Co2* 10 1000 1:105 5 2.86 97.14
Ni2* 10 1000 1:10S 5 2.30 97.70
Fe3* 2 200 1:10S 5 4.24 95.76
Sb3* 2 200 1:105 5 6.02 93.98
Cu2* 2 2 1:103 4 2.05 97.95
Cu2* 2 20 1:10" 4 3.07 96.93
Cu2* 2 200 1:105 5 11.38 88.62
Bi3* 2 10 1:5 -10 3 5 2.34 97.66
Pd2* 2 10 1:5 -103 5 2.40 97.60
From Braun, T. and Farag, A. B., Anal. Chim. Acta, 65, 115, 1973. With per-
mission.
samples tested (polyether and polyester) was between 0.4 to 1.0 and 1.5 to 2.0 min for
loaded and unloaded foams, respectively. The rate of gold sorption on active carbon
was very close to that of loaded foam (0.6 min ± 5%).
The separation of iron(III) from cobalt(II), copper(II), or nickel(II) has been inves-
tigated by reversed-phase foam chromatography in a TBP-HC1 system.155 Cobalt(II),
copper(II) and nickel(II) ions are not retained by the foam column and move with the
solvent front. Their elutions were completed with 5 M hydrochloric acid solution at a
flow rate of 1 mi min"1 (column diameter, 20 mm). Elution of iron(III) was then
carried out with 0.01 M hydrochloric acid. In view of the results obtained, cobalt(II),
copper(II), and nickel(II) cannot be separated from each other using this system.
The separation of iron and cobalt was studied in more detail as it was considered to
be of special practical importance. Carrier-free 59Fe isotope could be separated from
cobalt target material, used in its preparation, by the proposed reversed phase foam
chromatographic system.
From the mechanistic point of view the retention of iron, cobalt, and copper from
hydrochloric acid medium by TBP-loaded foam is quite similar to the liquid-liquid
extraction process. The distribution ratios and the optimal acid concentration for each
of aqueous-TBP (liquid) and aqueous-TBP (foam) systems are not significantly differ-
ent (Figure 57).
Furthermore, loaded and unloaded polyurethane foams behave differently during
the extraction of palladium and gold-thiourea complexes. The palladium-complex, for
example, which is completely retained by both loaded and unloaded foam columns,
was quantitatively eluted from the TBP-loaded foam columns by 100 ml water; similar
to the behavior in liquid-liquid extraction of palladium in a TBP-perchloric acid-thi-
ourea system. In contrast, the palladium complex which is retained on the unloaded
foam column is not eluted completely even by using 300 ml of water.41
Polyurethane foams loaded with methyl isobutyl ketone, diethylether, isopropyl
ether or ethyl acetate have been tested for the retention of gold(III) from aqueous
chloride medium.14 Using a short foam column it was possible to collect gold traces
(0.06 to 25 ppm) by percolating the aqueous solution (200 ml) through the column at
30 to 40 mi min"1 (column diameter, 20 mm). Gold(III) chloride was completely
DISTRIBUTION RATIO
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66
Table 49
UPTAKE OF GOLD BY DIFFERENT TREATED FOAMS
WHEN 200 ml OF SOLUTION WAS PASSED THROUGH
THE COLUMN
"8Au (0.06 ppm) Au (25 ppm)
Recovery
Solvent used for treatment Uptake (%) Uptake (%) (%)
Methyl isobuty] ketone 98.6 100 97.8

Diethyl ether 99.3 100 111.0
Isopropyl ether 99.1 100 101.8
Ethyl acetate 99.5 100 100.4
From Sukiman, S., Radiochem. Radioanal. Lett., 18, 129, 1974. With permis-
sion.
stripped from the foam column with 20 to 50 mi acetone at 3 mjf min"1 flow rate (Table
49).
On the other hand, polyester polyurethane foams loaded with several members of
the OV series of greases, SE-30, QF-1, DECS, and DC-200, have been prepared by
soaking the foam cylinders in a 5% solution of the coating agent in a pesticide grade
solvent (e.g., ethyl acetate), followed by squeezing several times to expel air bubbles
and then drying in air. 47 - 156 Preliminary experiments showed that the recovery of the
organochlorine pesticides examined from aqueous solution is generally improved by
loading the foam material with these stationary phases. The OV greases performed
very poorly and SE-30, QF-1, and DEGS gave relatively poor recovery with aldrin and
DDT pesticides. However, DC-200 gave better than 90% recovery of all the ten pesti-
cides examined [lindane (Lin), heptachlor (Hep.), aldrin (Aid.), heptachlor epoxide
(Hep Ep), endrin (End.), dieldrin (Diel), p,p'-DDE, o,p'-DDT, p,p'-TDE and p,p'-
DDT].
Four-liter aliquots of water spiked with the tested pesticides were allowed to perco-
late through columns (20 mm diameter) packed with four loaded polyurethane foam
plugs at a flow rate of 250 mjf min"1. Pesticides remaining in the effluent solution were
extracted repeatedly with 20% acetone solution in hexane and measured by gas chro-
matography after reducing the extracts to an appropriate volume. In some experiments
pesticides retained by the foam plugs were recovered with acetone and hexane and then
determined by gas chromatography. It was noted that the glass walls of the columns
sorb about one-third of the pesticides (cf. Table 50) and therefore care must be taken
to wash the inner walls of the column carefully with the solvents used to extract the
foams.156 On flushing loaded-foam columns (which previously sorbed the examined
pesticides) with clean water, some removal of eldrin, heptachlor, aldrin, and p,p'-DDT
was noticed. However, the major environmental contaminants, dieldrin and p,p'-
DDE, were not removed. It was also reported that the uptake of the tested pesticides
from very dilute solutions (0.0125 ppb level) by the foam is not ideal, but still the
majority of them are extracted (Table 51).
The possibility of using loaded foam columns for the extraction of organochlorine
pesticides from suspensions of two different types of soil has also been examined.156
The suspensions were allowed to stand for one day then 3 t were decanted into a 4-jf
bottle and the volume was made up to 4 I. The latter solution was then allowed to
percolate through the foam column at 30 mi min"1 flow rate. The foam columns were
found to perform reasonably, but both soils have the ability to retain tightly certain
pesticides especially p,p'-DDE (Table 52).
101
Table 50
EXTRACTION OF ADDED ORGANOCHLORINE PESTICIDES FROM
DISTILLED WATER BY POROUS POLYURETHANE COATED WITH DC-200.
FOUR PLUGS ONE ON TOP OF THE OTHER IN THE COLUMN WERE USED
AND ANALYZED INDIVIDUALLY (SPIKED AT 1 PPB - 4 t WATER)
% Recovery
Plug no. Lin Hep Aid HepEp End p,p'-DDE Diel o,p'-DDT p,p'-TDE p,p'-DDT
1 60 54 53 49 63 56 59 60 66 62
2 0 2 2 3 0 2 2 0 0 0
3 0 2 1 1 0 1 2 0 0 0
4 0 1 1 1 0 0 1 0 0 0
Column walls 40 39 40 32 35 39 33 38 32 38
Total recovery 100 98 97 86 98 98 97 98 98 100
From Uthe, J. F., Reinke, J., and Gesser, H. D., Environ. Lett., 3, 117, 1972. With permission.
Table 51
EXTRACTION OF ORGANOCHLORINE PESTICIDES FROM WATER
BY POLYURETHANE COATED WITH DC-200; FOUR LITERS OF
WATER WERE USED IN EACH CASE
% Recovery
Spiking level P,P'- o,p'- P,P'- P,P'-

(ppb) Lin Hep Aid HepEp End DDE Diel DDT DDD DDT
1.0 94 97 95 99 100 99 98 99 99 100

0.05 100 87 89 100 100 96 100 95 100 96
0.0125 99 79 85 100 92 87 83 72 100 75
From Uthe, J. F., Reinke, J., and Gesser, H. D., Environ. Lett., 3, 117, 1972. With permission.
Table 52
EXTRACTION OF ADDED ORGANOCHLORINE PESTICIDES FROM
LIGHT VARFED CLAY SUSPENSIONS BY POLYURETHANE FOAM
COATED WITH DC-200
P,P- o,p- P,P- P,P-

Spike Lin Hep Aid HepEp End DDE Diel DDT TDE DDT
1.0 ppb 89 85 64 98 100 60 96 67 73 63

Bottle 5 5 9 0 0 11 3 12 6 8
Eluant 9 9 16 4 0 24 6 25 16 23
Combination 99 95 89 102 100 94 105 103 95 95
0.0125 ppb
Column 88 75 82 93 96 80 83 80 92 87
Bottle 1 1 1 0 0 7 5 5 4 8
Eluant 14 13 12 7 3 15 10 20 13 21
Combination 103 89 95 95 106 106 103 106 110 117
Note: 4 I of suspension were used in each case. All values are expressed as a percentage of the added
material.
From Uthe, J. F., Reinke, J. and Gesser, H. D., Environ. Lett., 3, 117, 1972. With permission.
Further work on the extraction of organochlorine insecticides and polychlorinated

biphenyls from water with silicone oil DC-200-loaded polyurethane foam has been
carried out. 49 A comparison was made between the extraction efficiency of the grease-
loaded and unloaded foams for ten different insecticides using six foams of different
surface areas and bulk densities. In most cases, higher recoveries were obtained when
using unloaded foams (Table 53). A detailed study was then carried out with foam
sample A which was the most efficient. The effect of flow rate on the retention of the
different insecticides on both DC-200-loaded and unloaded foam columns was deter-
mined. At flow rates of 10 and 30 m£ miir1 (column diameter, 20 mm), the unloaded
foams were found to be more efficient, whereas at a flow rate of 250 ml min"1, the
loaded ones were more efficient. For the quantitative sorption of the different orga-
nochlorine insecticides and polychlorinated biphenyls, the aqueous solution should
have a 6 to 9 pH.
Sorbed insecticides are completely recovered from the foam column by elution with
50 ml acetone followed by 100 ml of /j-hexane. The eluate is dried with anhydrous
sodium sulfate, cleaned by passage through a Florisil® column, and finally its constit-
uents are identified and measured by gas chromatography.
Polyurethane foam loaded with Dow-200 silicone oil was found to extract, to various
extents, different phthalate esters (Table 54).60 The authors confirm the conclusion of
the previously described results for the decreased sorption of organochlorine insecti-
cides by loaded foam at low flow rates, as they observed similar behavior in the case
of phthalate esters.
Polyurethane foams loaded with gas chromatogaphic stationary phases (5 to 10 wt
%), e.g., SE-30, DC-200, or a nematic liquid crystal showed a small increase (4 to 9%)
in the recovery of benzo(a)pyrene over unloaded foam at a temperature of 62 ± 2°C
(Table 55).56 However, eluates from coated foam columns were found to contain large
amounts of the loading material which makes its concentration to smaller volumes
quite difficult.
b. Collection from Gaseous Media

Polyurethane foams loaded with silicone oils have also been tried for the collection
of various polychlorinated biphenyls in gaseous media using suitable high-volume air
samplers. In contrast to the noticed improvements of the sorption capabilities of po-
lyurethane foams to some organochlorine insecticides from aqueous solution by load-
ing the foam with silicone oils, the application of these loaded foams to the collection
of the above-mentioned pesticides from gaseous media does not offer any advantage.81
Doskey and Andren 86 reported decreased retention efficiencies of foams loaded with
DC-200 in the collection of some organochlorine insecticides from gaseous media.
Consequently, the use of unloaded foams is generally recommended for collections
from gaseous media.
2. Foams Loaded with Hydrophobic Chelating Reagents

Many hydrophobic chelating reagents have been physically immobilized by loading
on polyurethane foams. The reagent foams produced were successfully employed in
several separation and preconcentration processes. The foams combine both the selec-
tivity of the chelating reagent and the advantageous rapidity of kinetic processes be-
tween metal ions in aqueous solution and the reagent immobilized in the foam mem-
branes. This, together with the advantageous hydrodynamic properties of columns
packed with foam sorbents, yields fast separation and preconcentration of trace ele-
ments on such reagent foam columns. Reagent foams are prepared by two general
methods. The first is based on dissolving an appropriate amount of chelating agent in
a nonvolatile organic solvent (usually a plasticizer) and physically immobilizing the
103
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Table 54
RECOVERY OF
PHTHALATE ESTERS ON
FOAM COATED WITH 5 MG
OF DOW-200 SILICONE OIL
PER PLUG
Phthalate Recovery (%)
Dimethyl phthalate 13
(DMP)
Diethyl phthalate 70
(DEP)
Di-n-butyl phthalate 98
(DnBP)
Diamyl phthalate 49
(DAP)
Di-n-octyl phthalate 9.0
(OOP)
Butylbenzyl phthalate 74
(BBP)
From Gough, K. M. and Gesser, H. D.,

J. Chromatogr., 115, 383, 1975. With
permission.
Table 55
BENZO(A)PYRENE RETENTION FROM TAP WATER
WITH FOAM PLUGS COATED WITH
CHROMATOGRAPHIC PHASES"
Temp of
Cone of coated spiked % Reten-
on plug wt % water tion on
Chromatographic phase of foam foam
Uncoated 23 62.0
Uncoated 62 85.3
DC-200 5 62 87.5
DC-200 10 62 92.6
SE-30 10 62 91.2
Nematic liquid crystal 3.7 23 66.0
[N,N'-bis(p-methoxy-
benzylidine)-a,a'-bi-p-
toluidine]
Water volume, 4 I; flow rate, 250 mf min"' ± 10 ml; BaP cone 0.1 ppb.
From Saxena, J., Kozuchowski, J., and Basu, D. K., Environ. Sci. Tech-
nol, 11, 682, 1977. With permission.
solution on polyurethane foam, as described previously. The second method is based

on dissolving the chelating agent in a volatile organic solvent and after allowing the
foam material to swell in the latter, the solvent is gradually vaporized by gentle heating.
Evidently, the reagent foam prepared by the second method contains the chelating
agent as finely divided particles homogeneously distributed in the foam matrix. In both
methods, it is necessary to use solvents in which the chelating reagents are soluble. This
requirement is easily fulfilled in the second method owing to the wide range of volatile
105
solvents that can be employed. Solvents suitable for the first method are relatively
limited, as they have to play a dual purpose;158 they have to act as efficient nonvolatile
solvents for the chelating agents in question as well as plasticizers for the plastic foam
itself. Plasticizers are defined as essentially nonvolatile liquids used to modify synthetic
polymers. They do not chemically react with the polymers, but modify them through
the reduction of Van der Waals forces. The plasticized polymer is a dynamic system in
which individual plasticizer molecules have a varying degree of mobility within the
polymer matrix. Consequently, it was suggested that the application of plasticizers
could increase the permeability of the foam material which will enhance the rate of
sorption of metal ions from aqueous solution on the plasticized reagent foams. 158 This
was proved practically as will be described latter.
The plasticizers employed in plasticized reagent foam preparation include, TBP, a-
di-n-nonylphthalate, di-n-octylphthalate, dibutyl adipate, and some tertiary amines.
a. Dithizone Foam
Polyurethane foams immobilizing dithizone have been employed for the collection
of silver158 and mercury(II) 159 161 ions, and also methylmercury(II) chloride160 using
batch, column, and pulsated column methods. Zinc dithizonate was used instead of
dithizone alone as the latter is known to be chemically unstable and its instability is
enhanced when loaded on the foam. 158159
In batch experiments the collection rates of traces of silver and mercury have been
determined for plasticized and unplasticized dithizone foams. Both metal ions were
measured radiometrically in the aqueous solution. The collection rates with the plasti-
cized zinc dithizonate foams are generally better than with the unplasticized ones. Fig-
ures 58 and 59 show the effect of plasticizer on the rate of collection of silver and
mercury, respectively. Silver can be extracted from acidic and neutral aqueous solu-
tions on the reagent foam, but the rate of extraction from aqueous solutions of pH 4.5
to 6.5 is higher than that from more acidic solutions. Mercury is quantitatively ex-
tracted even from 2 M nitric acid solutions, but again the rate of extraction from
neutral aqueous solutions (pH ~ 6) is faster than from acidic media.
Silver and mercury were successfully recovered from the plasticized foam in batch
experiments by shaking with sodium thiosulfate solution. The optimum dithizonate
concentration of the loading solution is about 4 x 10~3 M.
Using short foam columns (1 cm diameter) packed with 1 g plasticized zinc dithizon-
ate foam (loaded with 1% zinc dithizonate solution), the breakthrough and overall
capacities were determined by allowing silver or mercury solution, containing 100 ^g
metal ion ml" 1 , to percolate through the foam column at 2 mi mm'1 flow rate. For
silver, the breakthrough and overall capacities were 11.6 and 18.5 peq g"1, respectively;
for mercury, they were 11 and 22.3 /êq g'1. Figure 60 shows, for example, the break-
through curve of silver. It was reported159 that breakthrough and overall capacities are
significantly decreased by washing the plasticized foam column with 1 I of distilled
water before capacity determination. However, the measured capacities are still higher
than those reported for other dithizone loaded granular supports.162-163
The separation of silver from a wide range of relative concentrations of lead and
copper was investigated using batch mode collection. Complete collection of silver was
obtained in the presence of as high as six orders of magnitude of lead (Table 56) but in
the case of copper, low recoveries were observed using the straight forward method.
The addition of a masking agent, e.g., EDTA, yielded a quantitative separation of
silver from copper even in the presence of a high excess of the latter (Table 56).
The preconcentration of small amounts of silver (1 pigl"1) and mercury (0.72 ^g!~')
has successfully been achieved by percolating the aqueous metal ion solution through
100 r--~
o
o
<
30
TIME (minutes)
FIGURE 58. Effect of shaking time on the sorption of silver by polyu-

rethane foam loaded with zinc dithizonate in various plasticizers and
chloroform. The loaded foam contained in each case 1% zinc dithizonate,
in (a) CHC13; (b) di-n-octylphthalate; (c) TBP; and (d) a-di-n-nonyl-
phthalate. (From Braun, T. and Farag, A. B., Anal. Chim. Acta, 69, 85,
20 30
TIME (minutes)
FIGURE 59. Effect of plasticizer on the sorption rate of mercury (II),

(a) TBP, (b) dibutyl adipate, (c) a-dinonyl phthalate, (d) di-n-octyl
phthalate, (e) CC14, (0 CHC13, (*) TBP-loaded foam alone (in the absence
of dithizone). (From Braun, T. and Farag, A. B., Anal. Chim. Acta, 71,
107
100
LLJ 50
x
10 20 30 40 50
EFFLUENT (ml)
FIGURE 60. Breakthrough curve for silver on a column of zinc

dithizonate foam. (From Braun, T. and Farag, A. B., Anal. Chim.
Acts, 69, 85, 1974. With permission.)
Table 56
COLLECTION OF TRACES OF SILVER IN THE
PRESENCE OF VARIOUS CONCENTRATIONS OF
LEAD AND COPPER
Amount Average
Ag in Ag* in acj Average Ag
Ag* Matrix matrix soln° on foam
Matrix (MB) (mg) (ppm) (%) (%)
H2O 100 10 0.7 99.3

H2O 1 0.1 1.4 98.6
—
H20 0.01 0.001 1.2 98.8
—
H;O Carrier-free — — 1.9 98.1
Cu2* 0.01 0.1 100 1.6 98.4
Cu" 0.01 1.0 10 2.2 97.8
Cu2' 0.01 10.0 1 2.5 97.5
Cu2* Carrier-free 1.0 — 2.0 98.0
Pb2* 0.01 0.1 100 2.3 97.7
Pb2* 0.01 1.0 10 1.8 98.2
Pb2* 0.01 10.0 1 2.9 97.1
Pb2* Carrier-free 1.0 — 0.8 99.2
• Average of 4 determinations.
From Braun, T. and Farag, A. B., Anal. Chim. Acta, 69, 85, 1974. With
permission.
a plasticized foam column at a flow rate of 50 to 60 ml miir1 (column diameter 25

mm, packed with 5 g loaded foam).
Polyurethane foam immobilizing solid dithizone reagent (i.e., prepared by the sec-
Table 57
EFFECT OF CONCENTRATION ON
EXTRACTION OF MERCURY
Compound Cone of Extracted by pHof

sample foam (%) sample
HgCl 2 0.002 ppb 98.4 5.5

HgCl2 4 ppb 98.5 5.5
HgCI2 40 ppb 99.1 5.5
HgCU 400 ppb 97.2 5.5
HgCl2 4 ppm 99.7 5.5
HgCl2 40 ppm 62.3 5.5
HgCl2 400 ppm 33.4 5.5
CH 3 HgCl 10 ppb 99.7 .3
CH 3 HgCl 100 ppb 99.7 .3
CH 3 HgCl 500 ppb 99.9 .3
CH3HgCl 1 ppm 100.0 .3
CH 3 HgCl 5 ppm 93.0 .3
CH 3 HgCl 10 ppm 98.9 .3
CH 3 HgCl 5 ppm 93.5 5.5
CH 3 HgCl 10 ppm 94.3 5.5
CH3HgCl 0.2 ppb 98.2 1.3
CH3HgCl 0.002 ppb 99.2 1.3
CH 3 HgCl 0.2 ppb 99.3 5.5
CHjHgCl 0.002 ppb 99.4 5.5
From Chow, A. and Buksak, D., Can. J. Chem., 53,

ond method using dithizone solution in acetone) has been tested for the collection of
mercury(II) and methylmercury(II)chloride from aqueous media. 160 The effect of ac-
idity on the extraction of both mercury compounds by dithizone foam columns has
been evaluated using 100 ml samples at flow rates of 1 and 3 mjf miiT1 (column diam-
eter, 20 mm). In both cases, mercury is retained efficiently on the foam column. Mer-
cury(II)chloride was extracted efficiently from aqueous solutions at pH values of about
5 to 10, while methylmercury(II)chloride is best extracted at pH 1.2. The extraction of
both mercury compounds in a wide range of concentrations has been investigated in
column mode experiments. As is clear from the results of Table 57, both merucry
compounds are quantitatively collected by the foam column up to a concentration of
5 to 10 ppm. At higher concentrations, however, the results were less satisfactory.
The mercury(II) ions and methylmercury(II)chloride were found to be firmly re-
tained on the reagent foam columns.160 Additional water (400 mi) washing only re-
moved 0.1% mercury. Mercury could, however, be quantitatively removed from the
foams simply by eluting with 100 mi of acetone. This procedure removed both the
dithizone and the mercury dithizonate simultaneously. Mercury in natural samples,
containing calcium, magnesium, aluminum, iron, zinc, chromium, lead, copper, man-
ganese, nickel, silver, lithium, and bismuth (of which the first four were above 1 ppm
level) and spiked with 0.002 ppb mercury(II) and methylmercury(II)chloride was suc-
cessfully collected by the dithizone foam column (Table 58).
The collection of mercury(II) from aqueous solutions by a pulsating column packed
with zinc dithizonate foams has also been examined.161 Closed and open pulsating
column arrangements were considered. In the open arrangement (Figure 9) each frac-
tion taken from the sample into the syringe on the upstroke (2) is rejected on the
downstroke (3) to the waste and the process is repeated with further fresh fractions of
sample. In the closed arrangement the syringe content is returned to the bulk sample
109
Table 58
EXTRACTION OF MERCURY FROM
VARIOUS MATRICES
Compound Matrix pH Extraction (%)
HgCl2 Double-distilled H2O 5.5 97.1

Double-distilled H2O 3.8 96.0
Tap H2O 6.5 88.5
Tap H2O 7.2 70.4
Tap H2O 1.3 98.3
River H 2 O° 8.1 78.7
River H 2 O 1.3 84.3
Raw sewage 6.9 63.7
Raw sewage 1.2 77.8
Treated sewage 7.4 71.1
CH 3 HgCl Double-distilled H2O 5.5 97.8
Tap H 2 O 6.5 89.9
Tap H2O 7.2 96.9
Tap H2O 1.3 97.1
River H2O° 8.1 94.2
River H2O 1.3 99.2
Raw sewage 6.9 95.2
Raw sewage 1.2 98.8
" Water taken from shoreline of Red River inside Winnipeg,

Manitoba, Canada.
From Chow, A. and Buksak, D., Can. J. Chem., 53, 1373,
many times. In both cases, separation is performed by repeating the inflow/outflow

cycle and each single cycle constitutes one pulse. In the open arrangement the extrac-
tion efficiency (£„„,„) is related to the distribution ratio (KD), number of pulses (n) and
the maximum volume concentration (p) (p = W 0 /V P , where W0 is the total sample
volume and V p is the compressed foam volume) by the equation:
"K" - ' (20)

nK D .
and similarly for the closed system by

F / (r\ — M K \ n ~|
n cl (21)
- p + K,, L \P + nK,,
Polyurethane foam cylinders impregnated with a CC14 solution of zinc dithizonate

with or without adding TBP (plasticizer) were used in pulsated column experiments.
The separation efficiency was generally increased by increasing the number of pulses.
Plasticized foams required a smaller number of pulsations (five pulsations) to reach
equilibrium values than unplasticized ones (ten pulsations). The results presented in
Table 59 show a comparison between the theoretical and the experimental efficiency
of mercury separation from various volumes of aqueous solution in the open arrange-
ment. The experimental values obtained by TBP plasticized zinc dithizonate foam
show closer agreement with the theoretical (calculated) ones.
Table 59
THEORETICAL (E,) AND
EXPERIMENTAL (E.) EFFICIENCY
OF 203Hg SEPARATION FROM
VARIOUS VOLUMES OF AQUEOUS
P H A S E (W0) I N T H E O P E N
ARRANGEMENT
Separation efficiency "fo, for
foam loaded with:
No. of Zn (HDZ)2 +
20m* Zn (HD)2 TBP
fractions W0
(n) ml E, E. E, E.
5 100 98.8 93.4 99.7 97.2

10 200 97.8 93.4 99.5 97.8
15 300 96.9 93.2 99.2 98.0
20 400 95.9 93.2 99.0 97.7
25 500 95.0 93.1 98.1 98.7
From Braun, T. and Palagyi, S., Anal. Chem., 51,

Several organic solvents have been examined for the recovery of the sorbed mercury
by the pulsated column method (Table 60). With the exception of methanol, all the
solvents tested gave quantitative elution.
It was also reported50 that cadmium and lead can be collected at pH 9 by a dithizone
foam column at 5 ml min"1 flow rate. Both metal ions can be recovered from the foam
column with a 4 Mnitric acid solution.
b. Diethyldithiocarbamate Foam
The possibility of using zinc diethyldithiocarbamate-foam (ZnDDC) for the collec-
tion of mercury(II) from aqueous solution (pH ~ 6) has also been reported.159 Quan-
titative and rapid collection of mercury from aqueous solutions (containing 0.72 ^g)
was possible using TBP-plasticized ZnDDC foam in batch experiments. More than
97% of mercury was collected after ~10 min shaking.
Braun and Farag164 indicated that sodium diethyldithiocarbamate is unsuitable for
the preparation of plasticized DDC-foam owing to its chemical instability and low
solubility in most nonvolatile organic solvents. Although the use of zinc foam of DDC
offers a solution to this problem, the diethylammonium form is more soluble in or-
ganic solvents and consequently it is recommended for the preparation of plasticized
DDC-foams. However, Valente and Bowen'65 employed NaDDC for loading the foam
material as saturated carbon tetrachloride solution (5% m/V). The unplasticized DDC
foam produced was found to immobilize loosely most of the NaDDC and only about
4% of the reagent is more strongly loaded.
The collection of cobalt (1 ppb) from aqueous solutions by TBP-plasticized diethy-
lammonium DDC foam was found to be pH-dependent.1" The collection is quite com-
plete from aqueous solutions of pH 4.5 to 5.5. Quantitative and fast collection of trace
amounts of cobalt were obtained in column operations using a short foam column (25
mm diameter, packed with 2 g plasticized foam) at a flow rate of 50 to 60 mi min"1.
A method for the separation of antimony(III) from antimony(V) using unplasticized
DDC-foam has been described using batch and column modes of extraction."5 At pH
9.5 antimony(III) is completely extracted while antimony(V) is not. The rate of reten-
Ill
Table 60
ELUTION OF 203Hg FROM FOAM
FILLINGS LOADED WITH
Zn(HDZ)z + TBP (FIVE
PULSATIONS FOR EACH
ALIQUOT
No. of 5-mt Elution

Solvent aliquots efficiency (%)
Methanol 10 78
Chloroform 5 100
Toluene 5 98
10 99
Acetone 5 98
10 100
From Braun, T. and Palagyi, S., Anal. Chem.,

Table 61
EFFECT OF pH ON THE SEPARATION OF
ANTIMONY (HI) FROM ANTIMONY (V) IN FOUR
TYPES OF WATER
Retention on foam (%)
Water pH Antimony (III) Antimony (V)
Distilled water 7.5 100 0.5

8.5 100 0
9.5 100 0
Treated sewage effluent 7.5 80 0
8.5 84 0.5
9.5 99 0
Sea water 7.5 96 0
8.5 99 0
9.5 98 0
Lake water 7.5 98 0.2
8.5 100 0
9.5 99 0
Note: Batch experiment in presence of excess of NaDDC; 30 min

shaking.
From Valente, I. and Bowen, H. J. M., Analyst, 102, 842, 1977.

With permission.
tion of antimony(III) is quite fast, the percentage of extraction reaching 100% after
about 15 min shaking. In batch experiments, antimony(III) was separated from anti-
mony(V) in four types of natural waters after adjusting their pH to 9.5 and adding a
sufficient amount of the solid NaDDC reagent (Table 61). The presence of arsenic(III),
tin(II), and zinc does not cause any interference as their DDC complexes are not sorbed
Table 62
EFFECT OF FLOW RATE ON THE EXTRACTION
EFFICIENCY OF MERCURY (II),
METHYLMERCURY AND PHENYLMERCURY
IONS AT pH 2 WITH PLASTICIZED DDC-FOAM
Confidence
Cone Flow rate E" Standard limit
Ion (fig I'1) (ml min"1) (%) deviation (± ts n"2)
Hg2* 20 50 99.4 0.2 ± 0.2

120 97.2 0.6 ±0.7
CH3Hg* 20 50 99.1 0.3 ±0.4
100 84.2 3.0 ± 3.8
PhHg* 100 7 99.7 0.1 ±0.1
50 97.0 1.2 ± 3 .1
Note: a-Dinonyl phthalate (0.25 ml g"1) was used as plasticizer.
Each result is the mean of five determinations.
From Braun, T., Abbas, M. N., Bakos, L., and Elek, A., Anal. Chim.
Acta, 131, 311, 1981. With permission.
on the foam. However, some other ions, e.g., silver, cadmium, iron(III), and mer-
cury(II) are largely sorbed, but the addition of EDTA to the aqueous solution prevents
the sorption of cadmium and iron(III). The application of the unplasticized DDC'foam
for the same separation in column operation has also been reported using a flow rate
of 5 ml min"1 (column diameter, 20 mm). The foam becomes saturated at antimony
concentrations of 130 mg g"1 foam. In both static and dynamic systems, antimony is
recovered from the foam with acetone and measured by atomic absorption spectrom-
etry or neutron activation analysis.
Antimony, indium, and mercury at parts per billion concentration levels have also
been preconcentrated using DDC-loaded polyester polyurethane foam in batch exper-
iments.31 In this case, 20 to 50 ml of the sample solution, containing a suitable concen-
tration of the element to be determined and adjusted to pH 2, were shaken with DDC-
polyester-foam for 1 hr. The foam was then squeezed to dryness and packed into pure
polyethylene capsules for irradiation for 5 or 10 min in the pneumatic tube system of
the reactor at a neutron flux of 3.1013 n-cm^-s" 1 . Under these conditions indium and
mercury were quantitatively collected by the reagent foam, while the percentage of
antimony collected was only 70%.
Braun et al.166 suggested the use of plasticized diethylammonium DDC foam for the
preconcentration of mercury(II), methylmercury(II), and phenylmercury(II) com-
pounds from natural waters. The extraction of mercury(II) ions was found to be quan-
titative over a wide pH range (0.5 to 8) using the column mode of extraction at 50 ml
min"1 flow rate (column diameter, 25 mm). A pH of ~2 was chosen because at this pH
organomercurials are also completely extracted. Using plasticized DDC foam columns,
flow rates up to 120 ml min"1 could be achieved without affecting the retention of
trace amounts of the inorganic mercury compound. The unplasticized DDC foam col-
umns gave lower retention efficiencies. The extraction rate of organomercurials is
slower than that of inorganic mercury(II) compounds (Table 62).
The collection of inorganic mercury and organomercurials (1 ng I"' level) from tap
water and water containing NaCl was found to be quantitative at a flow rate of 50 ml
min"1 (Table 63).166 It was indicated that mercury is firmly held on the DDC foam; i.e.,
113
Table 63
EXTRACTION OF MERCURY (II),
METHYLMERCURY, AND PHENYLMERCURY
IONS ADDED TO TAP WATER AND 0.5 MNaCl
SOLUTION AT pH 2 WITH PLASTICIZED DDC-
FOAM FOR FLOW RATES OF 50 Ml Min'1
Confidence
Concn E° Std. limit
Sample Ion (^g 1~') (%) dev. (± ts n""2)
Tap water Hg2* 2 99.4 0.3 ± 0,4

CH3Hg* 2 99.5 0.2 ± 0.3
PhHg* 10 96.4 1.2 ±1.5
0.5 MNaCl Hg2* 2 99.3 0.1 ±0.1
Each result is a mean of five determinations.
Braun, T., Abbas, M. N., Bakos, L., and Elek, A., Anal. Chim. Acta,
less than 0.3% of the total amount retained is leached by percolating 1 I of water
through the column. Inorganic mercury, organomercurials and the reagent itself are
completely eluted from the foam column with 100 ml of acetone.
c. l-Nitroso-2-Naphthol Foam
The collection of cobalt(II) from aqueous solution on plasticized l-nitroso-2-naph-
thol foam has been reported at an optimal pH value of 6.6 to 9.0 (Figure 61).1M The
rate of extraction of cobalt on this reagent foam is quite fast. Cobalt concentrations
ranging between 1 and 1000 /^g were quantitatively collected from aqueous solution
(pH 6.8) at a flow rate of 50 to 60 ml mirr1 (column diameter, 25 mm, packed with 2
g plasticized reagent foam).
d. Benzoylacetone Foam
Benzoylacetone-loaded polyurethane foam has been prepared by soaking the washed
and dried foam in an acetone solution of benzoylacetone followed by vacuum
drying. 167 The produced reagent foam was tested for the extraction and separation of
copper and cadmium. The extraction of both metal ions is pH-dependent and their
extraction curves are quite similar to those of the liquid-liquid extraction system. Table
64 shows the effect of flow rate on the completeness of the extraction of copper and
cadmium. Recovery of both ions from the reagent foam columns was successfully ac-
complished using 1.5 M hydrochloric acid solution.
The separation of copper and cadmium was possible with consecutive reagent foam
plugs. When the solution is adjusted to pH 4.86 and extracted with 5 foam plugs, 99.8
± 0.2% of copper is collected together with less than 1.0 /^g of cadmium. However,
separation in a dynamic system utilizing the pH-dependency of the extraction curves
was found to be less effective.
e. Dimethylglyoxime Foam
Polyurethane foams immobilizing dimethylglyoxime (DMG) have been prepared by
shaking the foam material with a solution of DMG in acetone for about 1 hr. 168 The
treated foam is squeezed first between sheets of filter paper to remove excess reagent
solution then dried under vacuum at room temperature to remove acetone. It was
100
o
LLJ
50
O
o
o
O
10
PH
FIGURE 61. Effect of pH on the sorption of cobalt (II) with TBP-

plasticized l-nitroso-2-naphthol foam. (From Braun, T. and Farag,
A. B., Anal. Chim. Acta, 76, 107, 1975. With permission.)
Table 64
EXTRACTION OF COPPER AND CADMIUM
BY BENZOYLACETONE-TREATED
POLYURETHANE FOAM
Flow rate AmtCu AmtCd

(ml extracted % Cu extracted % Cd
min-)- (eg)* extracted* (eg)' extracted1
1.5 175.5 100 174.4 99.4

2.0 175.5 100 — —
3.0 175.5 100 174.1 99.2
6.0 170.5 97.2 174.1 99.2
12 158.5 90.4 174.1 99.2
18 152.5 87.0 174.1 99.2
!50 123.5 70.4 160.1 91.2
• The column diameter was 40 mm.

' At pH 8.0.
' At pH 10.5.
From Lypka, G. N., Gesser, H. D., and Chow, A., Anal. Chim.
reported that in this unplasticized DMG-foam the major part of the reagent is impreg-
nated in the foam membrane as a solid solution of DMG in polyurethane, while some
of it may be chemically bonded to the polyurethane molecules, e.g., covalent bonding
between DMG and the foam polyol and urethane bonds. The optimal pH for the ex-
traction of nickel is in the range 8 to 10, but quantitative extraction is possible from
solutions of slightly lower or higher pH too, if the reagent foam contains excess DMG.
115
Table 65
EFFECT OF FOREIGN IONS ON THE SORPTION OF
Ni (II) BY DMG-TREATED FOAM"
Foreign ion Ni (II)
pH of Added Added Adsorbed Ratio of

Medium Ion (jig) 0*g) (%) Ni (II) to ion
8.1 Fe(II) 50 100 100 1:0.5

8.8 Fe(II) 100 100 98.5 1:1
8.5 Fe (II) 200 100 97.3 1:2
8.3 Fe (III) 200 100 100 1:2
7.7 Fe (III) 400 100 99.3 1:4
8.5 Cd (II) 200 100 99.2 1:2
8.5 Zn (II) 200 50 100 1:4
8.5 Cu (II) 100 50 100 1:2
8.5 Cu (II) 150 50 99.5 1:3
8.5 Co (II) 30 50 100 1:0.6
8.5 Co (II) 50 50 72.5 1:1
8.5 Co (II) 100 100 92.0' 1:1
8.5 Co (II) 200 100 90.0' 1:2
° Content of DMG on the treated foam: 5.8 x 10~2 mmol g"' foam; Me-
dium: 15.0 ~ 20.0 ml of 0.1 MNH«C1-NH 4 OH buffer; Foam taken:
ca. 50 ~ 90 mg
* The values determined with the treated foam containing DMG of 6.8 x
10"' mmol g~' foam.
From Lee, D. W. and Halmann, M., Anal. Chem., 48, 2214, 1976. With
permission.
However, in strongly alkaline solutions (pH ~ 11) the amount of nickel extracted is
significantly decreased.
It was reported that nickel reacts immediately with the DMG loaded on the foam to
form a pink colored complex, but the latter takes some time (30 min) to be held quan-
titatively on the foam. Consequently, shaking for 1 hr was chosen to ensure complete
sorption. From the mechanistic point of view, it was suggested that nickel in solution
reacts first with DMG released from the loaded foam to form insoluble Ni(II)-DMG
colloidal particles. The latter are sorbed by the foam and diffuse into the foam to form
a complex with the foam matrix. This mechanism was confirmed by the capability of
the untreated polyurethane foam to sorb Ni(II)-DMG colloidal particles from aqueous
solution producing a clear solution. This is considered to be a selective process as silver
chloride or ferrous hydroxide colloidal particles are not sorbed by the unloaded polyu-
rethane foam. Contrariwise, Ni(II)-salicylaldoxime and Cu(II)-salicylaldoxime colloi-
dal particles are sorbed by the unloaded foam. The extraction of Ni(II) by the DMG-
foam is unaffected by temperature in the range 20 to 60°C.
The mole ratio of Ni(II):DMG in the foam was found to be 1:2.6,16B which is smaller
than the theoretical ratio for Ni(DMG)2 complex (1:2). Therefore it seems that a part
of DMG in the foam is unavailable for the reaction with nickel. Separation of low
concentrations of nickel(II) (~5 ppm) on DMG-foam was found to be possible by both
static and dynamic methods. A mixture of 1 MHC1 and ethanol (1:1) was successfully
employed for the recovery of nickel from the reagent foam. In retention and elution
processes a flow rate of less than 1 ml min"1 (column diameter 15 mm) was used. The
presence of iron(III), zinc(II), cadmium(II), iron(II), and copper(II) ions did not affect
nickel retention by the DMG-foam (Table 65). Cobalt(II) interferes seriously, but its
60 90 120 150 180

SHAKING TIME (minutes)
FIGURE 62. Effect of time on the sorption of nickel on loaded polyurethane foams
at room temperature, (a) DMG-TBP: 3% DMG-TBP foam (100 mg), 900 ^g Ni 15 ml''
solution; (b) DMG: 9.3 x 10~s mmol DMG g"1 foam taken, 200 Mg Ni 13 mjT' solution;
(c) benzildioxime-TBP: 1.5% benzildioxime-TBP foam (100 mg), 900 ^g Ni 15 mr 1
solution; (d) benzildioxime: 1.2 x 10"4 mmol benzildioxime g"1 foam (60 mg), 400 ng Ni
20 mr 1 solution. (From Halmann, M. and Lee, D. W., Anal. Chim. Acta, 113, 383,
effect is completely eliminated by using a foam containing higher DMG-content (more

than 10"' Mmol DMG g~' foam). It is worth mentioning that DMG-foam having 6.8 x
10"' Mmol DMG g"1 can be prepared using saturated DMG-acetone solution for foam
loading. The expected capacity of this foam would be about 2.5 x IQ-' Mmol Ni(II)
g"1 which is about 50 times larger than the reported value with DMG-treated silicone
rubber foam (ca. S.KT3 Mmol Pd g-' foam). 169
/. a-Benzildioxime Foam
The main drawback of the DMG-loaded foam is that ca. 90% of the reagent is
removed from the foam during one elution step. TBP-plasticized DMG-foam was
suggested170 "' to solve this problem and also to improve the separation of nickel.
TBP-plasticized a-benzildioxime and 1,2-cyclohexanedione dioxime foams were also
prepared and critically evaluated for the extraction and separation of nickel. It was
reported that the addition of TBP plasticizer improves the performance of the reagent
foam. This is in agreement with the previously described conclusions with other reagent
foams. 158159164 Figure 62 shows that the fastest equilibration is achieved with the TBP-
plasticized DMG-foam and the slowest with the unplasticized benzildioxime-foam.
Sorption of nickel(II) on different TBP-plasticized dioxime foams is optimal at pH 9
to 10. In all cases 1 to 2 MHC1 was used for the recovery of nickel(II).
The retention of nickel(II) from aqueous alkaline solution by the dioxime loaded
foams was unaffected by the presence of the following ions and chelating agents:
Cu(II), Cd(II), Fe(II), Co(II), citrate, tartarate, and EDTA. In the presence of cyanide
ion, the sorption decreases.171
g. 1,2-Ethanedithiol Foam
Polyurethane foam loaded with a 1% solution of 1,2-ethanedithiol in benzene has
been examined for separation and preconcentration of antimony from natural
117
Table 66
INVESTIGATION OF SELECTIVITY
OF RETENTION ON LOADED
POLYURETHANE FOAM
Amount added to 50 ml % Extracted

Element water sample (mg) by foam
"Na 0.14 0
82
Br 0.04 0
203
Hg 8 x 10-3 82.0
"Zn 0.5 0
"3Sn 5 0
'0'Cd 0.2 0
"As 0.07 97.9
From Valente, I. and Bowen, H. J. M., Anal. Chim.

waters.172 Both antimony(III) and (V) were found to be sorbed from distilled, river and
sea water independently of their oxidation state and type of water used. In batch mode
extraction, 50 and 95% of antimony were sorbed after 1 and 3 min shaking, respec-
tively.
More than 97% antimony was extracted from aqueous solution at pH between 1 and
2.5. Above pH 4, the percentage sorbed sharply decreased. The sorption isotherm of
antimony measured at pH 1 was found to be linear over a wide range of antimony
concentrations. The formula of the extracted species was suggested to be Sb
(CH 2 -CH 2 -S 2 )C1. 172
The collection of traces of antimony (6 ^g Sbf"') on ethanedithiol-foam columns was
successfully carried out at a flow rate of 5 ml min"1 (column diameter, 15 mm). Anti-
mony was recovered from the foam columns with acetone at 1 ml min"1 flow rate.
The presence of sodium, zinc, cadmium, and bromine ions does not affect the col-
lection of antimony as they are not sorbed by the ethanedithiol-foam. However, mer-
cury and arsenic ions are quantitatively retained. No trials were made to separate these
metal ions from antimony. Table 66 shows the sorption of a series of elements in
solution at pH 1 by the reagent-foam.
h. Pyridylazo-Naphthol Foam
Plasticized and unplasticized l-(2-pyridylazo)-2-naphthol (PAN) foams have been
prepared and evaluated for the separation and extraction of cobalt(II), 24 - 172 " 175
iron(III),24 38 manganese(II),24 zinc(II),30 35•'" 17S mercury(II), 3031 ' 35 ' 173 175 copper(H),35
gold(III),31 indium(III),30 and cadmium(II) 173174 using batch and column techniques.
The collection of cobalt(II) and iron(III) from aqueous solutions by plasticized
PAN-foam was found to be quantitative over a wide pH range (4 to 9).24 Man-
ganese(II), however, is sorbed only above pH 9 (Figure 63). This behavior is the basis
for the separation of cobalt from manganese. The effect of 23 anions on the extraction
of cobalt, iron and manganese with plasticized PAN-foam has been examined.24 Cya-
nide, peroxide, periodate, and citrate mask all three metal ions, while borate, fluoride,
phosphate, and tartarate mask iron more than cobalt and have no effect on manganese
(Table 67).
The sorption rate of cobalt decreases in the order thiocyanate > oxalate, phthalate
> iodide > bromide, > nitrate, but the sorption rate of iron is highest from water. The
sorption rate of the three metal ions decreases in the order cobalt > manganese > iron.
The sorption rate of cobalt in thiocyanate medium on PAN-polyester foam is slower
FIGURE 63. Sorption of cobalt, iron, and manganese as a function of pH; (a) iron,
(b) cobalt, (c) manganese. (From Braun, T., Farag, A. B., and Maloney, M. P., Anal.
Chim. Acta, 93, 191, 1977. With permission.)
Table 67
EFFECT OF VARIOUS SALTS (0.1 M) ON THE EXTRACTION
OF COBALT, IRON, AND MANGANESE WITH PAN-FOAM
Extraction Extraction
Salts Co Fe Mn Salts Co Fe Mn
NH 4 -oxalate 98.0 98.7 98.6 Na-Acetate 85.8 97.3 97.5

KSCN 98.6 98.3 97.3 KBrO, 93.7 99.7 99.4
KH-phthalate 99.2 94.6 98.1 Na 2 SO 4 70.5 99.5 98.8
NaBr 98.0 98.5 98.6 (NH 4 ) 2 S0 4 58.6 99.2 98.9
Nal 99.0 100.0 99.1 Na 2 HPO 4 56.5 16.4 100.0
NaN0 3 98.8 99.0 98.9 KIC-3 70.2 97.1 98.5
KC1 94.4 99.2 98.4 KH-tartarate 86.2 22.0 96.1
NaCl 95.2 99.6 99.0 NaIO 4 ° 10.0 42.9 0.0
NH 4 C1 94.7 97.8 98.7 H 2 0 2 (l%) 52.5 7.3 —
Na2S203 94.6 99.3 99.1 Citric acid 18.9 72.4 81.6
H 3 BO, 90.6 15.4 98.5 KCN 1.2 25.3 21.3
NaF 89.8 31.6 96.2 H20 30.0 99.2 99.2
Saturated solution.
From Braun, T., Farag, A. B., and Maloney, M. P., Anal. Chim. Acta, 93, 191, 1977.
With permission.
than on the PAN-polyether foam. However, the sorption rate of cobalt on PAN-po-
lyester foam is improved in the presence of a plasticizer (cr-dinonyl phthalate).
Microgram amounts of cobalt were quantitatively collected on plasticized and un-
plasticized PAN-polyester foam from aqueous thiocyanate solution at flow rates up to
ca. 10 ml min~' (column diameter, 25 mm, packed with 5 g loaded foam). However,
cobalt could be quantitatively collected from aqueous thiocyanate solution at flow
rates up to at least 40 mi min"' using plasticized and unplasticized PAN-polyether
foam columns.24 In both cases cobalt could be recovered together with the PAN re-
agent from the foam columns by elution with acetone.
The quantitative collection of manganese by plasticized and unplasticized PAN-po-
lyester foam columns was possible only at flow rates as low as 1 mi min~'. The collec-
tion of various concentrations of manganese and cobalt was achieved at flow rates 1
119
Table 68
CONCENTRATIONS OF COBALT
OR MANGANESE ON
PLASTICIZED AND
UNPLASTICIZED PAN-
POLYESTER POLYURETHANE
FOAM COLUMNS
Relative
Amount of Average accuracy
metal taken extracted of mean Std.
(jig) (X, %) (%) dev. (s)
Cobalt
Carrier- 98.6° 1.4 0.235
free 98.7' 1.3 0.497
0.2 98.6° 1.4 0.273
98.6* 1.4 0.187
2.0 98.8° 1.2 0.464
98.6* 1.4 0.141
20.0 99.2° 0.8 0.212
98.7* 1.3 0.570
200.0 95.8° 4.2 1.868
97.1* 2.9 0.540
Manganese
0.2 98.5° - 1.5 0.700
2.0 98.4° - 1.6 0.510
20.0 98.2° -1.8 0.866
200.0 96.7° -3.3 1.520
° Plasticized
* Unplasticized
From Braun, T., Farag, A. B., and Maloney, M.

P., Anal. Chim. Acta, 93, 191, 1977. With per-
mission.
and 5 to 10 ml min"1, respectively (Table 68). The separation of cobalt from man-
ganese was successfully carried out from aqueous thiocyanate solutions adjusted to pH
4 to 5. At this pH manganese is not retained by the PAN-foam column while cobalt is
quantitatively sorbed. Cobalt is then eluted with acetone.
Unplasticized PAN-polyether foams were subjected to an investigation of the
amount of the leached reagent. Generally, leaching of PAN from the foam-column by
the percolation of distilled water was found to depend on the initial concentration of
the reagent on the foam and the volume of water percolated (Figure 64).172° As is
obvious from these curves the amount of reagent leached is relatively small at the lower
PAN concentration (0.86 wt%) on plasticized PAN-foam.
Unplasticized PAN-polyether foam columns have been successfully employed for
the preconcentration of cobalt from extremely dilute aqueous solutions (0.1 ppb) con-
taining potassium thiocyanate.1720 The solution was adjusted to pH 4 to 9 and perco-
lated through the column at a flow rate of 100 ml min"1 (column diameter, 25 mm).
The retained cobalt and the reagent were completely eluted from the foam column with
acetone at a flow rate of 3 mi min"1 and cobalt determined spectrophotometrically
using PAR reagent. The collection of traces of cobalt from 10-i water samples has also
been reported.172"
30r-
T
i? 20
o
LU
X
LU
_1
<
10
I
3 4 5
WATER VOLUME (L)
FIGURE 64. PAN leached from loaded foam at different initial

PAN concentrations. (From Braun, T, and Abbas, M. N., Anal.
Chim. Acta, 119, 113, 1980. With permission.)
An automatic batch squeezing procedure has been described for the collection of
cobalt(II), zinc(II), cadmium(II), and mercury(II) from large volumes of water by a
PAN foam. 173 - 174 A semiquantitative determination of cadmium in river water has also
been reported. 174
Unplasticized and a-dinonyl phthalate-plasticized PAN-foams can be used also for
the collection of zinc(II), mercury(II), and copper(II). 35 The optimum pH of the sorp-
tion of these metal ions is 8 to 9.
Further work on the sorption of zinc(II), mercury(II), gold(III), and indium(III)
from aqueous thiocyanate solutions onto unplasticized PAN-foams has also been re-
ported. 3031 The distribution ratios were found to depend strongly on the thiocyanate
concentration. For example, in the case of zinc at pH 6, distribution ratios of 32 and
22,600 were measured in the absence and in the presence of thiocyanate (0.2 M), re-
spectively. In the case of mercury, the distribution ratio increases by increasing the
thiocyanate concentration and reaches a constant value of about 2000 at thiocyanate
concentrations above 0.05 M. The distribution ratios of indium were 4 and 6270 in the
absence and presence (0.2 M) of thiocyanate, respectively.
/. Other Reagent Foams

Polyurethane foam loaded with LIX 65N(alkyl /3-hydroxybenzophenone oxime) and
Kelex® 100 (7-dodecenyl 8-hydroxyquinoline) solutions has been prepared and evalu-
ated for some selective separations in batch and column modes.176 LIX-loaded foam
was prepared by soaking the foam in 1:1 (v/v) chloroform LIX solution (50% ih ker-
osene). The excess solution was removed by squeezing as usual and chloroform was
removed under vacuum. The Kelex®-foam was prepared by soaking the foam material
in Kelex ©-chloroform solution (1:3 v/v).
The total capacity for copper at pH 4 was found to be 14.3 and 25.1 mg copper g"1
LIX- and Kelex®-foam, respectively. In the case of LIX-foam, it was indicated that
121
10
TIME (minutes)
FIGURE 65. Sorption rates of the LIX 65N and Kelex 100 foams with copper (II) and
iron (III). (From Vernon, F., Sep. Sci. Technol., 13, 587, 1978. With permission.)
Table 69
RETENTION OF VARIOUS METAL IONS BY THE FOAM
COLUMNS FROM pH 6 SOLUTIONS USING AN ELUTION
RATE OF 0.3 mi MIN M
Percentages of metals retained by the column
Column Cd Co Cr Cu Hg Mn Ni Pb U Zn
LIX 65N 0 94.3 0 94.6 99.4 0 98.6 80 100 0

Kelex 100 98.3 97.5 0 100 100 71 97.2 96.6 100 100
From Vernon, F., Sep. Sci. Technol., 13, 587, 1978. With permission.
all ligand molecules are available for bonding with the formation of a 1:2 (metal-to-
ligand) complex (the measured value on the foam was 1:1.95). However, in the case of
Kelex®-foam, about 25% of the reagent is not available for chelation as the total
capacity of the foam represents a metal:ligand molar ratio of 1:2.7. This was attributed
either to the presence of some impurities in the Kelex® reagent or to some steric hindr-
ance. The rate of sorption of copper and iron is shown in Figure 65. The half-lives of
equilibrium sorption of copper are 1.25 and 0.25 min for LIX and Kelex®, respec-
tively. In the case of iron(III) they are 4.5 and 3.25 min.
The collection capabilities of the reagent foams were examined by percolating a so-
lution containing ten trace metals buffered at pH 6 through foam columns at a flow
rate of 0.3 ml min'1 (column diameter, 10 mm). As is clear from the results of Table
69, Kelex®-foam is more efficient for the recovery of all metal ions tested. However,
the LIX-foam is more selective. Attempts were made to separate these metal ions on
the reagent foam columns making use of the differences in kinetical behavior and
stability of metal complexes. A flow-rate of 3 m£ min'1 was employed.
3. Reagent Foams in Qualitative and Semiquantitative Analysis

A very attractive and useful application of reagent foams seems to be the sensitive
detection and semiquantitative determination of different inorganic species in aqueous
solutions. Foams loaded with chromogenic organic reagents (they are called "Chrom-
ofoarns" by Braun and Farag178) will develop characteristic color reactions on the foam
membranes in contact with aqueous solutions containing traces of ions chelated by the
chromogenic reagents. Plasticizing the foam increases the sensitivity of color forma-
tion. A qualitative detection test is usually done by shaking one or more cubes of the
appropriate chromofoam with 1 to 3 m£ of the aqueous metal ion solution for 1 to 2
min in a normal test tube. The chromogenic reagent solution which is homogeneously
distributed on the relatively high available surface area of the foam material can func-
tion as an effective collector for metal ion traces. This together with the relative ease
of observing colored reaction products on the surfaces of the white foams allows a
high sensitivity for the chromofoam test. Furthermore, the chromofoam can be packed
in columns producing foam beds suitable for the detection of very low concentrations
of several metal ions by percolating their aqueous solution through the foam column
at reasonable flow rates. Detections at the ppb level could be easily achieved by per-
colating relatively high volumes of the aqueous solution (up to 1 i) through the foam
columns. 178 In this multistage column sorption process, the reagent foam collects metal
ions from aqueous solution up to the observable sensitivity limit of the color reaction
with the reagent on the foam. Consequently, this column foam test significantly im-
proves the sensitivity of detection tests by allowing detections in extremely dilute solu-
tions. Also, chromofoams could be employed in pulsated column operations.
A further advantage of the chromofoam test is its suitability for semiquantitative
analyses. This was achieved by using comparation color scales in batch operation or
by measuring the length of foam color zones on columns after percolation of the test
solutions. In the case of batch and pulsated methods, the color density on the reagent
foam cube was found to depend on the concentration of metal ions in aqueous solu-
tion.
Qualitative and semiquantitative determinations of zinc(II),178 lead(II),178 cop-
per, 178182 cobalt(II),178 chromium(VI), 179 nickel,180 iron(III),181 cadmium(II), 173174 mer-
cury(II), 173174 and tin(II)173'174 have been carried out using various chromofoams. As a
general rule, the sensitivity of the reagent foam tests is better than that of normal spot
tests.178 Also, the performance of plasticized reagent foams was found to be better
than the unplasticized one.
Plasticized dithizone foam was prepared by loading foam cubes (5 mm edge) with
0.05% (w/v) solution of dithizone in a-dinonylphthalate.178 Saturated rubeanic acid
solution in a-dinonylphthalate (0.1% w/v) was used for loading the foam to produce
rubeanic acid foam. Amberlite® LA-1-foam was prepared by using 50% solution of
Amberlite® in a-dinonylphthalate. The loading solution of 1,5-diphenylcarbazide-
foam was prepared by dissolving 0.1 g of the solid reagent in 10 mjf benzene followed
by the addition of 10 ml of Alamine 336.179 The dimethyl glyoxime loading solution
was prepared by dissolving about 0.2 g of DMG in 10 mi Alamine 336.18° Saturated
solution of biacetylmonoxime-benzoylhydrazone in dibutyl or dioctyl phthalate (ca.
0.1% w/v) was employed for preparing plasticized biacetylmonoxime benzoylhydra-
zone foam.182
Table 70 shows a comparison between the results obtained with several chromo-
foams in batch and column tests and those reported in the literature with the usual and
modified spot tests. The standard color scales used in the different foam tests for
semiquantitative analyses are shown in Table 71. The effect of relatively high concen-
trations of diverse ions on the detection of 1 /^g of cobalt(II) and chromium(VI) with
Amberlite® LA-1 and diphenylcarbazide foams, respectively, are presented in Tables
72, 73, and 74.
Squeezing173-174 and pulsating column181 methods have also been employed for the
detection of some metal ions in aqueous phases. In the later method181 color compari-
123
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Table 72
EFFECT OF DIVERSE IONS ON THE DETECTION OF 1 OF COBALT (II)
Amount Volof
Foreign Compound added aq soln Cobaltrforeign
ion added (mg)- (ml) ion Notes
Cations forming thiocyanate complexes
Fe(II) Fe(NH 4 ) 2 (S0 4 ) 2 1.0 2 1 l . O x 103 One drop of satd KF soln

added
3
Fe (III) FeCU 2.0 3 1 2.0 x io 1 ml satd KF soln added
3
Cu(II) CuS04 2.0 3 1 2.0 x 10 Traces of solid KI and
Na 2 S 2 O 3 added
4
Pb (II) Pb(N0 3 ) 2 40.0 2 1 4.0 x 10 White ppt formed, but did
not interfere
Mn (II) MnSO. 4.0 2 1 4.0 x 103 Yellow foam in blank
Cd (II) CdSO, 4.0 2 1 4.0 x 103
Ni(II) Ni(NO,)2 1.0* 2 1 l.Ox 103 Pale green foam in blank
Ag(I) AgNO3 10.0 2 1 l.Ox 10-
T1(I) T12SO4 20.0 3 1 2.0 x 10" White ppt formed
Hg (II) Hg(N03)2 2.0 2 1 2.0 x 103
Bi (III) Bi(N03)3 2.0 2 1 2.0 x 103 White ppt formed
Au (III) AuCl3 1.0' 2 I l.Ox 103 Pale orange foam in blank
Anions forming cobalt (II) complexes
s2cv- Na2S2O3 20.0 3 1 : 2.0 x 104

Oxalate Na 2 (COO) 2 5.0 2 1 : 5.0 x 103
Acetate CH3COONa 20.0 3 1 : 2.0 x 104
Tartarate KHC 4 H 4 0 6 10.0 2 1 : 1.0 x 10"
Other ions
Ba (II) BaCl2 20.0 3 1 2.0 x 104

Ca (II) CaCl2 20.0 3 1 2.0 x 104
Mg (II) MgCl2 20.0 3 1 2.0 x JO 4
Sr (II) Sr(N03)2 20.0 3 1 2.0 x 104
Ce (IV) Ce(SO4)2 1.0 2 1 l.Ox 103 Yellow foam in blank
Zr (IV) Zr(S04)2 2.0 2 1 2.0 x 103
Rb(I) Rbl 20.0 3 1 2.0 x 10"
Li (I) LiBr 2.0 3 1 2.0 x 103
As (111) As2O3 2.0 2 1 2.0 x 103
Cr(III) KCr(S04)2 1.0' 2 1 l.Ox 103 Violet foam in blank
vcv NH 4 V0 3 7.0' 2 1 7.0 x 103 Satd KF soln (0.1 ml) added
Yellow foam in blank
W(V- Na 2 WO 4 5.4 3 1 5.4 x 103
SeCV- Na2SeO3 16.0 f\
1.6 x 10"
HPO<!- Na2HP04 16.0 2 1.6x 104
Br KBr 20.0 3 2.0 x 104
cio4- NaClO4 20.0 3 2.0 x 104
r KI 20.0 3 2.0 x 104
S2052- K2S205 20.0 3 2.0 x 104
cio3- NaClO3 20.0 3 2.0 x 104
so32-2 Na2SO3 20.0 3 2.0 x 10-
s2os - K2S20. 1.0 2 l.Ox 103
MnO, KMnO 4 2.0= 2 2.0 x 103
F- NaF 20.0 3 2.0 x 104
BKV KBrO 3 20.0 3 2.0 x 10"
Ascorbate L-ascorbic acid 20.0 3 2.0 x 10-
Table 72 (continued)
EFFECT OF DIVERSE IONS ON THE DETECTION OF 1 ^g OF COBALT (II)
Note: Except where mentioned otherwise, the color of the foam in a blank test was white. In case of
ions which interfere by their own colors in solution, it was found better to take out the foam cube
(after shaking with the test solution) and to shake it with few milliliters of water. The blue color,
which appears in the presence of cobalt (II), was then better observed.
The amount of the foreign ion below which the detection of 1 f/g of cobalt can easily be achieved.
6
Value obtained by comparison with a blank test.
' 0.5 ml 1 MHC1 and 1 ml Na2(COO)2 (10 mg mf' 1 ) added, and mixture heated to ca. 80°C. After
cooling 1 ml KSCN solution added; cobalt is then detected as usual with reagent foam.
From Braun, T. and Farag, A. B., Anal. Chim. Acta, 73, 301, 1974. With permission.
Table 73
EFFECT OF DIFFERENT CATIONS ON THE
DETECTION OF 1 ^g OF CHROMIUM (VI)
Maximum tolerable
Maximum tolerable concentration of
Foreign Compound amount of the interfering ion
ion added foreign ion/mg" relative to Cr (VI)
La (III) La(N03)3 10 104

Ce (IV) Ce(SO4)2 10 104
Co (II) Co(NO 3 ) 2 -5H 2 O 1 103
Fe (III) FeCl3* 10 104
Ni (II) NiSO 4 -7H 2 O 10 10"
T1(I) T1N03 1 103
In (III) InCl 3 -7H 2 O 1 103
Ba (II) BaCl2 10 104
Ca (II) CaCl2< 10 10"
Sr (II) SrCl2 10 104
Rb(I) RbNO 3 10 10"
Mg (II) MgCl2 10 104
NH4* NH4C1 10 10-
• The amount of foreign ion below which the determination of 1 pig of

chromium (VI) in 2 ml of aqueous solution can be easily achieved.
* The foam color in the blank test [i.e., in the absence of chromium (VI)]
was yellow.
A few drops of 1 Nperchloric acid were added to the CaCU solution.
From Farag, A. B., El-Wakil, A. M., and El-Shahawi, M. S., Analyst 106,
son was made using a constant number of pulses in a fixed volume of solution. A
standard color scale was developed under identical experimental conditions. In the
other method,173'174 variable numbers of squeezes were employed until the colored re-
action products first appeared on the reagent foam. In this case, the number of
squeezes needed is a function of solution concentration, and by comparison with a
standard known concentration, the concentration of the unknown solution could be
determined semiquantitatively. The formal method was employed for the detection of
iron with plasticized amine-foam, while the latter has been used for the detection and
semiquantitative determination of cadmium, tin, and mercury with PAN foam. 173174
The detection and semiquantitative determination of phosphate ion has been devel-
127
Table 74
EFFECT OF VARIOUS ANIONS ON THE DETECTION OF 1 Mg OF
CHROMIUM (VI)
Maximum tolerable
Maximum tolerable concentration of
amount of the interfering ion
Foreign ion° Compound added foreign ion/nig* relative to Cr (VI) Notes
Acetate CH3COONa 10 Drops of 0.1 N perchloric

acid were added
Oxalate Na 2 C 2 0 4 10 10' Oxidation by bromine
water was carried out
followed by addition of
drops of 0.1 M perch-
loric acid
Tartarate KNaC 4 H 4 O 6 10 10" Conditions as mentioned
for oxalate
2
s2o3 - Na2S2O3 0.1 102 Oxidation by bromine
and the excess of bro-
mine was eliminated by
heating
ci- NaCl 10 10"
Br NaBr 10 10"
CNS- KCNS 10 104 Drops of 0.1 Afperchloric
acid were added
3
P04 - Na3PO. 10 10- pH Adjusted to about 1
HPO42- Na 2 HPO 4 10 10- pH Adjusted to about 2
H 2 P0 4 - NaH 2 PO 4 10 10"
HCCV KHCOj 10 10" pH Adjusted to about 2
B40,2- Na 2 B 4 O,-10H 2 O 10 104 pH Adjusted to about 2
NOr NaNO 2 10 10" Oxidation by Br 2 was car-
ried out followed by ad-
justing pH to about 2
r Nal 10 10"
Formate HCOONa 10 10" Oxidation by Br 2 was car-
ried out followed by ad-
justing pH to about 2
so322- Na2SO3 0.1
so4 - Na2SO4 0.1 102
vor NH 4 VO 3 < 0.1 102
MoO42- (NH 4 ) 2 MoO 4 - 10 10" Drops of a saturated so-
lution of oxalic acid were
added
MnO4- KMnO 4 0.5 2 x 102
L-Ascorbate L-Ascorbic acid 0.1 102 Oxidation by bromine
followed by removal of
excess of bromine
With metal ions that interfere due to their own color in solution, it was found better to take out the foam
cube (after shaking with the test solution) and to shake it with a few milliliters of water. The red-violet
color that appears in the presence of chromium (VI) was then better observed.
The amount of the foreign ion below which the detection of 1 ^g of chromium (VI) in 2 ml of aqueous
solution can be easily achieved.
The foam color in the blank test [i.e., in the absence of chromium (VI)] was yellow.
From Farag, A. B., El-Wakil, A. M., and El-Shahawi, M. S., Analyst, 106, 809, 1981. With permission.
oped using TBP-plasticized Amberlite® LA-2-foam in the molybdate form. 184 The
reagent foam was prepared by loading the clean dried foam cubes (20 pieces, 10 mm
edge) with 5 nuf of 10% tetrahydrofuran solution of Amberlite® LA-2 (molybdate-
form) and 0.5 mi TBP. The solvent was then evaporated slowly from the foam mate-
rial at room temperature. The batch version of the foam test involves first collection
of the phosphate on the reagent foam cube followed by reduction with tin(II) chloride
solution. As low as 0.2 ppm phosphorus as phosphate could be detected by this pro-
cedure. The semiquantitative determination of phosphate was also possible by com-
paring the blue color produced on the foam with that of a standard color scale (0, 0.2,
0.5, 1.0, and 2.0 ppm phosphate). The investigators184 plasticized the foam with TBP
which is actually an organic phosphate compound and mentioned that the color inten-
sity on the foam decreases with the decrease the amount of plasticizer. Moreover, no
color was developed in the absence of TBP. It was also reported that a high color
intensity of the foam is obtained in blank tests when high concentration of tin(II)
chloride solution is used.184 In our opinion more work must be done to clarify the role
of TBP in this process.
It is worth mentioning that unloaded polyether polyurethane foam has also been
employed for the detection and semiquantitative determination of alkylbenzenesulfon-
ate (ABS) from aqueous media containing Crystal Violet (CV) or Methylene Blue
(MB).59 It was indicated that polyester polyurethane and other foams such as polyvi-
nylchloride, polystyrene, and polyethylene give less satisfactory results for this test.
In the batch version of the above-mentioned method, 1 mf of 1 Nsulfuric acid and
2 to 5 mjf of 10~3 M CV solution were added to the sample solution and the whole
mixture diluted to 100 nuf with distilled water. A polyurethane foam chip was then
soaked in the produced solution for 5 min. As low as 5 ppm ABS could be detected
using a suitable standard color scale. The limit of detection could be decreased to 0.1
ppm by employing columns (8 mm diameter, containing 0.19 g foam) at a flow rate of
20 to 30 mi min"1.
4. Foams Loaded with Liquid Ion Exchangers
a. Anion Exchange Foams
1. Tri-n-Octylamine-Foam
The preparation and application of a polyurethane foam loaded with a liquid anion
exchanger was first described by Braun et al.185 They used tri-n-octylamine (TOA)-
foam for the separation of cobalt from nickel in a hydrochloric acid system. As is
known, TOA reacts with hydrochloric acid according to the equation:
(R 3 N) 0 + H " + Cl ^(R3NHCD0 (22)
where
R = -CH2-(CH:)6-CH, (23)
The amine salt thus formed acts as a liquid anion exchanger and reacts with the
metal chloride complex present in aqueous solution:
(R 3 NHC1-) 0 + (MCl;;;;,,)1R1. ?± (R,NH m MCl, n , n ) ( ; + m(Cr) aq
where o and aq, stand for organic and aqueous phase, respectively.
129
100
LU
O
CC
LU
Q_
250 300
FIGURE 66. Breakthrough curve for cobalt. Support: poly-

ether-type polyurethane foam. Weight of packing: 2.4323 g.
Flow rate: 1 ml mirr 1 . Stationary phase: 17.7% TOA-HCI.
Cobalt concentration: 0.07 mg ml''. (From Braun, T., Huszar,
E., and Bakos, L., Anal. Chim. Acta, 64, 77, 1973. With per-
mission.)
The separation of cobalt from nickel by extraction with TOA-foam from hydrochlo-
ric acid medium is based on the tendency of cobalt to form relatively stable extractable
chlorocomplexes (mainly CoCl42"). Nickel, however, is not extractable from hydro-
chloric acid solutions with long-chain amines. This was exactly the case with TOA-
foam as the distribution ratio of nickel was found to be negligible at all the acid con-
centrations tested (0 to 9 MHC1).
It was mentioned that as the amount of TOA-HCI loaded on the foam increased the
elasticity of the foam decreased. High amine salt loading (ca. 67 wt%) was found to
be unsuitable for efficient separation. However, separation on very low amine salt
loading (3.8%) was incomplete. Loadings in the range 11.4 to 17.7% were found to be
the most suitable in batch and flow modes of separation. The breakthrough capacity
curve (Figure 66) obtained on columns loaded with 17.7% TOA-HCI, and cobalt feed
solution with a concentration of 0.07 mg mi"1 was found to be quite sharp.
Figure 67 shows, for example, the separation of carrier-free 58Co from nickel. Nickel
was eluted with 8 MHC1, while cobalt is completely retained. Cobalt is then quantita-
4MHCI IMHCk
20
16
Ni Co
4.67mg 40/jg
LU 12
O
cr
I t
20 40 60 80
ml
FIGURE 67. Nickel-cobalt separation. Stationary phase:

11.4% TOA-HC1. Nickel elution: 94.5%; cobalt elution:
99.5%. Support: polyether-type polyurethane foam. Flow rate:
1 mt min" 1 . (From Braun, T., Huszar, E., and Bakos, L.,
lively eluted with 1 M HC1. The separation of traces of cobalt from a wide range of
relative concentrations of nickel (1:108) is shown in Table 75.
It is worth noting that TOA-loaded silicone rubber foam has also been employed for
the separation of rhodium and iridium in hydrochloric acid solution containing chlor-
ine using batch and columns methods.186 Iridium was completely retained (98.5 ±
0.9%) by this reagent foam from 6 MHC1 containing sodium chlorate (as a source of
free chlorine) while rhodium (99%) remains in the aqueous solution.
b. Amberlite® LA-2 Foam

An anion exchange foam containing Amberlite® LA-2 has been employed for the
separation of cadmium(II) in hydrochloric acid solution.175 It was indicated that co-
balt(II), copper(II), lead(II), and nickel(II) are not significantly sorbed by this reagent
foam at any acidity. Generally, the sorption of the Amberlite® LA-2 foam was found
to be similar to that of solid resin exchangers loaded with the anion exchanger or
solvent extraction system employing Amberlite® LA-2.
Quantitative separations of cadmium-zinc and copper(II)-iron(III) pairs were
achieved in flow experiments employing a flow rate of 1 mjf min"1 (column diameter,
15 mm).175
c. Aliquat Foam
Polyurethane foam loaded with Aliquat 336 (methyltricaprylyl ammonium chloride)
has been evaluated as anion exchange foam, 187 and its utility for the separation of iron,
131
Table 75
NICKEL-COBALT SEPARATION
Taken Found
Ni to Co Ni Co Ni Co Ni Co
ratio (mg) (mg) (mg) (mg) (%) W
1 0.537 0.500 0.558 0.509 103.9 101.7

0.537 0.500 0.542 0.498 100.9 99.6
0.537 0.500 0.531 0.510 98.7 102.0
10 0.537 5.10-2 0.547 4.97. 10-2 101.9 99.1
0.537 5.10-2 0.540 5.04.10-2 100.6 100.8
0.537 5.10-2 0.551 4.99. 10-2 102.6 99.7
10' 0.537 5.10-3 0.547 4.93.10'3 101.9 98.6
0.537 5.10-3 0.527 5.05. 10'3 98.1 100.9
0.537 5.10-3 0.542 5.06.10-3 100.9 101.2
103 0.537 5.10- 0.532 5.04.10- 99.0 100.7
0.537 5.10- 0.539 4.96.10- 100.4 99.1
0.537 5.10- 0.544 5.15.10- 101.3 102.9
10s 4.19 4.10-8 4.17 4.06. 10-" 99.5 101.6
4.19 4.10'8 4.22 4.04. 10-« 100.7 100.9
4.19 4.10-8 4.23 3.99.10- 101.0 99.8
From Braun, T., Huszar, E., and Bakos, L., Ana/. Chitn. Acta, 64,
cobalt, nickel, and cadmium from hydrochloric and hydrobromic acids has been
tested. Nickel and cobalt showed no extraction in the range of acidity examined (1 to
8 M HC1 or HBr). However, cadmium and iron were retained on the Aliquat-foam.
The retention of cadmium was found to be quantitative at all conditions studied, while
the extraction of iron was noticed at acidities above 5.8 and 8 Min hydrobromic and
hydrochloric acids, respectively.
On the basis of these results it was possible to separate iron or cadmium from cobalt
and nickel in batch and flow systems. In 6 M hydrochloric acid solution cadmium and
iron were completely retained by the reagent foam while cobalt and nickel were not
absorbed by the foam. The elution of cobalt or nickel was achieved with 3 M HC1,
then iron with 0.1 ML-ascorbic acid, 0.1 MHNO 3 or 1 MNaF, and finally cadmium
with 1 M nitric acid solution. The quantitative separation of various relative concen-
trations of these metal ions has also been carried out using Aliquat-foam columns at a
flow rate of 2 to 4 mt min'1 (column diameter, 15 mm).
d. Cation Exchange Foams

Polyurethane foam loaded with a liquid cation (ethyl-hexyl phosphoric acid) exchan-
ger has been used for the separation of trace thorium in natural waters.188 A bis(2-
ethyl-hexyl) phosphoric acid/tributyl phosphate/carbon tetrachloride (2:5:93, v/v/v)
mixture was used as loading solution. The loaded foam thus produced was employed
for the collection and separation of thorium in 800 mt aqueous solution adjusted to
pH 1 at a temperature of 30 to 45°C by a batch extraction method. Stirring for 20 min
was found to be quite suitable for the complete retention of thorium. Thorium was
recovered by wet oxidation of the foam with concentrated nitric and perchloric acids,
followed by spectrophotometric determination of thorium with arzenoazo(III) at 665
mm. Table 76 shows the effect of some foreign ions on the retention of 2.12 ^g thorium
by the cation exchange foam.
Table 76
INTERFERENCE OF FOREIGN IONS BY THE
DETERMINATION OF THORIUM
Amount
added Th found Absolute Relative
Ion added (mg) (Mg) error error (%)
Fe (III) 10 1.97 -0.15 -7.1

Al(III) 10 1.97 -0.15 -7.1
Ca(II) 100 2.0 -0.12 -5.7
Mg (II) 100 2.30 +0.18 +8.5
Zn (II) 5 2.25 +0.13 +6.1
Ti (IV) 1 2.20 +0.08 +3.8
U(VI) 0.01 2.50 +0.38 + 17.9
0.02 2.72 +0.60 +28.3
Mo (VI) 5 2.05 -0.07 -3.3
Pb (IV) 1 2.15 +0.03 + 1.4
Co (III) 5 1.80 -0.32 -15.1
523 2.0 -0.12 -5.7
La (III) 0.4 1.85 -0.27 -12.7
Cu (II) 5 1.97 -0.15 -7.1
Ce(III) 0.4 2.25 +0.13 +6.1
Zr (IV) 0.0074 7.90 +5.78 +272.6
Zr (IV) 0.0074 2.05 -0.07 -3.3
NO3- 100 2.15 +0.03 + 1.4
PCV- 50 2.50 +0.38 + 17.9
Note: 2.12 ^g Th and 800 mt H 2 O were used for each experiment.
• Adding 1 mt saturated oxalic acid solution before development.
From Xie Chang-Sheng, Acta Chim. Sinica,40, 605, 1982. With permission.
5. Heterogeneous Ion Exchange Foams

There has been a continuous interest in preparing ion exchange materials with re-
duced solid-phase mass transport in order to increase the rate of the exchange process.
The preparation of pellicular resins,189 19° in which a solid core is surrounded by a thin
film of cross-linked ion exchange material and superficially sulfonated resins has been
described. 191 ' 192 Although the results obtained by these pellicular ion exchangers are
very promising, their low capacity remains a serious limitation. On the other hand,
many investigators, e.g., Pinfold and Karger, 194 have shown that the exchange proc-
esses on finely pulverized ion exchange resins proceed substantially faster than the
same processes on beads of the same composition. However, the use of fine grains
causes difficulties even in the batch technique, since they form colloidal suspensions.
One acceptable solution to this problem is the preparation of heterogeneous ion ex-
change foams in which finely ground commercial ion exchange resins are embedded
into the thin membrane walls of a polyurethane foam matrix of open-cell polyether
type. 195 The mechanical properties of these ion exchange foams are the same as those
of foam containing no ion exchanger, and the distribution of the exchanger particles
within the foam membranes proved to be uniform.
Sorption of copper(II) by the ion exchange foam occurs in one fast step (Figure 68),
i.e., gel diffusion is not the rate-controlling step as in the case of common ion exchange
resins. The half-life of equilibrium sorption as calculated from the curves of Figure 68
is 0.6 min. This value is exactly the same as that obtained with superficially sulfonated
styrene-divinylbenzene resin.191 However the capacity of the ion exchange foam is
about one order of magnitude higher than that of surface-sulfonated pearl polymers.
133
100 a-
50 70 90
TIME (min)
FIGURE 68. Rate of sorption of copper (II) on ion-exchange foam

at room temperature, (Cu2*), 5 mg. (From Mazurski, M. A., Chow,
A., and Gesser, H. D., Anal. Chim. Acta, 65, 99, 1973. With permis-
sion.)
Sharp breakthrough curves were obtained for copper(II) on columns packed with het-
erogeneous cation exchange foam.
The elution of copper with 0.5 M hydroxylammonium chloride solution was exam-
ined at 50°C using flow rates ranging between 2 and 10 mi min"1 (column diameter,
15 mm). Only a slight increase in peak width with increased flow rate occurs but the
elution of copper is quantitative even at flow rates as high as 10 mf min"1. Figure 69
shows the effect of flow rates on the elution of copper from cation exchange foam
column and cation exchange bead columns (Varion KS). With the foam columns, mi-
crogram and milligram amounts of copper could be retained and eluted quantitatively
with hydroxylammonium chloride solution.
The selectivity of the ion exchange foam was determined by measuring the cation
exchange distribution ratios of cadmium(II), zinc(II), iron(III), and calcium(II) over a
wide range of HCl-ethanol mixtures.1960 The results obtained show that the selectivity
of the ion exchange foam is about the same as the original exchange beads (Varion
KS). Evidently this experiment indicates that the ion exchange foam functions well in
water-miscible organic solvents, and swelling of the foam support in this medium does
not limit its application. This was further confirmed by the results obtained for the
separation of cadmium, zinc, iron, and calcium on foam columns. It was found that
these cations are eluted by HCl-ethanol mixtures (Figure 70) in the same order as for
AG 50 W-X8 sulfonated polystyrene cation exchange resin (100 to 200 or 200 to 400
mesh particle size).
6. Foams with Anchored Functional Groups

The preparation of cellular (foamed) plastics to which specific functional groups are
chemically bonded has also been described. 195196197
25.0 25.0 25.0
4ml min
20.0 - 20.0 20.0 -
15.0 - 15.0 15.0 -
o u
6? 59
.(b)
10.0 - 10.0 10.0 -
5.0
0.0 0.0
0 100 200 0 100 200 0 100 200
EFFLUENT (ml) EFFLUENT (ml) EFFLUENT (ml)
FIGURE 69. Effect of flow rate on the elution of copper (II) with 0.5 Mhydroxylam-
monium chloride solution at 50°C. (a) Ion-exchange foam column; (b) ion-exchange
bead column. (From Braun, T. and Farag, A. B., Anal. Chim. Acta, 68, l\9, 1974.
With permission.)
Gesser et al.196 heated polyurethane foam cylinders during an electrical discharge

with hydrogen sulfide to anchor sulfhydril groups on the foam membranes. Columns
packed with the SH-foam were evaluated for the sorption of mercury(II)chloride and
methylmercury(II)chloride from dilute aqueous solutions. Quantitative retention of
mercury was obtained by percolating 100 mi of solution having concentrations of 0.4
to 0.0004 ppm through SH-foam columns at 40 ml. min"1 flow rate (column diameter,
20 mm). The collection efficiency of the SH-foam columns decreased on using higher
concentrations of mercury (e.g., 4 ppm) due to overloading. The effectiveness of the
SH-foam is said to be unaffected by the storage time before use. Freshly prepared and
1-month-old foams gave similar sorption values for 0.04 ppm of mercury.
The effective capacity of the SH-foam columns is much lower for methylmer-
cury(II)chloride. This was attributed to the steric hindering effect of the methyl group.
The fraction of mercury sorbed on the foam column generally increased as the concen-
tration decreased. Mercury(II) was recovered from the SH-foam by 2 M hydrochloric
acid in a Soxhlet extractor.
Although the SH-anchored polyurethane foam has low capacity and its preparation
is quite complex, the preparation of such a foam is considered to be a valuable contri-
bution to studies of anchoring functional groups on the foam.
Braun et al.195 have described various methods for the indirect introduction of func-
tional groups (ionogenic groups) into the skeleton structure of the foam. Two different
methods are possible. The first method is based on a polymer analog reaction after the
foam has been loaded with an easily transformable polymer. A styrene-polyurethane
135
25.0
20.0
15.0
10.0
5.0
0.0
100 200 300 400 500 600 700
EFFLUENT, ml
FIGURE 70. Elution curve for Cd(II)-Zn(II)-Fe(III)-Ca(II)

mixture on a cation-exchange foam column of 12-cm bed
height at room temperature. (From Braun, T. and Farag, A.
B., Anal. Chim. Acta, 68, 119, 1974. With permission.)
copolymer was prepared by this method and the anion exchange groups then intro-
duced by chloromethylation and amination. The mechanical properties of this foam
depend on the polymerization conditions and the amount of styrene. At about 20%
polystyrene content the elasticity of the foam significantly decreased, i.e., permanent
deformation occurred on pressure. Further increase in the polystyrene content led to a
rapid breakdown of mechanical properties; at about 40% polystyrene the foam be-
haved as a rigid material of brittle structure. The second method is based on radiation
grafting of open-cell polyurethane foams with methacrylic acid. This process fixes an
ionogenic group on the foam membranes and leads to the final product in a single step.
Foams prepared by this method are weak carboxylic ion exchange with excellent prop-
erties and fair ion exchange capacities.
IX. OTHER ANALYTICAL USES OF UNLOADED AND LOADED

RESILIENT POLYURETHANE FOAMS
A. Column Redox Reactions

The analytical applications of a redox system consisting of tetrachlorohydroquinone
3 4 5
NUMBER OF PULSES
FIGURE 71. Effect of the number of pulses on the reduction efficiency of the pulsed
column, (a) With 2 g of loaded foam; (b) with swollen foam. Cerium (IV) sulfate con-
centration 0.005 M; volume of the solution 5 ml; at room temperature. (From Braun,
T.,Farag, A. B., and Klimes-Szmik, A., Anal. Chim. Acta, 64, 71, 1973. With permis-
sion.)
immobilized in the wall membranes of flexible polyether polyurethane foam in conven-

tional and pulsated column operations have been described by Braun and Farag.197"-198
The redox reagent was immobilized physically in the foam membranes in two different
ways. In both cases tetrachlorobenzoquinone (chloranil) was dissolved in chloroben-
zene or methyl/sobutylketone and the foam was then allowed to swell in this solution.
The swollen foam was then either dried in an oven at 80°C to remove all the solvent,
or squeezed between sheets of filter paper keeping a certain amount of the solvent in
the foam. Foams prepared by complete evaporation of the organic solvent actually
hold the reagent as finely divided particles. Care must be taken during preparation of
reagent foam by this method because rapid evaporation of the solvent or the use of
higher concentrations of the reagent will produce foams holding the reagent in bigger
crystals which does not favor the kinetics of the succeeding redox reactions. However,
the presence of solvent together with the reagent (as in the case of reagent foams pre-
pared by the second method) offers a suitable solution to this problem and the redox
reaction between metal ion in aqueous solution and the organic reagent in the foam
membranes was found to be faster. 198 Chloranil loaded on the foam was completely
reduced to tetrachlorohydrobenzoquinone before use with a 0.2 Msolution of ascorbic
acid. Figure 71 shows, for example, the effect of the number of pulses in the pulsated
column system (closed operation) on the reduction efficiency of cerium(IV) with te-
trachlorohydrobenzoquinone loaded on polyurethane foam prepared by the two pre-
viously described procedures.
The effect of flow rate and temperature on the reduction efficiency of cerium(IV),
vanadium(V), and iron(III) has been examined in normal column experiments.197 It
was found that cerium(IV) is completely reduced to cerium(III) by percolating eerie
sulfate solution in 1 M sulfuric acid through the redox column at room temperature
employing a flow rate as high as 11 ml min"1 (column diameter, 15 mm). In the case
137
Table 77
DETERMINATION OF CERIUM
(IV), VANADIUM (V), AND IRON
(III) BY COLUMN "MEMORY"
Amount (mg)
Ion
determined Present Found Average
Ce (IV) 76.57 78.15

77.38
76.21 76.68
76.21
75.44
V(V) 21.22 21.27

21.83 21.35
20.94
Fe (III) 54.06 52.13

54.33 53.59
54.33
From Braun, T., Farag, A. B., and Klimes-

Szmik, Anal. Chim. Acta, 64, 71, 1973. With
permission.
of vanadium(V) and iron(III), however, room temperature reduction was quantitative

only at flow rates of 4 and 2 mf min~', respectively. Increasing the temperature of the
foam-filled column to 35°C, by circulating thermostated water through the external
jacket of the column, was found to increase the reduction efficiency of vanadium(V)
and iron(III). 197 At this temperature quantitative reduction of vanadium and iron is
obtained using flow rates of 7 and 6 ml muT1, respectively.
Determination of the above-mentioned metal ions by the redox-foam column
method was achieved by measuring the amount of tetrachlorohydroquinone oxidized
on the column (due to the effect of the percolated metal ion) by passing a known
volume of standard solution of ascorbic acid through the column and titrating the
effluent with standard iodine solution. The results obtained1970 using this column
"memory"198 method are given in Table 77. It was reported that the proposed reagent
foam columns could be used over 30 reduction cycles without losing their efficiency.
In the case of the pulsated column method, a similar temperature effect was ob-
served. The breakthrough capacities of pulsated columns for cerium(IV), vana-
dium(V), and iron(III) were determined at room temperature and after preheating the
solution before reduction to about 80°C.198 Figure 72 shows, for example, a plot of
the percentage of reduced cerium against the volume of cerium(IV) sulfate solution
used at room temperature and at 80°C. As is clear from these curves, the breakthrough
capacity curve obtained in the case of preheating the aqueous metal ion solution before
reduction is sharper than that obtained at room temperature. Similar results were re-
ported for the reduction of vanadium and iron using the pulsated column method.
Analyses of different concentrations of cerium(IV), vanadium(V), and iron(III) by
the pulsated foam column method were successfully carried out with an average rela-
tive error of ± 2.2% (Table 78).
100 I I
o
CJ 50
Q
LLI
L.
oc
I I
10 20 30 40 50 60
ml Ce(S0 4 ) 2
FIGURE 72. Breakthrough capacity curves for cerium (IV). (a) At

room temperature; (b) after preheating the solution to approximately
80°C. Weight of the swollen foam 2 g; cerium (IV) sulfate concentra-
tion 0.1 M. (From Braun, T., Farag, A. B., and Klimes-Szmik, A.,
B. Isotope- and Redox-Exchange Separations with Polyurethane Foams

Owing to the increased use of nuclear energy for the production of electricity, con-
siderable attention is devoted to the protection of the environment against radioactive
contaminations.200 203 Rapid radiochemical separations based on selective isotope- and
redox-exchange reactions have successfully been carried out with various radioactive
elements. The most important types of isotope exchange separations can be classified
in the following main categories: (1) isotope exchange between preformed solids (pre-
cipitate) and aqueous solution;204'207 (2) isotope exchange between a metal amalgam
and metal ions in aqueous solution;208 209 (3) isotope exchange between metallic mer-
cury and ionic mercury in aqueous solution;210-211 (4) isotope exchange between a
water-immiscible organic solvent and aqueous solution;212-213 and (5) isotope exchange
between an immobilized reagent and aqueous solution.214-215
Polyurethane foams immobilizing finely divided precipitates216'218 or hydrophobic
organic reagents219 have been examined for many isotope- and redox-exchange sepa-
139
Table 78
DETERMINATION OF CERIUM (IV), VANADIUM (V), AND
IRON (III) BY THE PULSED COLUMN TECHNIQUE
Temp of Metal ion (mg)

Eluting the metal Error Average
Element solution ion soln (°C) Taken Found
Ce4 1 MH 2 SO 4 Room temp 6.87 6.67 -2.9

1 MH 2 SO 4 Room temp 6.87 6.87 0.0
1 MH 2 SO 4 Room temp 13.75 13.54 - 1.5 ± 1.
1 MH Z SO 4 Room temp 13.75 13.54 - 1.5
1 MH 2 SO 4 Room temp 20.62 21.02 + 1.9
1 MH 2 SO 4 Room temp 20.62 20.01 - 3.0
MH2SO4 ca. 80 1.95 1.89 -4.1

MH 2 SO 4 ca. 80 1.95 1.99 + 1.9
MH2SO4 ca. 80 3.91 3.81 -2.8
MH2SO4 ca. 80 3.91 3.74 -4.2 ± 2.9
MH2SO4 ca. 80 5.86 5.67 -3.2
MH 2 SO 4 ca. 80 5.86 5.91 + 0.9
Fe3 0.03 MHC1 ca. 80 5.31 5.41 + 1.9

0.03 MHC1 ca. 80 5.31 5.41 + 1.9
0.03 MHC1 ca. 80 10.65 10.81 + 1.5
0.03 MHC1 ca. 80 10.65 11.08 + 4.1 + 0.9
0.03 MHC1 ca. 80 15.98 16.08 + 0.6
0.03 MHC1 ca. 80 15.98 16.21 + 1.5
" Elution with 1 Msulfuric acid. Cerium (IV) solution at room temperature.
* Elution with 1 Msulfuric acid. Vanadium (V) solution at 80°.
e
Elution with 0.03 Mhydrochloric acid. Iron (III) solution at 80°.
From Braun, T. and Farag, A. B., Anal. Chim. Acta, 65, 139, 1973. With permission.
rations using batch, normal column, and pulsating column operations. The membrane-
like structure of the polyurethane foams together with the excellent hydrodynamic
properties of columns packed with them, allowed in these cases relatively fast flow
rates in column experiments. The resilient character of open-cell polyurethane foams
enabled their application in pulsating column operations. The automation of the latter
procedure provides a simple method which can be very useful in routine field analysis.
It eliminates the transportation of bulky samples into the laboratory for analysis as
preconcentration can easily be made in the field.
I. Isotope-, Redox- and Precipitate-Exchange Separations on Finely Divided Precipi-

tate Immobilized on Open-Cell Polyurethane Foams
Isotope exchange separation of radionuclides via their exchange reactions with one
of their fairly insoluble precipitate is the most widely used method in static (batch) and
dynamic (flow) systems. Braun and Farag216 suggested immobilization of very finely
divided precipitate, e.g., silver sulfide, in the membranes of polyurethane foam, and
the silver sulfide foam thus produced was evaluated for isotope exchange separation
of radioactive silver. They prepared silver sulfide foam by mixing a heterogeneous
cation exchange foam with silver nitrate solution to change it to silver-form followed
by precipitating silver sulfide in the foam by treatment with a 5% solution of sodium
sulfide.195 It was indicated that the cation exchange capacity of the foam after precip-
itation of Ag2S is identical to its original capacity, which allows repetition of the pre-
cipitation cycle several times to ensure formation of the desirable amount of precipitate
Table 79
CONCENTRATIONS OF
RADIOSILVER BY ISOTOPE
EXCHANGE REACTION ON
COLUMNS PACKED WITH Ag2S"
FOAM
Average' Ag Relative
Amount of exchanged accuracy
Ag taken on foam of the mean
(X, %)
0.1 99.2 0.8

1.0 98.6 1.4
10.0 98.8 1.2
100.0 98.7 1.3
Note: The flow rate was 20 ml cm"2 min" 1 .
° Average of four determinations.
From Braun, T. and Farag, A. B., Radi-

ochem. Radioanal. Lett., 19, 275, 1974. With
permission.
in the foam. Obviously, this procedure could be employed also for the immobilization
of other precipitates in foam membranes. The rate of isotope exchange separation of
silver on Ag2S foam was found to be quite fast as the exchange yield reaches 99% after
less than 10 min shaking. The exchange yield is slightly decreased by increasing nitric
acid concentration in the aqueous solution. It reaches 96% in 4 M nitric acid. Fast
collection of various concentrations of radiosilver has successfully been carried out on
columns packed with 2 g of Ag2S-foam using a flow rate of 40 mi min"1 (column
diameter, 15 mm) (Table 79). Polyurethane foam immobilizing finely divided copper
has also been prepared by a similar procedure.217 In this case heterogeneous ion ex-
change foam is changed to copper-form followed by the reduction of ionic copper in
the foam to metallic form with a sodium hydrosulfite (Na2S2O4) solution.
Copper-foam has successfully been used for redox-exchange separation of radiosil-
ver from aqueous solution. The rate of redox-exchange retention of silver as measured
in batch experiments was found to be quite fast. The retention was increased by in-
creasing the acid concentration up to 2 M HNO3 and decreased as the acid concentra-
tion was increased. This was attributed to the significant dissolution of copper at high
acid concentrations. Good separation yields of silver were obtained with copper foam
columns employing flow rates of 20 mjf min'1 (column diameter, 15 mm).
Gimesi and Banyai218 immobilized finely divided silver chloride (or silver iodide) or
colloidal silver on open-cell polyurethane foams by soaking the foam material in 10
vol% TBP solution in ethanol followed by mixing the squeezed foam with 0.1 M silver
nitrate solution. The foam thus produced is heated either with acidic sodium chloride
(or sodium iodide) solution to precipitate finely divided silver halide in the foam mem-
branes, or with ascorbic acid to produce colloidal silver on the surfaces of the mem-
branes. The researchers described rapid procedures for the retention and concentration
of radioiodine using these silver foams. Radioiodine in the iodide form was retained
by precipitate-exchange on silver chloride foam columns and by isotope-exchange on
silver iodide foam columns. Polyurethane foam impregnated with colloidal silver binds
141
Table 80
ANALYSIS OF SAMPLES BY
APPLICATION OF POLYURETHANE
FOAMS
13>
Moisture I added Radioactive
Sample (%) (Bq/g)" yield (%)
Retention of m I on a column of polyurethane foam impreg-

nated with AgCl
Wheat flour 11 2 80—90

Potato 80 0.2—2 77—81
Cabbage 95 0.2—2 80—82
Meat 70 2 75—80
Retention of 131I on a column of polyurethane foam impreg-

nated with colloidal Ag; expulsion of I2 with CO;
Wheat 7 0.4 88—92

Potato 80 0.4 83—87
Cabbage 95 0.2 85—90
Meat 70 0.4 73—75
Retention of 131I on a column of polyurethane foam impreg-

nated with colloidal Ag; steam distillation of the liberated Iz
Cereals 8 0.04
Potato 75 0.04—4 75—80
Salad 90 0.04—4
Note: Detection of the y-activity of the columns with a well-

type Nal (Tl) detector.
• Dried sample
From Gimesi, O. and Banyai, E., Mikrochim. Acta, II, 313,

iodine vapors containing 13I I, according to the reaction:
2 Ag col , + "I, vap -» 2 Ag*Ip,,, (24)
Gimesi and Banyai218 described a micro-method for the determination of radioiodine

using colloidal silver foam. The method is based on the liberation of radioiodine vapor
from the sample solution with hydrogen peroxide in a Wagner-Parnas apparatus and
quantitative retention of the steam-distilled iodine on a silver impregnated foam col-
umn. Carbon dioxide was employed in some experiments to expell iodine vapors from
the aqueous solution for subsequent retention on the silver foam column. Iodine was
determined directly on the foam by measuring the radioactivity of the 131I. A thorough
study was made of methods for digestion of various foodstuffs without loss of iodine,
and the prepared foam columns were successfully employed for the determination of
iodine in various samples (Table 80).
2. Isotope-Exchange Separations on Hydrophobic Organic Phases Immobilized in

Open-Cell Polyurethane Foams
TBP-plasticized iodine foam has been prepared by allowing the foam to swell in an
10 —
0.01
FIGURE 73. Effect of the concentration ratio of iodide ion in aqueous solution and
on foam on the isotope exchange yield with TBP-plasticized iodine foam. (From Braun,
T. and Farag, A. B., J. Radioanal. Chew.., 25, 5, 1975. With permission.)
iodine solution in TBP.219 This foam was found to retain iodine firmly and is suitable
for the isotope exchange separation of radioiodide in batch and flow operations. The
reaction of radioiodide and the immobilized iodine in the foam can be represented by
the following equation:
2 *r (aq) + I, (foam) ^ 21 (aq) + *I, (foam) (25)
where the asterisk denotes the radioisotopes of iodine. The exchange of the iodide ion
by the iodine foam was found to be quite fast as the equilibrium value is reached after
less than 10 min of shaking in the batch extraction mode. The highest exchange yield
was obtained from aqueous solutions having pH values lower than one. In flow exper-
iments, the exchange yield (the percentage retention of radioiodide on the foam col-
umn) was determined as a function of the ratio of total amount of exchangeable ion in
solution (I~) and total amount of exchangeable ion in foam (I 2 ). A flow rate of 6 to 8
mi min~' (column diameter, 15 mm) has been employed in these experiments. Figure
73 shows that the experimental points are more or less on the theoretical curve (solid
line) calculated by Eckhardt et al.220 using the equation:
— = _ = (!- e (26)
a L
143
Table 81
CONCENTRATIONS OF
RADIOIODIDE BY ISOTOPE
COLUMNS PACKED WITH TBP-
PLASTICIZED IODINE FOAM
Average Relative
Amount of I" exchanged accuracy
r taken on foam" of the mean
(^g) (X, %) (%)
Carrier-free 98.1 - 1.9

0.1 97.9 -2.1
1.0 98.1 -1.9
10.0 98.0 -2.0
100.0 98.7 -1.3
1000.0 98.8 -1.2
Note: The flow rate was 3 to 4 ml cm"2 min~'.
Average of four determinations.
From Braun, T. and Farag, A. B., /. Radioanal.

Chem.,25, 5, 1975. With permission.
where F = total amount of exchangeable iodine in the foam,

L = total amount of exchangeable iodide in the solution,
a = total activity originally present in the solution, and
b°° = activity of the foam after the passage of the radioiodide solution through
it.
When the concentration of the exchangeable ion in the foam bed is equal to its
concentration in the aqueous solution, L = F (L/F = 1), the fraction of the exchanged
ion b°°/a will be equal to 0.632. That is, the exchange yield is equal to 63.2%, assum-
ing that the isotope-exchange equilibrium is attained rapidly and all iodine in the foam
is available for this exchange reaction. The experimental value was found to be about
63% which indicates that the entire iodine-coated membranes of the plasticized foam
were involved in the exchange process under the experimental conditions used.219 That
is why the mobility of iodide ion in the iodine foam is very high.
The separation of radioiodide on iodine foam columns proved to be quite selec-
tive.219 Complete retention of iodide ion was obtained in the presence of as high as
100-fold excess of each of 24 Na, 42K, 38C1, and 83Br. Collection of various concentra-
tions of radioiodide by isotope exchange reaction on columns packed with TBP-plas-
ticized iodine foam has successfully been carried out (Table 81).
Palagyi et al. 221 - 222 suggested the preparation of an iodine foam by immobilizing a
solution of I2 in toluene diluted liquid anion exchanger (e.g., Alamine 336 or tri-n-
octylamine) in the foam membranes. They employed the I2-(Alamine)-foam columns
for collection of radioiodide from fresh milk and also from formaldehyde preserved
milk samples. It was indicated that the presence of formaldehyde did not affect the
separation of radioiodide. On the contrary formaldehyde improved separation (Figure
74). The separation efficiency of radioiodide is also influenced by the quality of milk,
flow rate of the sample, and to some extent the age of column filling. In the case of
milk with high fat content it was necessary to use lower flow rates. In all the cases, it
80 -
50 -
20 40 60 80 100
FORMALDEHYDE, ml
FIGURE 74. Effect of formaldehyde (given in ml I ' of milk) on the separation effi-
ciency (%) under static conditions. (From Palagyi, S. and Markusova, R., Radiochem.
Radioanal. Lett., 32, 103, 1978. With permission.)
was possible to separate 131I from a 1-jf milk sample with over 80% separation effi-
ciency in less than 15 to 20 min, including washing the foam cubes and their prepara-
tion for radioactivity counting. Since 1 g of foam filling can easily be pressed into a
volume of 3.5 mi, a higher than 250-fold preconcentration of the separated radioiod-
ine could be attained.
Distribution of the radioactivity of the collected iodine is shown in Figure 75. Ob-
viously, this distribution is a function of the method used for packing the foam into
the column.
Iodine solutions in toluene in the presence and absence of a liquid anion exchanger
(e.g., TOA) have also been employed for the preparation of iodine foam. 222 The rate
of separation of radioiodide by iodine foams was found to be quite high with equilib-
rium attained in less than 10 min. Generally polyurethane foams treated with the iodine
solution containing TOA showed better separation efficiencies than those loaded with
iodine solution only. In the absence of TOA, the separation of radioiodide by iodine
foam proceeds by an isotope exchange mechanism according to the equation:
2 m r (aq) + L, (foam) = 2 T (aq) + '"I 2 (foam) (27)
whereas in foams treated with a solution of I 2 in TOA, the mechanism is more compli-
cated.
The efficiency of iodine separation is slightly decreased by increasing the flow rate,
but separation is quite complete at flow rates as high as 150 mi. min"1 (column diame-
ter, 10 mm) (Table 82). The separation efficiency is generally decreased by increasing
the volume of the sample analyzed. The proposed method was successfully employed
for the separation of 13II from natural waters and there is practically no interference
from foreign ions usually present in hard water. 222
The application of pulsated column methods for the separation of radioiodide by
iodine foams has also been described.223'226 The separation of radioiodide in these sys-
145
10 15 20 25
FIGURE 75. Distribution of the I3 'I radioactivity along the column (radioiodine was separated at 60 ml
min~' flow rate, gamma-radioactivity was measured under a 0.5-cm Pb-slit, the column bed height is indi-
cated by arrows and the background level by dotted line). (From Palagyi, S. and Markusova, R-, Radi-
ochem. Radioanal. Lett., 32, 103, 1978. With permission.)
Table 82
SEPARATION OF 131I UNDER VARIOUS CONDITIONS (100 AND
1000 ml OF 0.0001 MNal IN 0.1 M HC1 AND 1.0 g OF FOAM
TREATED WITH 2.5 mi OF 0.1 MI 2 SOLUTIONS);
THEORETICAL VALUES IN PARENTHESIS
Separation efficiency in
100-mjf sample 1000-m/ sample
Method of Flow rate I2 in Iz in 10% li in j in 10

separation mt min"1 toluene TOA toluene TOA
10 92.1 95.0 85.0 90.8

50 91.8 94.7 84.9 90.7
Dynamic technique 100 91.2 94.5 83.7 89.9
150 90.6 94.2 81.3 87.7
(99.0) (90.6)
Static technique Shaking 96.0 98.5 71.9 77.6
10 min (98.0) (83.3)
From Palagyi, S. and Bila, E,, Radiochem. Radioanal. Lett., 32, 87, 1978. With permis-
Table 83
THEORETICAL (Et) AND
EXPERIMENTAL (E«)
EFFICIENCY OF >31I
SEPARATION FROM VARIOUS
VOLUMES OF AQUEOUS
PHASE (W0) IN THE OPEN
ARRANGEMENT, USING I2-
AMINE-FOAM FILLING
No. of 20 Separation effi-

ml ciency (%)
fractions
(n) W. (ml) E, E.
5 100 100.0 98.9

10 200 100.0 98.8
15 300 100.0 98.7
20 400 99.9 98.6
25 500 99.9 98.5
30 600 99.9 98.6
35 700 99.9 98.5
40 800 99.8 98.4
45 900 99.8 98.4
50 1000 99.8 98.4
From Braun, T. and Palagyi, S., Anal.

Chim., 51, 1697, 1979. With permission.
terns in an open or closed arrangement depends on the number of pulses and the resi-
dence time of the aqueous phase in the syringe assuming that all other factors (e.g.,
solution pH, concentration of I2 on the foam, concentration of I" in aqueous solution,
etc.) are kept at the optimum values. It was found that for foam loaded with I2-amine
complex,606 2 to 3 pulses were quite enough to reach equilibrium (practically 100%
separation efficiency), but for foams loaded with iodine, about five or more pulses
were necessary. The effect of residence time of the aqueous phase in the iodine foam
syringe (pulsed column) during one particular pulsation was found to be insignificant.
In closed and open arrangements of the pulsated column operation, the separation
efficiencies measured were in good agreement with those theoretically calculated.60b
Slight differences were observed in the case of adding a liquid anion exchanger to the
iodine loading solution (Table 83). The most suitable concentration of iodide carrier
lies between 10~5 to 10'3 MNal (Figure 76).
The pulsating column method was successfully employed for the separation of 131I
from natural waters.60* Radioactivity was measured directly in the syringe. The results
obtained in an open arrangement and given in Table 84 show that foam cylinders
loaded with I2-Alamine 336 complex can be stored for more than 10 days.
It was also reported that the closed arrangement of the pulsated column method can
be easily automated.224 This offers the basis for a new type of device applicable in
environmental radioactivity monitoring. Iodine was separated from tap water (1 jf)
using the automatic pulsating column method with almost 95% efficiency after 500
pulses (i.e., 1 hr). Increasing the iodine content (e.g., 2.5-fold) on the foam, the num-
ber of pulses could be reduced to 200 to obtain the same separation efficiency of ra-
dioiodide(i.e., 95%).
The separation of radioiodide from fresh and formaldehyde preserved milk samples
147
100
80
,,r 60
40
10" 10" 10" 10" 10"
FIGURE 76. Effect of the concentration of I" on the efficiency of 13I I separation
from 200-m.f sample in the open arrangement. (From Braun, T. and Palagyi, S., Anal.
Chem., 51, 1697, 1979. With permission.)
Table 84
EFFECT OF STORAGE OF THE FOAM
FILLING ON EXPERIMENTAL
EFFICIENCY (E.) FOR W a = 200 mi
E,, %, for foam loaded with

Time of storage,
days in toluene I2 in dilute amine
0 93.4 98.8
1 93.5 98.9
2 92.1 98.9
4 92.6 98.7
7 90.0 98.5
11 89.5 98.5
From Braun, T. and Palagyi, S., Anal. Chem., 51, 1697,

by the pulsating foam column method has also been reported.225 Both open and closed
arrangements gave good separation yields. A concentration factor of more than 500
with recoveries of greater than 95% could easily be achieved.
The separation of radiosilver by isotope exchange separation of silver dithizonate
foam has been described.219 The isotope exchange reaction of silver on silver dithizon-
ate foam can be represented by the following equation:
*Ag + (aq) + AgHDz (foam) = Ag + (aq) + *AgHDz (foam) (28)
where the asterisk denotes the radioisotope of silver. The rate of retention of radiosil-
ver from nitric acid solution on TBP-plasticized silver dithizonate foam as examined
Table 85
COLLECTIONS OF VARIOUS
CONCENTRATIONS OF
RADIOSILVER BY ISOTOPE
COLUMNS PACKED WITH
SILVER DITHIZONATE FOAM
Average Ag Relative
Amount of exchanged accuracy
Ag taken on foam of the mean
^g X(%) (%)
0.01 97.7 -2.3

0.1 98.4 -1.6
0.5 98.5 -1.5
1.0 98.6 - 1.4
From Braun, T. and Farag, A. B., 3. Ra-

dioanal. Chem.,25, 5, 1975. With permission.
in batch experiments was found to be quite fast. In column experiments, quantitative

recoveries of radiosilver were obtained at flow rates of 5 mi min~' (column diameter,
15 mm) (Table 85).
C. Polyurethane Foams for Trapping Volatile Combustion Products in Organic Mi-

croanalysis
On the basis of the successful results obtained for the quantitative retention of var-
ious inorganic and organic species in aqueous and gaseous media on polyurethane
foams, Farag et al. 227 ~ 2 2 9 suggested the application of these foams for trapping some
volatile combustion products in organic microanalysis. Untreated polyether polyure-
thane foam was found 227 quantitatively to retain iodine produced during the combus-
tion of iodoorganic compounds by various packed and empty tube combustion meth-
ods. 227 A short layer of the foam material placed at the cooler end of the combustion
tube selectively and completely removed iodine from the combustion products which
were then swept as usual by the oxygen gas stream to the water and carbon dioxide
absorption tubes. Furthermore, a standard Pregl absorption tube packed with 0.5 g
dry foam maintained at room temperature and connected between the combustion and
the water absorption tubes (anhydrone tube) proved to trap iodine produced during
the combustion of iodoorganic compounds by four different combustion procedures.
Iodine was determined simultaneously with carbon and hydrogen from the gain in
weight of the foam sorption tube. The combustion methods examined were the rapid
straight empty tube, 228 the rapid empty tube method of Belcher-Ingram, 229 rapid flash
combustion,230 and the cobaltocobaltic oxide method 231 (packed tube combustion
method). Figure 77 shows a schematic diagram for the position of the foam sorbent in
external and internal sorption of iodine in the rapid straight empty tube method. The
results obtained for the simultaneous microdetermination of carbon, hydrogen and
iodine in several iodoorganic compounds by the above-mentioned combustion methods
employing the foam material for the external sorption of iodine are summarized in
Table 86. Obviously, the use of inexpensive polyurethane foam for the retention of
iodine at room temperature instead of other sorbents, e.g., silver which is usually used
for the sorption of iodine at high temperatures, is attractive. The useful life of the
foam sorption tube (containing 0.5 g foam) was found to be about 15 to 20 analyses
149
a. External Absorption of Iodine

Extension Metal Piece
1900-9501 r
Soda-
Asbestos
Pure Dry 1^ 1£ II I 1 Polyurethane Anhvdronp
to- U Combustion Run! Electric Furnace Foam Tube Tube Anhydrone
Oxygen ^ M
I
Combustion Run ^=5Û. Compressed Air
'^ Butane Gas
Mixture
Anhydrone Soda-
b. Internal Retention of Iodine Tube Asbestos
|900 - 950[
Anhydrone
FIGURE 77. The rapid straight empty tube apparatus. (From Farag, A. B., Attia, M. E., and Hassan, H.
N. A., Indian J. Chem., B20, 693, 1981. With permission.)
depending on the percentage of iodine. Presence of other halogens and sulfur interfere
with the proposed method because they are sorbed to a certain extent on the foam.
Polyurethane foam was suggested as a suitable material to form a filter bed on which
mercury vapors, 228 produced during the decomposition of organomercury compounds
with various dry-combustion methods, could be retained. A layer of about 7 cm packed
in the cooler part of the combustion tube was examined by repeatedly analyzing phen-
ylmercuric acetate and other organomercury compounds employing the rapid straight
empty tube combustion method. Correct carbon and hydrogen results were obtained
in more than 20 runs by using the same sorption tube which indicate the complete
retention of mercury vapors produced during the decomposition of organomercury
compounds. The use of a short foam layer eliminates the troubles frequently caused in
the determination of carbon and hydrogen in organomercury compounds due to the
high volatility of mercury produced during the decomposition of these compounds.
Also, the application of the foam sorbent, at room temperature, for the retention of
mercury in organic compounds is more convenient than any other expensive reagent
(e.g., gold, 232 usually employed for the same purpose). Furthermore, 0.5 g untreated
polyurethane foam packed in a standard Pregl absorption tube connected between the
combustion and water absorption tubes was successfully employed for the quantitative
retention of mercury in organic compounds.228 In this case, mercury could be deter-
mined together with carbon and hydrogen from the increase in weight of the absorp-
tion tube. The foam tube was found to function efficiently also with other combustion
methods; namely, the rapid empty tube method of Belcher-Ingram, the rapid flash
combustion method, and the cobaltocobaltic oxide method. Table 87 shows, for ex-
ample, the results obtained for the simultaneous determination of carbon, hydrogen
and mercury in various organomercury compounds using the rapid straight empty tube
method. A manganese dioxide tube or silica gel (suitably treated with a sulfuric-
chromic acid mixture) tube connected as usual between the water and carbon dioxide
absorption tubes was employed for the elimination of nitrogen combustion products
produced from the combustion of organic compounds containing nitrogen.
Organomercury compounds containing halogens have been successfully analyzed
(Table 87). The halogens (chlorine or bromine) were sorbed on a silver wool layer
placed in the combustion tube after the main combustion furnace and kept at 550°C
by means of a short furnace.
Table 86
SIMULTANEOUS MICRODETERMINATION OF CARBON, HYDROGEN,
AND IODINE IN ORGANIC COMPOUNDS
Found (%)
^•dlV,.
Compound (%) A B C D
lodobenzoic acid C 33.95 33.90 + 0.153 34.02 + 0.144 34.19 + 0.126 34.04 ± 0.232
H 2.03 2. 16 ±0.067 2.10 ± 0.122 2.21 ±0.126 2.20 + 0.083
I 51.17 51. 39 ±0.102 51.02 ±0.148 50.96 ± 0.071 51.03 ±0.251
Phenyl(trimethyl)- C 41.08 41.18 ± 0.235 41.18 + 0.232 41. 17 ±0.155 41.03 ±0.315
ammonium iodide H 5.36 5.46 ± 0.092 5.39 ± 0.293 5.47 ±0.158 5.29 + 0.214
I 48.23 48.27 + 0.369 48.31 ±0.145 48.26 + 0.184 48. 14 ±0.373
lodoform C 3.05 3.24 ± 0.093 3.31 ±0.045 3.29 ± 0.032 3.30 + 0.055
H 0.26 0.39 ± 0.048 0.64 + 0.045 0.60 ± 0.083 0.56 ± 0.071
I 96.69 96.53 ± 0.248 96.54 + 0.338 96.54 ± 0.228 96.57 ± 0.114
p-Iodoanisole C 35.92 36.04 ±0.319 36.16 ± 0.138 35.89 + 0.148 35.87 ± 0.232
H 3.02 3.17 + 0.057 3.32 + 0.032 3.16 + 0.214 3.17 ±0.129
I 54.23 54.27 ± 0.337 54.22 + 0.342 54.24 + 0.226 54.23 ± 0.277
o-Idophenol C 32.76 32.85 + 0.174 33.02± 0.077 32.86 + 0.236 32.76 ± 0.182
H 2.29 2.37 ± 0.022 2.64 ± 0.077 2.38 ±0.241 2.43 + 0.235
I 57.68 57.55 ± 0.227 57.49 ± 0.311 57.59 ± 0.254 57.48 + 0.084
Research (I) C 49.12 49. 30 ±0.261
C, 6 H V4 N 3 OI H 3.61 3. 80 ±0.107
I 32.44 32.57 ±0.161
Research (II) C 44.92 44.99 ± 0.283
C 16 H, S N 3 0 5 I H 3.35 3. 54 ±0.188
I 26.37 26.38 ±0.172
Research (III) C 50.39 50.47 ±0.149
C17H16N,OI H 3.98 4.04 ± 0.227
I 31.32 31.31 +0.218
Research (IV) C 31.96 31.06 ±0.212
C7H6O NI H 2.30 2.43 ± 0.239
I 48.25 48.28 ± 0.186
Research (V) C 37.66 37.65 ±0.189
C,H6NO2I H 2.11 2.13 + 0.214
I 44.21 44.24 ±0.179
Research (VI) C 35.45 35.41+0.199
C,H8N03I H 2.64 2.77 ± 0.099
I 41.60 41.60 ±0.223
Note: Each datum given for percentage is an average of four determinations. A = rapid straight
empty tube method; B = rapid empty tube method of Belcher-Ingram: C = rapid flash com-
bustion method; D = cobalto-cobaltic oxide method.
From Farag, A. B., Attia, M. E., and Hassan, H. N. A., Indian J. Chem., 20B, 693, 1981. With
permission.
Table 87
SIMULTANEOUS MICRODETERMINATION OF CARBON,
HYDROGEN, AND MERCURY IN ORGANOMERCURY
COMPOUNDS BY THE RAPID STRAIGHT EMPTY TUBE
METHOD OF KORSHUN AND KLIMOVA
31U
Av found' dev
Compound Element Calc W (s)
Phenylmercuric acetate C 28.54 28.52 0.212

H 2.39 2.50 0.089
Hg 59.57 59.48 0.222
Mercuric benzoate C 36.32 36.43 0.230
H 3.04 2.93 0.103
Hg 43.34 43.38 0.279
Mercuric acetate C 15.07 14.86 0.112
H 1.90 2.16 0.055
Hg 62.94 62.88 0.218
Mercuric oxalate C 8.32 8.34 0.185
H 0.00
Hg 69.50 69.54 0.279
Mercuric tartarate C 13.77 13.70 0.233
H 1.15 1.29 0.148
Hg 57.53 57.56 0.259
Fluoresce in mercuric acetate C 33.92 33.93 0.215
H 1.89 1.98 0.126
Hg 47.22 47.23 0.235
Research (I) C 10 H M N 2 O 5 Cl 4 Hg C 20.75 20.64 0.145
H 4.17 4.30 0.211
Hg 34.66 34.64 0.307
Research (II) C,H 14 NO 3 Cl z BrHg C 20.17 20.22 0.258
H 2.63 2.75 0.231
Hg 37.45 37.57 0.227
Fluoresceinmercuric acetate C 33.92 33.93 0.215
H 1.89 1.98 0.126
Hg 47.22 47.23 0.235
Research (I) C 10 H J6 N ; O s Cl 4 Hg C 20.75 20.64 0.145
H 4.17 4.30 0.211
Hg 34.66 34.64 0.307
Research (II) C,H I4 NO,Cl 2 BrHg C 20.17 20.22 0.258
H 2.63 2.75 0.231
Hg 37.45 37.57 0.227
Average of four determinations.
From Farag, A. B., Attia, M. E., and Hassan, H. N. A., Anal. Chem., 52, 2153,
Untreated polyurethane foam retains to some extent chlorine and bromine produced
from the combustion of chlorinated and brominated organic compounds. Unfortu-
nately, the retention of these halogens is not quantitative.229 On the other hand heter-
ogeneous cation exchange foam in the silver form was found to retain these halogens
more efficiently than the untreated foam.229 A standard Pregl absorption tube filled
(two-thirds) with 1 g of the vacuum-dried silver foam, backed with anhydrone (anhy-
drous magnesium perchlorate) and connected between water and carbon dioxide ab-
sorption tubes, proved to retain quantitatively chlorine and bromine produced in the
153
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155
decomposition of organochlorine and organobromine compounds, respectively. As in

the case of iodine 227 and mercury, 228 simultaneous determination of carbon, hydrogen,
and halogen was achieved by gravimetric methods. The results obtained by three dif-
ferent rapid empty tube combustion methods are summarized in Table 88. Using the
proposed silver foam tube at room temperature is obviously more convenient than
using a silica absorption tube packed with silver gauze at 500°C for the sorption of
these halogens.
D. Polyurethane Foams for Trapping Enzyme Inhibitors and the Immunoadsorption

of Cells
The most serious disadvantage of using enzymes in routine analyses is their high
cost, which limits the application of large amounts of these expensive chemicals. Bau-
man et al. 234 - 235 suggested the immobilization of enzymes on open-cell polyurethane
foams in order to increase the utility of these enzymes in various analytical applica-
tions. They described a method for the preparation of immobilized horse-serum cho-
linesterase products in which the enzyme in a starch gel is physically entrapped on the
surface of open-cell polyurethane foam pads. The starch gel was prepared by mixing
starch powder with 0.1 M tris (hydroxy-methyl)-aminomethane buffer, pH 7.4, and
the cool slurry was poured into a boiling mixture of the tris buffer and glycerine. The
starch solution was then cooled to 47°C and a solution of horse-serum cholinesterase
in tris buffer (at 47°C) was poured on it. The enzyme-starch solution was gently stirred
for 10 sec, and immediately poured onto an open-cell polyurethane foam sheet. The
solution was gently worked into the foam with special care to minimize foaming; then
the foam pad was gently squeezed to remove the excess liquid. The pad was set into a
refrigerator to gel and then dried in a vacuum desiccator (containing no desiccant)
overnight.
The immobilized enzyme pad could be used to monitor water and air continuously
for atmospheric pollutants which inhibit cholinesterase. The air was sampled and a
solution of substrate (5 x 10"" Mbutyryl-thiocholine iodide in tris buffer, pH 7.4) for
the enzyme was pumped simultaneously and continuously through the immobilized
enzyme pad; the activity of the enzyme was monitored continuously by passing an
electric current through platinum electrodes in contact with the immobilized enzyme
pad and observing changes in the electrode potential. The method is based on the
hydrolysis of butyrylthiocholine iodide to the easily oxidizable thiocholine iodide and
butyric acid as long as the enzyme cholinesterase is active in the foam pad according
to the equation:
CH 3 r
' Ch F
CH 3 -N + —CH 2 -CH 2 -S-C-C 3 H 7 —>
I II
CH3 0
CH3r
CH 3 -N + -CH 2 -CH 2 -SH + C 3 H 7 COO" (29)
CH3
At a constant current of 1 Â, a potential of approximately 150 mV will be established

across the cell (Figure 78). If no enzyme is present in the pad, no thiol will be formed
and the potential will rise to that of iodide/iodine couple (350 to 400 mV).
* 5/8 Dia. ».
3/B
t /
1 Dia.
1 I
O
O
o O O
I C ) ° 0 § 0 ° C>
^
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1/16 Dia Holes
Platinum
™w<r~(\CKv.tt'/.Ks:p*
HolderS.
O—Ring
° Enzyme Pad
Platinum Anode
Fritted Disc
FIGURE 78. Details of enzyme pad, O-ring and grid electrode assem-
bly. (From Bauman, E. K., Goodson, L. H., Guilbault, G. G., and Kra-
mer, D. N., Anal. Chem., 37, 1378, 1965. With permission.)
The immobilized cholinesterase can be used analytically in much the same way that
the soluble enzyme is used, that is, to determine concentration of a substrate, an inhib-
itor that inactivates the enzyme, or an activator that provides an acceleration in enzyme
activity.
On the basis of this work, Goodson and Jacobs236 designed an automatic system for
monitoring water supplies for organophosphates (Figure 79). Ten gallons of river water
can be passed through an enzyme pad without any detectable loss in enzyme activity.
In one test, the authors pumped city tap water through a single enzyme pad for 68 hr;
more than half of the enzyme activity was lost, but the residual enzyme activity was
still enough to produce an alarm in the instrument.
Several proteins and aluminum hydroxide were tested for sorption of cholinesterase
to increase its retention by a starch gel matrix.237 The sorbed cholinesterase was then
applied to sheets of open-pore polyurethane foam for evaluation. Enzyme pads pre-
pared by coprecipitation of cholinesterase with aluminum hydroxide gel followed by
entrapment in starch gel on the surface of open-pore polyurethane foam gave improved
157
ate
Water/Air Inlet
-Enzyme Holder
f- to> Waste
FIGURE 79. Cross section of electrochemical enzyme cell showing connections for the constant current
supply and the electrometer. (From Goodson, L. H. and Jacobs, W. B., Control of Hazardous Material
Spills, U.S. Environmental Protection Agency, Washington, DC, 1973, 129. With permission.)
activity and washout resistance. The foam pads have high enzyme activity and are easy
to prepare in large quantities, uniform in their activities, and suitable for use in the
electrochemical cell system for monitoring either air or water for cholinesterase inhib-
itors. When 2700 i of water were pumped through an enzyme pad to monitor organo-
phosphates in a water supply, a useful quantity of enzyme remained in the pad at the
end of the test period.
A detailed study has been made of the sensitivity of the "Continuous Aqueous Mon-
itor System" with cholinesterase-treated polyurethane foam pads for a variety of pes-
ticides.238 The sensitivity of the system was greater for P=O than for P=S compounds.
Response of the system to carbamate-type insecticides is good, and there is no response
to chlorinated hydrocarbon insecticides, herbicides, fungicides, or rodenticides.
Reticulated polyester polyurethane foams, the cells of which are free of residual
membranes, proved to be a suitable matrix for immunoadsorption of cells without
appreciable mechanical entrapment.239 Although the untreated foam has a high affinity
for guinea pig erythrocytes, the adsorption is not specific. The nonspecific affinity can
be greatly reduced by pretreating the foam with various polyanions, e.g., carboxyme-
thyl cellulose, polyacrylic acid, gammaglobulin, and gum arabic. Immunospecific
binding of erythrocytes can be achieved by adding antierythrocyte antibody to a gum
arabic solution used to protect the foam. The foam columns are mounted in a horizon-
tal position and rotated centrifugally to prevent rapid sedimentation of cells before
they come in contact with the foam surfaces. A single antibody-coated foam disk (1
in. diameter, 0.5 in. thick) can bind up to 3 x 10* guinea pig erythrocytes. The specific-
ity of this method was further proved by the finding that erythrocytes coated with
heptens were bound specifically to foam coated with their corresponding antihepten
antibodies, with a low background of cross-reactivity.
159
Chapter 2
OPEN-PORE POLYURETHANE (OPP) SORBENTS
I. INTRODUCTION
As shown, foamed polyurethane sorbents have been utilized for numerous analytical
chemistry applications, mostly in the area of collection, separation, and recovery of
inorganic and organic compounds from aqueous solutions and gaseous media. On the
other hand, however, open-pore polyurethane (OPP) sorbents have been employed
mostly in column chromatographic applications. OPP was first applied to column
chromatography by Salyer et al.240 241 and it subsequently found utility in gas242 24S and
liquid chromatography. 242 ' 246 " 248 Recently it has been applied for the recovery and/
or removal of various compounds from water. Navratil et al. 249 ' 251 tested it to recover
some polynuclear aromatic hydrocarbons (PAHs) and surfactants from water, and
others 61 - 252 have tested it for the removal of amines, nitrogen heterocyclics, phenols,
and PAHs from coal conversion waste water streams.
The favorable properties of OPP are what make it a useful separation material and
chromatographic support. Its unique polymer structure is not a resilient network of
membranes on dodecahedral cells as found in foamed polyurethane but is composed
of agglomerated hollow spherical membranes bonded to each other in a rigid, highly
permeable structure; its permeability facilitates high solvent and gas flow rates. The
spheres are very uniform with diameters of 1 to 10 îrn, much smaller than cells of
foamed polyurethane. OPP is unique among supports used in column chromatography
in that it is polymerized in situ and adheres to the column walls thus reducing channel-
ing effects.
Jefferson and Salyer253 were the first to prepare OPP by relatively slow precipitation-
polymerization of an isocyanate and a polyol in carbon tetrachloride-toluene solution.
By controlling the reaction conditions, a polymer with specific density, porosity, and
surface characteristics can be prepared. It can be tailored to specific separation appli-
cations by chemically bonding functional groups at the —OH and —OCN sites. It is a
high-capacity support material, and stationary phases can be added to coat it or pref-
erably incorporated into its structure during its preparation.
The synthesis, properties, and applications of OPP have been admirably re-
viewed, 3.96.97.254-256 {,ut no); (.Q jjjg (jgpjh attempted here. An extensive overview follows
on its preparation, effect of synthesis conditions on OPP properties, compatibility and
other properties of OPP, analytical applications (gas and liquid chromatography and
collection and concentration methods), and miscellaneous applications (removal and
recovery of various organic compounds from waste water).
II. OPP PREPARATION
A. Synthesis and Reagents

The polymer is produced from relatively inexpensive precursors by a condensation
reaction of a polyaryl-polyalkylene-polyisocyanate and a polyol at room temperature
in the presence of a catalyst.253-254* The reaction mode involves the nucleophilic addi-
Usmani and Salyer256 point out that OPP structures can also be made from other thermosetting resins
and especially urea/formaldehyde/melamine/formaldehyde and copolymers thereof.
tion of a hydroxyl group to an isocyanate to yield a substituted amide ester of carbonic

acid (polyurethane):
H O
R—NCO + R' OH -> R—N—C—OR' (30)

The chemical reactions taking place in the polymerization of urethanes are reviewed
in Chapter 1. A suggested mechanism for OPP formation has been proposed as fol-
lows: 256 "The polyisocyanate and polyol component react to form organic-soluble,
short-chain oligomers. As the step-growth polymerization proceeds, molecular weight
promotion and onset of reactions which produce branching and cross-linking makes
the reaction product insoluble in the processing solvent and the product exhibits gel-
like properties; i.e., is semidispersed in a swollen phase. More molecular weight in-
crease, branching, and cross-linking make the resultant product completely insoluble
in the organic solvent. Removal of the solvent then produces the OPP structure."
The isocyanate can also react with other active hydrogens such as in amines, organic
acids, glycols, and in particular, water. The reaction of isocyanate with water produces
an amine and carbon dioxide; thus isocyanate is destroyed and CO2 causes voids to
form within the OPP structure. This reaction necessitates the drying of all reagents and
the exclusion of atmospheric water during the preparation of OPP. The condition of
the isocyanate can be checked by observing a broadening of the infrared absorption
bands at 3.0 p<m (NH 2 stretch) and 6.02 ^m. 244
Various isocyanates have been used to prepare OPP. The first type used a mixture
of polyaryl polyalkylene polyisocyanates obtained by phosgenating the reaction prod-
uct of aniline with formaldehyde. 253 The polyisocyanate has the formula:
OCN
NCO
where n has an average value of 0.5 to 2.0, containing about 40 to 50°7o diisocyanate,
the balance being tri-, tetra-, and pentaisocyanates. The material, referred to as "crude
MDI," has a functionality of about 2.5 NCO groups per molecule and an equivalent
weight of 131. Kaiser Chemicals' NCO-10, having an average functionality of ~2.3
and an equivalent weight of 132 to 135, has also been used, but is not now commer-
cially available.243 244 Most of the reported work have used OPP prepared with Mobay
Chemical Company's (Pittsburg, Pennsylvania) Mondur MR. 61 - 243 ' 253 Both NCO-10
and Mondur MR are mixtures of 4,4'-diphenylmethane diisocyanate and lesser
amounts of the tri-, tetra-, and pentaisocyanates.243 247 Mondur MR has an average
functionality of approximately 2.7 and an equivalent weight of 132.247
The usual polyol used is Union Carbide's (New York, New York) NIAX Polyol LA-
475 (polypropylene glycol), a mixture of pentahydroxyl compounds synthesized from
the total oxypropylation of diethylene triamine. The oxypropylation of the amine hy-
drogens yields the following intermediate pentahydroxyl compound:
OH
I
CH 3 —CH—CH 2 OH
N— [—CH 2 CH2 N(CH2 —CH-CH 3 ) 2 ],

161
and oxypropylation proceeds at the hydroxyl hydrogens until the average equivalent
weight of the mixture has reached 118 (functionality of five hydroxyl groups per mol-
ecule). 247
OH
I
-N-CH 2 -CH-CH 3 + CH 2 CH-CH 3 ->
\/
0
CH 3 OH
_ N _[CH 2 -C-0]—CH 2 -CH-CH 3 (31)

H
When using LA-475, no external catalyst is required as the reaction is self-catalyzing

because of the presence of the tertiary nitrogens in the structural backbone of the LA-
475 polyol monomer."
Other investigators have used the polyol monomer EPON 1001 (Shell Chemical
Company, Houston, Texas) to improve the stability of OPP at elevated temperatures.
It is an epoxide terminated polymer based on bis-phenol A with an average hydroxyl
functionality of 2.9 and an equivalent weight of 344. 245248 Because EPON 1001 has no
strongly acidic or basic functional groups that are self-catalyzing, triethylamine is
added as a catalyst.
The polymerization reaction is usually carried out in a carbon tetrachloride-toluene
(40:60 volume ratio) solvent mixture. Carbon tetrachloride, toluene, and other solvents
have been tested. However, the carbon tetrachloride-toluene mixture is most favorable
since it has a density equal to the precipitated polymer beads (1,19 g cm~ 3 ). 244 The
polymer beads remain suspended in the solvent and form a more uniform polymer
distribution. 244 Other important properties of this solvent mixture are that the mon-
omer reactants are soluble, but not the OPP polymer, and the solvents are inert both
to the reactants and products.
B. OPP Column Preparation

In preparing columns of OPP, glass or metal columns can be used, but careful clean-
ing, and in the case of glass, hydrofluoric acid etching of the inside walls, 249 ensures a
good column wall-OPP bond. Columns made of aluminum or copper can be bent to
any desired shape after being filled with polymer. For its preparation, plastic labware
is usually used since OPP does not adhere to polyethylene, polypropylene, or Teflon.
The polymer's precursors are placed in separate but equal volumes of the solvent
mixture. For example, 2.0 g Mondur MR in 25 mi solvent and 4.0 g LA-475 in 25 ml
solvent are used to prepare OPP with an OH/NCO functionality of 2.2. The reactant-
solvent mixtures are combined and mixed well. Before gelation starts taking place (5
to 20 min), the mixture is injected into the column using a disposable plastic syringe.
As the column is being filled, it is agitated or rotated to prevent the formation of air
pockets. 244 During polymerization (2 to 4 hr), the sealed column is rotated to ensure
uniform polymer distribution and prevent any settling. The reaction time, controlled
by the temperature, nature of solvent, concentration of reactants, OH/NCO ratio, and
catalysts, can continue up to 4 days and produce OPP with decreased surface area and
porosity. 242 Therefore it is necessary to remove unreacted monomer and rinse the OPP
with neat solvent upon reaching the optimum polymerization time. The solvent can be
removed and the OPP dried either by inert gas purging or heating in a vacuum oven
(60 °C). Denton et al. 252 report that flushing the OPP with n-heptane, methanol, water,
and again with n-heptane, and drying and storing in air, increased the life of the col-
umn.
The monomer reactants should be between 15 wt% and 30 wt% to produce good
OPP columns. 254 If the concentration of monomers is less than 15 wt%, the matrix
will be fragile and the resulting shrinkage will cause the OPP to pull away from the
column walls. If >30 wt% monomers are used, it will crack and open undesirable
channels.
The polymerization proceeds readily at ambient temperatures. Lower temperatures
increase gel time whereas higher temperatures decrease gel time. Reaction at both ex-
tremes of temperature may produce an undesirable OPP structure. 254 The lower reac-
tion temperature produces a less rigid structure while high temperatures may cause
convection currents in the reaction mixture, which could disrupt gel formation and
weaken the OPP structure. These and other preparation factors also have an effect on
its properties; they will be discussed in the next section.
III. PHYSICAL AND CHEMICAL PROPERTIES OF OPP

The polymer can be prepared with a number of different formulations. Upon vari-
ation of the monomer concentrations and reaction conditions during the preparation
of OPP, its density, porosity, and surface are changed. The diameter of OPP spherules
can be changed by altering the temperature of the reaction mixture or with the use of
catalysts such as tertiary amines or various organometallic compounds. OPP can be
tailored to specific separation applications by chemically bonding functional groups at
the -OH and -NCO sites of OPP. This section will review the effect the conditions of
OPP preparation has on its different physical properties as well as its various other
properties.
A. Effects of Synthesis Conditions on OPP Properties

The density (0.1 to 0.5 g cm'3) and porosity, and hence the permeability of OPP,
can be changed by varying the concentrations of the monomer reactants, the solvent,
and the reaction conditions. Table 89 illustrates the effect of total reactant concentra-
tion and solvent on OPP density, porosity, and A shore hardness.3 9 6 9 7 - 2 5 3 2 5 7 As the
reactant concentrations are increased, the OPP density and shore A hardness increased
while the porosity decreased using either carbon tetrachloride or toluene. The density
and shore A hardness values are higher and the porosity lower for OPP prepared in
carbon tetrachloride rather than in toluene. The polymer prepared in a mixture of
carbon tetrachloride-toluene had properties similar to OPP prepared in toluene alone,
whereas xylene produced a much different product. Herman and Field248 determined
the dependence of the average OPP particle diameter on the total concentration of
monomer reactants (bulk density). For OPP prepared using either excess polyol or
excess isocyanate monomer, the particle size initially decreases then approaches a lim-
iting value of approximately 1.5 ^m as the bulk density is increased (Figure 80). The
inflection point at 0.18 g cm~3 agrees with the recommended bulk density for liquid
chromatography studies.246 An increase in the uniformity of particle size and particle
sphericity was also observed as the bulk density was increased.248
A more dense OPP matrix is also produced with increased polymerization time.
Shorter reaction time produces OPP with better porosity and larger spherules, as is
illustrated by the electron micrographs shown in Figure 81.
The diameter of spherules can be varied by changing the conditions under which
polymerization occurs. In the presence of catalysts and at higher temperatures, smaller
163
Table 89
THE EFFECT OF REACTANT CONCENTRATION AND
SOLVENT ON SOME PROPERTIES OF OPP°
Density Shore A Porosity"
Total monomer (g cm'3) hardness"
reactants
ecu Toluene ecu Toluene ecu Toluene
12 0.26 0.14 0 0 79 90
15 0.32 0.18 40 0 77 86
17 0.33 0.24 57 0 74 82
20 0.38 0.27 65 28 74 81
25 0.38 75
25" 0.36 79 74
25' 0.24 0 80
° OPP prepared with Crude MDI and LA-475 at OH/NCO = 1.0.

* Determined using ASTM D676.
Determined using a Beckman Model 930 Air Comparison Pycnometer.
* Carbon tetrachloride: toluene solvent mixture (1:1 weight ratio).
Xylene solvent.
From Jefferson, R. T. and Salyer, I. O., U.S. Patent 3, 574, 150, 1971.
10
9
OH/NCO = 0.5
8
I 5
I I
0.1 0.2 0.3
BULK DENSITY (g/cm 3 )
FIGURE 80. Dependence of the average OPP particle diameter on the initial mon-
omer bulk density for OPP prepared at 21 °C, Bulk density defined as the total grams
of monomers per milliliters of monomers and solvent. (From Herman, D. P. and Field,
L. R., J. Chromatogr. Sci.,99, 123, 1974. With permission.)
3!
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FIGURE 82. Dependence of average OPP particle diameter on the amount of catalyst
added and reaction temperature for OPP with a bulk density of 0.215 g cm'3, (a) OH/
NCO = 0.5; (b) OH/NCO = 2. (From Herman, D. P. and Field, L. R., J. Chromatogr.
Sci.,99, 123, 1974. With permission.)
spherule diameters result.243 Figure 82 shows the dependence of the average OPP par-
ticle diameter on the amount of catalyst added and the reaction temperature.248 The
particle diameters decreased with increased catalyst concentrations and reaction tem-
perature. Herman and Field248 showed that increasing the temperature of reaction re-
sults in decreasing the magnitude of the effect of catalyst concentration on particle size
and vice versa. Denton et al.252 observations are in agreement with the above data.
Figures 83 and 84 show electron micrographs of OPP prepared with various catalysts
and under different temperatures, respectively. There is a general increase in the for-
mation of more uniform spheres as the catalyst was added and changed from DBTDL
and EuFOD. The OPP particles became more oblong and mishappen as the reaction
temperature was decreased, but the low-temperature formations exhibited more fine
structure.
The effect of isocyanate functionality was briefly studied and found to exert little
influence on the OPP density and porosity, 3 9 6 9 7 2 5 3 2 5 7 but was claimed to influence the
average surface area (0.4 m2 g~'). 242 However, the OH/NCO functionality ratio does
appear to affect the OPP density, shore A hardness, and porosity (Table 90), and
average particle diameter (Figure 80). Scanning electron micrographs of polyurethane,
prepared with OH/NCO functionality ratios of 1 and 2.2 (Figure 85), show that the
lower functionality produces a more uniform and well formed OPP.
The OH/NCO ratio can be varied to leave either excess hydroxyl groups or isocyan-
ate groups on the OPP and change the surface functionality of the OPP. 246 OH/NCO
ratios were varied from 1:30 to 10:1. Useful gels were found to be formed in the range
of 1:2.0 to 2.0:1; gels just outside this range were slow in forming. 249 The OPP pre-
pared from a 1:2 ratio of Mondur MR-LA-475 as compared to the 1:1 formulation
had less polar character.245
167
(DBTDL)
FIGURE 83. Electron micrographs of OPP prepared using different catalysts. DBTDL = dibutyltindilaur-
ate; EuFOD = 2,2-dimethyl-6,6,7,7,8,8,8-heptafluro-3,5-octanedione, europium(III). OH/NCO = 2.2;
24°C; 59 hr. (From Denton, M. S., Dinsmore, S. R., Brand, J. I., Beams, J., and Ball, F. L., Sep. Sci.
Technol., 15, 587, 1980. With permission.)
(EuFod)
FIGURE 83 (continued)
169
(NONE)
FIGURE 84. Electron micrographs of OPP prepared at different temperatures. OH/NCO = 2.2; 59 hr.
(From Denton, M. S., Dinsmore, S. R., Brand, J. I., Beams, J., and Ball, F. L., Sep. Sci. Technol., 15,
171
(24° C)
173
Table 90
THE EFFECT OF OH/NCO FUNCTIONALITY RATIO
ON SOME PROPERTIES OF OPP
Total monomer
reactants Density Shore A Porosity'
(wt%) OH/NCO (gem" 3 ) hardness- (%)
18 0.95 0.23 — 86
1.00 0.24 10 81
25 1.00 0.38 88 75
1.03 0.38 90 74
1.05 0.33 85 77
1.11 0.41 91 70
° Determined using ASTM D676.

* Determined using a Beckman Model 930 Air Comparison Pycnometer.
From Jefferson, R. T. and Salyer, I. O., U.S. Patent 3,574,150, 1971.
B. Compatibility and Other Properties of OPP

The highly cross-linked composition of OPP makes it relatively resistant to chemical
attack. Polyurethane is compatible with a number of solvents and dilute acids. Table
91 shows its weight losses after passing 1 I of various solvents through 10-cm columns.
There is a general decreasing (OH/NCO= 2.22) weight loss with decreasing organic
solvent polarity. Hansen and Sievers247 proposed that as the OPP swells it loses un-
reacted polyol or possibly some low molecular-weight oligomers are removed from it;
they concluded that no gross dissolution or destruction of OPP is occurring, especially
since the polymer with OH/NCO ratio of one has a very small weight loss (Table 91).
Lynn et al.,246 measured the effect of various solvents on OPP length increase and
found that only dimethylformamide severely altered the OPP. Navratil et al. 249 found
that the OPP-column bond could withstand fairly high pressures after prolonged con-
tact of various organic solvents, water, and dilute acids. However, dilute bases broke
the OPP to glass column bond easily.
The OPP structure is compressible, and complete recovery does occur for compres-
sion of less than 20% without damage to the particles.256 A comparison of the stress-
strain compressive strength of OPP with that of conventional rigid and flexible forms
is shown in Figure 86.257
Polyurethane with two different formations (OH/NCO = 1.0 and 2.2) was found to
have no cation exchange properties but exhibits low-capacity, weak-base anion ex-
change characteristics. 249
Polyurethanes are not usually very thermally stable, but this property was found to
be improved by the amount and type of polyol used. Thermogravimetric analysis of
the 1:1 Mondur MR-LA-475 polymer system in nitrogen showed thermal decomposi-
tion beginning at 200°C, 10% and 27% weight loss at 250°C and 300°C, respectively,
and almost complete destruction at 500°C.244 OPP prepared from Mondur MR-EPON
1001 in a 1:2 weight ratio (OH/NCO = 0.77) showed only 0.6% and 2% weight losses
at 250°C and 300°C, respectively.245 OPP containing a greater proportion of Mondur
MR showed even higher temperature stability.
IV. ANALYTICAL CHEMISTRY APPLICATIONS
The unique preparation method and properties of OPP make it valuable for many
types of analytical chemistry applications, including chromatographic separations. The
FIGURE 85. Electron micrographs of OPP prepared with different OH/NCO functionality ratios (left
micrograph = OH/NCO = 1.0; right micrograph = OH/NCO = 2.2). 0°C, 59 hr. (From Denton, M. S.,
Dinsmore, S. R., Brand, J. I., Beams, J., and Ball, F. L., Sep. Sci. Technol., 15, 587, 1980. With permis-
sion.)
175
Table 91
OPP-SOLVENT COMPATIBILITY
Percent weight loss of OPP after passing

Solvent 1 I of solvent through 10-cm column
polarity
Solvent (AY OH/NCO = 2.22 OH/NCO = 1.00
n-Heptane 7.4 0.2

Cyclohexane 8.2 0.8
Hexanes 2.2
Ethylacetate 8.6 6.9
Toluene 8.0 9.4
Chloroform 9.1 9.9
Tetrahydrofuran 9.1 9.5 1.7
1,2-Dichlorethane 9.7 8.9
Dichloromethane 9.6 1.5
Methanol 12.9 1.2
Ethanol 11.2 1.2
/sopropanol 10.2 8.8 1.0
Hydrochloric acid ( 1 M ) 7.6
Nitric acid (1JW) 1.2 (gain)
Water 21.0 2.5
Ammonium hydroxide (1 M) 3.5
Sodium hydroxide (1JW) 1.1
Note: 0.197 g nvT1 bulk density, OH/NCO = 2.22 or 1.00.
• Hildebrand solubility parameter.
From Hansen, L. C. and Sievers, R. E., /. Chromatog.,99, 123, 1974; and Navratil, J.
D., Sievers, R. E., and Walton, H. F., Anal. Chem.,49, 2260, 1977. With permission.
method of polymer synthesis allows easy preparation of almost any size or configura-
tion of gas or liquid chromatographic column. The packing is uniform and adheres
tightly to column walls, preventing channeling. OPP can be tailored to many specific
applications by addition of liquid phases to the starting monomers to give a polymer
with a uniform phase distribution. If the liquid phase contains groups capable of re-
acting with the OPP, then a bonded phase can be obtained. Various types of fillers
(including particulate nickel, activated carbon, etc.) can be incorporated into OPP
during polymerization. 258 The narrow spherical size distribution and openness of the
gross packing structure of the polyurethane result in good mechanical strength, high
permeability, and high capacity supports for high-speed, low-pressure drop chromat-
ographic separations as well as for collection, recovery, and concentration purposes.
A. Gas-Solid Chromatography
The application of uncoated OPP for gas-solid chromatographic separation was sug-
gested in 1968.240 Salyer, Ross, and Jefferson 2 4 1 2 4 2 showed that eight normal hydrocar-
bons could be separated and eluted in the order of their increasing boiling points (Fig-
ure 87). Hileman et al.243 reported that polar compounds containing protons capable
of hydrogen bonding are separated and eluted in the probable order of the acid
strength (Table 92) of the available proton. The elution order results from the abun-
dant tertiary nitrogen atoms and carbonyl groups which make the uncoated OPP very
susceptible to hydrogen bonding.
The polar nature of OPP was used to separate geometrical isomers of various metal
chelates. C/sand trans isomers of Cr(tfa)3 (Figure 88) were completely resolved within
177
3000
1000
cc
H
tn
500
100
10 20 30 40 50 60 70 80 90 100
STRAIN, %
FIGURE 86. Compression stress-strain curves of conventional rigid and flexible ure-
thane foams compared with OPP. (From Doyles, E. N., The Development and Use of
Polyurethane Products, McGraw-Hill, New York, 1971. With permission).
6 min.243 The complete separation of cisand trans isomers of Rh (tfa)3 were also com-
pletely resolved on OPP.244 The difference in the polarity of the isomers results in the
elution of the trans isomer in half the time of the polar cis isomer. This separation
technique was used to perform rate and equilibrium studies of cis-trans isomerization
of Cr(tfa) 3 in the gas phase.259
Separations on uncoated OPP involve gas-solid adsorption as demonstrated in a
study of retention times and peak shapes of dodecane with varying sample sizes. 243 - 244
Decreasing retention times and increasing tailing was observed with larger samples,
typical of gas-solid chromatography. Overloading becomes a problem with sample
sizes over 0.4 mg.
An important consequence of the gas-solid behavior of OPP is that once the mini-
mum HETP has been obtained, the efficiency of the column does not decrease with
increasing flow rate over a wide range. 243 244 Hileman 244 showed, using a van Deemter
plot, that there was no loss in plate number with flow rates as high as 150 ml min"1.
This behavior corresponds to a small mass transfer term in the van Deemter equation
and shows that equilibrium in the adsorption process is achieved very rapidly.
The permeability of OPP columns was found to be substantially better than micro-
range silica columns and comparable with Chromosorb® W.243 Table 93 lists the
permeability, porosity, and theoretical plate number of OPP of varying bulk density
and Chromosorb® W of varying mesh size. OPP bulk densities of 0.15 to 0.18 g cm"3
are recommended. Higher OPP densities give columns with low permeability and re-
duced efficiency in plate number and resolution; lower densities result in column chan-
neling. A summary of conditions used for gas chromatographic separations of various
materials on OPP is given in Table 94.
C8
C9
C12
VI
12 16 20 24
MINUTES
FIGURE 87. Separation of C<,-C16 normal ali-

phatic hydrocarbons by GC on uncoated OPP. Col-
umn: 1.2 m x 6 mm I.D. and 40 to 120°C at 5°
min~'. Helium flow rate: 60 mf mhv1. (From Ross,
W. D. and Jefferson, R. T., J. Chromatogr. Sci.,8,
Table 92
RELATIVE RETENTION DATA OF
VARIOUS POLAR COMPOUNDS ON
UNCOATED OPP"
Relative retention Boiling point,

Compound time
(CH 3 ) 2 CHOH 1.0 82

CH 3 CH 2 OH 2.0 78
CH3OH 9.6 64
CC14 1.0 77
CHC13 1.05 61
CH2C12 1.6 40
Column 1 m x 4 mm I.D. containing 0.13 g cm OPP

with OH/NCO = 1.0.
From Hileman, F. D., Sievers, R. E., Hess, G. G., and

Ross, W. D., Anal. Chem., 45, 1126, 1973. With permis-
sion.
179
1.0
Trans
LU
C/5
O
Q-
cc
cc
tr
O
o
LU
CC
oL /
L I
0 2 4 6
RETENTION TIME (minutes)
FIGURE 88. Separation of geometrical iso-

mers of Cr (tfa) 3 by GC on uncoated OPP.
tfa = l,l,l-trifluoro-2,4-pentanedione. Col-
umn: 2.5 m x 4 mm I.D. at 100°C. Helium
flow rate: 40 ml min'1. (From Hileman, F.
D., Sievers, R. E., Hess, G. G., and Ross, W.
D., Anal. Chem., 45, 1126, 1973. With per-
mission.)
B. Gas-Liquid Chromatography
Less polar gas chromatographic columns of OPP can be prepared by using station-
ary phase. The liquid can be either coated on the OPP or incorporated into the polymer
by addition of the stationary phase to the precursor solutions. Coating the OPP with
a stationary phase masks the gas-solid properties completely, so that the material
adopts the characteristics of a gas-liquid substrate. Thus, instead of an adsorption
mechanism occurring, a solution process takes place and yields a more linear isotherm,
resulting in symmetrical peaks and constant retention times over a wide range of sam-
ple sizes. The liquid phase yields greater sample capacity with efficiencies of 900 to
1200 plates per meter. 243 The resolution and theoretical plate number improve for cer-
tain compounds. 244
Loss of the polar character of OPP in using liquid coatings was illustrated by Hile-
man et al.243 Although various metal chelates could be separated on an OPP column
coated with DC-550 (Figure 89), the c/sand trans isomers of Cr(tfa) 3 and Rh(tfa) 3 are
Table 93
CHARACTERISTIC PARAMETERS FOR 1-METER OPP
AND CHROMOSORB® W COLUMNS
Theoretical
Column Permeability Porosity plate
type (cm1 x 10-') number* Resolution*
OPP
g cm'3'
0.106 16.0 90.9
0.130 6.26 88.2 483 4.30
0.154 2.92 87.0 772 5.13
0.178 1.14 85.5 800 5.50
0.198 1.05 84.5 700 5.14
0.243 0.44 75.8 602 4.65
Chromosorb* W
mesh size
40/60 8.86 89.0
60/80 4.71 87.6
80/100 3.14 88.6
100/120 2.71 85.5
For dodecane.
* Average of resolution between three pairs of n-hydrocarbons (n-C,, and n-C,2,
n-Cu and n-C13, n-C13 and n-C14).
' Bulk density.
d
Serious channeling.
From Hileman, F. D., Sievers, R. E., Hess, G. G., and Ross, W. D., Anal.
Chem.,45, 1126, 1973. With permission.
not resolved.241-243 On an OPP column coated with Carbowax® 400, methanol,

ethanol, j'sopropanol, and tert-butanol are eluted in the order of their boiling points,
rather than the inverted order observed on uncoated polyurethane.243-244 Other exam-
ples of separations using OPP coated with Carbowax® 400 are shown in Figures 90
and 91.
Hileman et al.243 found that for optimum gas-liquid performance, the weight percent
of liquid phase should be between 5 and 50. Small samples overloaded columns con-
taining less than 5 wt% liquid phase and decreased column efficiency (because of the
large mass transfer term in the van Deemter equation) resulted at loading >50 wt%.
The permeability of the coated columns containing up to 25 wt% liquid phase varied
less than 10% from the permeability of the uncoated OPP.244
Liquid phases, which are included in situ with the polymer reactants, provide a good
distribution of stationary phase, resulting in higher plate numbers (C term or mass
transfer aspect of van Deemter equation minimized); likewise, resolution should im-
prove since it serves as both a measure of solvent (liquid phase) and column efficiency
(HETP).244 Although the chromatograms were not obtained under identical condi-
tions, Figures 92 and 93 show the separation of aliphatic hydrocarbons on coated and
in situ loaded liquid phase OPP, respectively. When the liquid phase contained groups,
such as hydroxyl, capable of reacting with the isocyanate, a bonded liquid phase could
be obtained, offering the advantage of low column bleed.244
A very important physical property of OPP in its use as a gas chromatographic
support is its temperature stability. Polyurethane prepared with the polyol LA-475
begins to decompose around 200°C; therefore, for normal GC work, a sustained upper
temperature limit of 160°C to 170°C is recommended.243 In short-term temperature
Table 94
SUMMARY OF CONDITIONS USED FOR GAS CHROMATOGRAPHIC
SEPARATIONS OF VARIOUS COMPOUNDS USING OPP COLUMNS
Compounds separated (given in or- OPP Column size Column temp. Helium flow rate
der of elution) (m x mm I.D.) (°C) (ml min~') Ref.
Hexane, heptane, octane, nonane 1.2x0.06" 40 to 120 at 60 242

(2), decane, dodecane, tetrade- 5° min~'
cane, hexadecane (17)°
Hexane, heptane, octane, nonane 0.5 x 0.06' 30 to 100 at 60 242
(6) 10° min'1
Hexane, heptane, octane, nonane 1.2x0.06" 50 to 140 at 60 242
(24) 5° min"1
Hexane, benzene, toluene, xylene 1.2x0.06" 50 to 140 at 60 242
(13) 5° min-'
Benzene, toluene, m-xylene, o-xy- 1 X4' 110 40 243
lene (9)
n-Propanol, n-butanol, n-pentanol, 1 X4- 100 55 243
n-hexanol (20)
Ethanol, n-propanol, n-butanol, n- 1.2x4' 120 60 245
pentanol
3-MethyI-2-butanone, cyclopentan- 1 .2 x 4« 175 27 245
one, cyclohexanone, menthone,
isophorone (11)
Diethyl ether, methyl Fenac, methyl 1.2x4' 175 27 245
2,4-D (20)
Be(tfa)2l Al(tfa)3, Cr (tfa)3 Rh(tfa) 3 1.1 x l- 136 25 243
(7)
Cis Cr(tfa)3, trans Cr(tfa)3 (5) 0.25 x 4* 100 40 243
Approximate elution time (minutes) shown in parenthesis.
' Uncoated OPP.
Coated with 10% Dow Corning Silicone Fluid 550.
d
Incorporated with 10% Dow Corning Silicone Fluid 550.
• Coated with Carbowax® 400.
' 2:1 LA-475-Mondur MR (other OPPs have 1:1 functionality).
• 2:1 EPON 1001-Mondur MR coated with Carbowax® 20M.
• tfa = 1,1,1 -trifluoro-2,4-pentanedione.
Be (tfa), I
Al ( t f a ) ,
Cr (tfa).,
Rh (tfa)..
12
MINUTES
FIGURE 89. Separation of four

metal chelate by GC on OPP
coated with 10% DC-550: tfa =
1,1,1 -trif luoro-2,4-pentanedione.
Column: 1.1 m x 1 mm I.D. and
136°C. Helium flow rate: 25 ml
min" 1 . (From Hileman, F. D.,
Sievers, R. E., Hess, G. G., and
Ross, W. D., Anal. Chem., 45,
programmed runs, an upper limit of 200°C can be used. However, with OPP prepared
with the polyol EPON 1001, the column can be operated at temperatures as high as
225 ° C 245
Besides improving the temperature stability of OPP, Chen, et al.245 also reported
reducing peak tailing for chromatograms of polar molecules. They found by increasing
the OH/NCO functionality from 1 to 2 decreased the polarity of the OPP and gave
good gas chromatographic separations of, and symmetrical peaks for, polar com-
pounds including alcohols. Figures 94 and 95 illustrate these improvements.
OPP has proven to be useful for both gas-solid and gas-liquid supports for gas
chromatographic separations. Although the range of separations that can be per-
formed by GC is limited, the prospects from improvement are bright because of the
variety of OPP columns which can be prepared. However, OPP has found a wide
acceptance as a separation media in liquid chromatography.
183
' , n-Butanol
n-Propanol ~
n-Pentanol
o
Q-
n-Hexanol
to
LU
QC
DC
O
O
LU
I-
LU
Q
I
12 16 20 24
MINUTES
FIGURE 90. Separation of C3-C6 normal alcohols by GC on OPP

coated with Carbowax* 400. Column: 1 m x 4 mm I.D. and 100°C.
Helium flow rate: 55 ml min"1. (From Hileman, F. D., Sievers, R. E.,
Hess, G. G., and Ross, W. D., Anal. Chem.,45, 1126, 1973. With
permission.)
C. Liquid Chromatography
Successful liquid chromatography (LC) separations have been achieved with OPP
columns by various investigators. Applications have included the separation of metal
chelates,242 alcohols,247 dichloroanilines, aromatic hydrocarbons, 247248 keto-steroids,
etc. 249 The high permeability and small particle size of OPP allow efficient separations
to be made using inexpensive high-speed, low-pressure LC equipment. Table 95 sum-
marizes the conditions used for LC separations of various materials on OPP columns.
The chemical and physical stability of OPP, coupled with the ability to change po-
rosity and functionality, make it an excellent support for LC. A wide variety of sol-
vents are compatible with OPP as described in Section III.B. The mechanical proper-
ties of OPP permit injections of samples directly on the column without any syringe
needle blocking. No inlet or outlet filters, which contribute to band spreading, are
required since the OPP bonds to the column wall. Column length can be significantly
increased to generate a greater total number of theoretical plates before exceeding the
pressure (100 kg cm~2) wherein the polymer begins to collapse. However, because of
the excellent permeability of OPP, low pressures (<10 kg cm"2) yield typical high speed
LC flow rates; the requirement for expensive high pressure pumps is thus eliminated.
OPP has a wide dynamic sample loading range compared to alumina and silica type
adsorbents used in LC. Columns of 2 mm diameter and 1 meter length will take up to
50 ^g of 2,4-dichloroaniline before the peak broadens, and even larger sample sizes do
I C6 C7 C8 C9 T
cc
o
I-
o
LU
I-
m
D
MINUTES 12
MINUTES
FIGURE 91. Separation of aromatic hydrocarbons by FIGURE 92. Separation of C6-C, aliphatic hy-
GC on OPP coated with Carbowax^ 400. Column: 1 m drocarbons by GC on OPP coated with 10 wt%
x 4 m m I.D. and 110°C. Helium flow rate: 40 ml min"1. Dow Corning Silicone Fluid 550. Column: 0.5 m
(From Hileman, F. D., Sievers, R. E., Hess, G. G., and x 6 mm I.D. and 30 to 100°C at 10° min-. He-
Ross, W. D., Anal. Chem., 45, 1126, 1973. With per- lium flow rate: 60 ml min"1. (From Ross, W. D.
mission.) and Jefferson, R. T., /. Chromatogr. Sci., 8,
not decrease peak symmetry indicating a more liquid-liquid partitioning type of chro-
matography. 246
Compared to GC, slightly higher bulk density formulations of polymer result in
more efficient LC columns. Lynn et al.,246 used an OPP with a density of 0.18 g ml'1
while Hansen and Sievers247 found better results using a 0.197 g mi~' material. Herman
and Field248 observed that polyurethane with densities as high as 0.243 g mi' 1 yielded
favorable results.
Herman and Field248 found that plate number efficiencies of OPP columns can be
increased by ~60% when multiple in situ polymerizations are performed. They ob-
served that a normal polymerization yields OPP with a packed bed matrix having an
abnormally large, open structure compared to a packed column of porous spherical
silica of comparable size; thus band broadening is increased with OPP because of
extensive axial molecular diffusion and mass transfer. The OPP matrix also contains
local inequalities in the packing density; i.e., the individual particles formed in clusters
185
FIGURE 93. Separation of C6-C, aliphatic hydrocarbons by

GC on OPP incorporated with 10 wt. % Dow Corning Silicone
Fluid 550. Column: 0.5 m x 6 mm I.D. and 50 to 140°C at 5°
min"1. Helium flow rate: 60 ml min"'. (From Ross, W. D. and
Jefferson, R. T., J. Chromatogr. Sc/.,8, 386, 1970. With per-
mission.)
leaving large voids between the clusters, which causes significant band broadening due
to eddy diffusion.
The multiple in situ polymerizations were performed by quickly pumping fresh so-
lutions of premixed reaction monomers into previously formed, in situ polymerized
OPP columns and allowing particle formation to occur within their interstitual
voids. 248 By partially filling the voids of the columns, the resulting matrices possess
lower intestinal porosities as well as more uniform distributions of particle density,
thus resulting in more efficient columns. Figure 96 shows flow-efficiency plots of re-
duced plate height vs. reduced velocity for singly, doubly, and triply polymerized OPP
columns. Although OPP column efficiencies were improved by multiple polmeriza-
tions, the performance of these columns does not compare favorably with that of mi-
croparticulate silica columns. Further significant improvements in OPP column effi-
ciencies may require a new set of reaction conditions that reduce interparticle bonding
(clustering) and yield more uniform packed bed structures. 248
LC separations have been improved by altering the synthesis conditions of OPP.
The effect of OH/NCO functionality was evaluated by Lynn et al.246 Figures 97 and
98 show the separation of dichloroanilines on OPP with different OH/NCO function-
alities. Measurements on the 2,6-dichloroaniline peak indicate an efficiency of 1085
theoretical plates per meter with an inlet pressure of only 4.9 kg cm"2 and a flow rate
of 0.25 mi min' 1 . The OPP with an OH/NCO of 2 gave 1720 theoretical plates per
FIGURE 94. Separation of alcohols by GC on 2:1 LA-475-Mondur MR column, (a)

Ethanol, (b) n-proponol, (c) n-butanol, (d) n-pentanol. Column: 1.2 m x 4 mm I.D.
and 120°C. Flow rate: 60 mi min-. (From Chen, T. M., Hess, G. G., and Sievers, R.
E., J. Chromatogr., 134, 170, 1977. With permission.)
6 12
TIME (mm)
FIGURE 95. Separation of ketones by GC on a column

coated with Carbowax® 20M on OPP formed from EPON
1001 and Mondur MR in a 2:1 weight ratio: (a) 3-methyl-l-
butanone, (b) cyclopentanone, (c) cyclohexanone, (d)
methone (e) isophorone. Column: 1.2 m x 4 mm I.D. and
175°C. Helium flow rate: 27 ml min" 1 . (From Chen, T. M.,
Hess, G. G., and Sievers, R. E., J. Chromatogr., 134, 170,
187
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FIGURE 96. Plots of reduced plate height vs. mobile phase reduced velocity for (a) 0.48 m x 3.9 mm I.D.
column of singly polymerized OPP column; (b) doubly polymerized OPP; and (c) triply polymerized OPP.
All OPP columns were OH/NCO = 0.5, bulk density = 0.243 g m/~'. Mobile phase and the solute were 1,2-
dichloroethane and p-chlorophenol, respectively. (From Herman, D. P. and Field, L. R., /. Chromatogr.
Sci., 20, 55, 1982. With permission.)
FIGURE 97. Separation of dichloroanilines by LC on OPP of OH/

NCO = 1.5. (a) benezene, (b) 2,6-dichloroaniline, (c) 2,4-dichloroan-
iline, (d) 2,3-dichloroaniline, (e) 3,5-dichloroaniline, (f) 3,4-dichlo-
roaniline. Column: 1 m x 2 mm I.D. Solvent: 20% isopropanol in n-
heptane at 0.26 ml min~'. Inlet pressure 4.9 kg cm"2. (From Lynn, T.
R., Rushneck, D. R., and Cooper, A. R., /. Chromatogr. Sci., 12,
189
15 20 25
ELUTION TIME (minutes!
FIGURE 98. Separation of dichloroanilines by LC on OPP of OH/

NCO = 2.0. (a) Benezene, (b) 2,6-dichloroaniline, (c) 2,4-dichloroan-
iline, (d) 2,3-dichloroaniline, (e) 3,5-dichloroaniline, (f) 3,4-dichlo-
roaniline. Column: 1 m x 2 mm I.D. Solvent: 20% /sopropanol in n-
heptane at 0.26 m/ min~'. Inlet pressure 3.5 kg cm"2. (From Lynn, T.
R., Rushneck, D. R., and Cooper, A. R., J. Chromatogr. Sci., 12,
meter at 0.26 mi min"1 using an inlet pressure of 3.5 kg cm 2. The values of HETP for
OPP are similar to those obtained with porous layer bead, Corasil® II, and consider-
ably larger than the values obtained with small particle porous silica 5 to 10 mm. 246
Hansen and Sievers247 evaluated the performance of OPP with OH/NCO = 2.2 and
1.0. With the excess polyol, phenol eluted later, gave a more symmetrical peak and
had much higher sample loadings.
Herman and Field248 investigated retention and selectivity differences of OPP having
excess surface hydroxyl or nitrile functional groups. Table 96 shows that EPON-type
columns are less retentive for acidic solutes than their LA-475 counterparts because of
the tertiary nitrogens in the monomer backbone of the LA-475 (which are not present
in the EPON). Nitrile surface-bonded OPP exhibits a lower degree of selectivity for
acidic solutes than the excess polyol types because of more potential hydrogen bonding
on a hydroxyl surface compared to that on a nitrile surface.
Larger selectivity differences were observed between polyol and nitrile surface
Table 96
ELUTION BEHAVIOR OF PHENOL AND p-
CHLOROPHENOL ON EXCESS POLYOL
AND ON NITRILE BONDED OPP COLUMNS
Capacity factors
Sep.
Column Phenol p-Chlorophenol factor
EPON — OH 0.31 0.67 2.2

EPON — C = N 0.91 1.69 1.9
LA475 — O H 2.40 4.59 1.9
LA475 — C= 1.37 2.46 1.8
From Herman, D. P. and Field, L. R., /. Chromatogr. Sci.,

bonded OPPs when a mobile phase of low polarity was used."8 Several polar com-
pounds were not retained on an excess polyol OPP when 10% dichloroethene/heptane
mobile phase was used. Similar behavior was observed by others,247 where OPP acted
as a zero capacity support using .n-heptane as the eluting solvent, but adding only small
amounts (10%) of a polar solvent to n-heptane retained polar solvents to some extent.
This behavior was believed to result from nonswelling of the polymer in a nonpolar
solvent, resulting in reduced effective surface area. However, the polar solvents tested
above were retained on a LA-475 nitrile column showing that this polymer swells under
nonpolar conditions.
Herman and Field248 found that OPP prepared with no polar hydroxyl or nitrile
surface bonded functional groups (prepared by terminating the urethane chains of the
EPON-based OPP with ethoxyl groups) had greater selective hydrophobic retention
characteristics.
Stainless steel microcapillary columns of OPP were demonstrated for several sepa-
rations. Figures 99 and 100 show the separation of eight polar compounds and keto-
steroids in less than 25 and 30 min, respectively. These results indicate that microcap-
illary OPP, in conjunction with low dead volume injectors and detectors (to reduce
band broadening), may have some utility because of the relative ease of OPP prepa-
ration.248
D. Collection, Concentration, and Other Methods

Although the use of OPP as either a GC or LC support appears to have some limi-
tations, its high sample capacity has made it an attractive sorbent for removing dis-
solved organics from aqueous solutions.249 "2 OPP columns have been evaluated for
the collection and preconcentration of polynuclear aromatic hydrocarbons (PAHs)
e.g., biphenyl, phenanthrene, pyrene, etc., from water. 249 With pyrene as a model
compound, solutions containing 1 ^g of pyrene per liter of water have been concen-
trated 200-fold by passing 1 I of the solution through a 5 cm x 0.3 cm I.D. column and
eluting the pyrene with 5 mi of methanol. Recovery of pyrene was approximately
100%. OPP with an OH/NCO functionality ratio of 2.2 exhibited a higher pyrene
recovery and faster elution properties than Amberlite® XAD-2 (Rohm and Haas), Bio-
Rad® AG MP-50 (Richmond, California) polystyrene polymers, and OPP with an
OH/NCO ratio of 1.0. Figure 101 and Table 97 show the results. The data in Table 98
demonstrate the excellent recovery of PAH using OPP under a variety of conditions.
OPP was shown to be a very effective sorbent for removing and concentrating linear
alkylate sulfonate (LAS) from water for a preconcentration step prior to analysis of
191
12 16 20 24 28
MINUTES
FIGURE 99. Separation of various polar compounds

by LC. (a) Benzene, (b) nitrobenzene, (c) aniline, (d) p-
chloroaniline (e) benzyl alcohol, (f) ocresol, (g) m-cre-
sol, and (h) phenol. Column: 2.9 m x 300 ^m I.D.; OH/
NCO = 2, bulk density = 0.243 g ml'1. Mobile phase:
75:24.5:0.5 hexane/dichloroethane/isopropanol at 0.1
ml min"1. (From Herman, D. P. and Field, L. R., /.
Chromatogr. Sci., 20, 55, 1982. With permission.)
LAS in detergent.250•"' Figure 102 shows the breakthrough capacity and elution behav-
ior of LAS on an OPP column. Table 99 shows that OPP has the highest breakthrough
capacity for LAS, but the lowest capacity for total organic carbon (TOC) compared to
Amberlite® XAD-4 (Rohm and Haas) and Amoco GX-31, active carbon; the differ-
ence in breakthrough capacities was suggested as a method for separating LAS from
TOC.250
Other analytical chemistry uses of OPP include its use as a thin-layer chromatogra-
phy support for the separation of Camptothecin from a crude extract of Camptotheca
acuminata using benzene-acetone-methanol as the developing solvent.241
V. MISCELLANEOUS APPLICATIONS
A. Preparative Chromatography
Several properties of OPP make it a very attractive material for preparative chro-
(b)
(c)
10 20 30 40
MINUTES
FIGURE 100. Separation of keto-steroids by LC. (a) proges-

terone, (b) deoxycorticosterone, (c) 17-a-hydroxyprogesterone.
Flow rate = 0.035 ml min'1. Column: 2.9 m x 300 ^m I.D.;
OH/NCO = 2, bulk density = 0.243 g mjf-'. Mobile phase:
75:24.5:0.5 hexane/dichloroethane/isopropanol at 0.1 ml
min" 1 . (From Herman, D. P. and Field, L. R., J. Chromatogr.
Sci., 20, 55, 1982. With permission.)
matographic work. OPP adheres tightly to the walls of the column thus preventing
channeling at the adsorbent-wall interface which is a potential problem with granular
adsorbents. The high liquid phase loading of the polymer yields high capacity columns.
These two properties, along with the lower cost of the material, make OPP useful as
preparative columns.
Ross and Jefferson 241 - 242 demonstrated the preparative-scale gas chromatographic
separation of nonane, heptane, and pentane; the support was 2.4 m x 5.7 cm and
coated with Dow Corning Silicone Fluid 550. No commercial preparative-scale liquid
chromatographic separations of the polymer have been reported, although the appli-
cations appear promising because of its versatility, high capacity, and low cost.
B. Wastewater Treatment
OPP has been used for the removal and recovery of various compounds from waste-
water. The polymer was tested for its ability to remove detergents, corrosive anions,
and coal conversion by-products from wastewater streams. 251 - 252
A comparison of OPP to activated carbon and other popular adsorbent materials
for detergent and chloride removal from wastewater was reported. 252 Several other
adsorbents outperformed polyurethane for detergent removal, but not for chloride or
193
i n i
O = OPP (OH.'NCO - 1.0)
A = BIO - RAD AG MP - 50
O -Amberhte XAD - 2
O =-- OPP (OH/NCO - 2.2)
o
o >
o
z
LU
y
LL
LL
LU
z
g
i-
o
LU
_1
0.2 _)
O
0
0.1
20 40 60 80 100
PYRENE PASSED (/jg)
FIGURE 101. Breakthrough results for pyrene on various polymers.

C/Co = concentration of pyrene in effluent divided by concentration
of pyrene in feed. (From Navratil, J. D., Sievers, R. E., and Walton,
H. F., Anal. Chem.,49, 2260, 1977. With permission.)
Table 97
VOLUMES OF METHANOL AND ETHANOL
REQUIRED TO ELUTE PYRENE FROM
VARIOUS POLYMERS-
Polymer Methanol (ml) Ethanol (mi)
OPP (OH/NCO = 2.2) 2.0 ±0.6 1.4 ±0.2

OPP (OH/NCO = 1.0) 2.3 ± 0.5 —
Bio-Rad® AG MP-50 3.4 ±0.6 —
Amberlite^ XAD-2 5.9+ 1.2 5.4+ 1.4
Columns 5 cm x 0.3 cm I.D., loaded with 5 \i% of pyrene.
From Navratil, J. D., Sievers, R. E., and Walton, H. F., Anal.

Chem., 49, 2260, 1977. With permission.
the anionic surfactant constituent of the detergent, LAS (see Section IV.D). Open-pore
polyurethane prepared under a variety of conditions was compared to three common
commercial adsorbents for TOC, total phenol, etc., removal from both synthetic and
actual coal conversion wastewater, 612 " Figures 103 and 104 show respectively TOC
and phenol breakthrough curves for these materials. The data indicate that in compar-
Table 98
RECOVERY OF PAH WITH OPP (OH/NCO = 2.2)
PAH Flow rate (I hr1) PAH Loaded (/jg) Recovery %
Benzo[a]pyrene 1.8 4 95 ± 6
Biphenyl 0.9—1.5 5—6 98 ±5
Fluoranthene 0.5—1.0 4—5 77 ±4
0.5—1.0 1—2.5 97 ± 3
Naphthalene" 0.1 5 56 ± 3
0.1—1.0 1—2.5 98 ± 10
Phenanthrene 0.8—1.0 5 58 ±1
0.8—1.0 1—2.5 92 ±9
Pyrene 0.6—0.8 1—4 100 ± 2
1.2—1.7 4—5 89 ±3
Pyrene (XAD-2)° 0.6 4 79 ± 8
• Required 10 mf of methanol to elute quantitatively; others needed only 5 mjf.
From Navratil, J. D., Sievers, R. E., and Walton, H. F., Anal. Chem., 49, 2260,
400 500 600

DETERGENT Iml)
FIGURE 102. Breakthrough and elution results of linear alkylate sulfonate on 10 cm

x 0.4 cm J.D. column of OPP (OH/NCO = 2.2; density = 0.20 g ml' 1 ). (From Smith,
C. M., Navratil, J. D., and Plock, C. E., U.S. Department of Energy Report RFP-
2813, Rockwell International, Golden, Colorado, 1979. With permission.)
ison to other polymers, OPP has an intermediate capacity for TOC and exhibits very
little breakthrough of phenols. The in situ polymer also has the advantage of eluting
better than the other sorbents. 61252 Table 100 shows the breakthrough data of the in-
dividual organic compounds making up the TOC.61 For both OPP and XAD the pri-
mary amine and the pyridine break through readily, and phenol to a slight degree.
OPP ranks nearly as well as activated charcoal on a capacity per weight of sorbent
basis; the low density of the polymer is an important factor in large-scale usage. With
individual compound class breakthrough data, a tertiary water cleanup process can be
tailored to suit particular needs. OPP offers a promising alternative to commonly used
charcoals and polymers for wastewater cleanup. Comparative cost and elution char-
acteristics are among its advantages. 61252
195
Table 99
BREAKTHROUGH AND ELUTION DATA FOR
SORBENTS"
Breakthrough capacity*
Elution'
Sorbent LAS TOC TOC
OPP (OH/NCO = 2.2) 620 13

Amberlite* XAD-4 310 120
Amoco GX-31 83 70
Data average of two determinations; average precision ±30%.

* Milliliter of detergent passed per milliliter of sorbent when ratio of
linear alkylate sulfonate (LAS) or total organic carbon (TOC) in
the effluent to LAS or TOC in the feed is 0.3.
' Milliliter of methanol to elute 30% of TOC from a milliliter of
sorbent.
From Smith, C. M. and Navratil, J. D., Sep. Sci. Technol., 14, 255,
C0 = 34 mg/l LAS (Linear Alkylate Sulfonate)

/CQ = LAS concentrate concentration in effluent divided
by LAS in influent
Flow Rate - 1 - ml/min
200 400 600 800 1000

DETERGENT SOLUTION (ml)
(2.6 grams detergent per liter solution)
FIGURE 103. Breakthrough curves for TOC on various ad-

sorbents. Columns: 0.3 m x 2.5 cm I.D. C/Co = concentration
(i.e., TOC in ppm) of effluent divided by concentration of
feed. One aliquot = 34 ml. (From Denton, M. S., Dinsmore,
S. R., Brand, J. I., Beams, J., and Ball, F. L., Sep. Sci. Tech-
nol., 15, 587, 1980. With permission.)
• X A D -2
O OPP
D Columbia
A Ambersorb X E - 348
o.o
7 8 9 10 11 12 13 14 15 16 17 18 19 20
ALIQUOT NUMBER
FIGURE 104. Breakthrough curves for phenol on various adsorbents. Columns: 0.3
m x 2.5 cm l.D. C/Co = concentration (i.e., TOC in ppm) of effluent divided by con-
centration of feed. One aliquot = 34 mt. (From Denton, M. S., Dinsmore, S. R.,
Brand, J. I., Beams, J., and Bali, F. L., Sep. Sci. Technol., 15, 587, 1980. With per-
mission.)
C. Other and Potential Uses

OPP can be tailored for filtration applications by density, particle size, and porosity.
It may find use in dust masks, furnace filters, and vacuum cleaners as well as cigarette
filter use. 259 - 260 Composite OPP structures containing metallic (e.g., nickel) fillers were
prepared and then fired to remove the OPP matrix to obtain porous metal structures
that retain the shape and form of the initial OPP casting.261 The polymer may be
fabricated into membranes and used for hollow-fiber applications including supports
for solvent extractants.262
197
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209
INDEX
A preconcentration of, 112, 116

quantitative elution of, 30
separation of, 110, 116
ABS, see Alkylbenzene sulfonate
sorption of, 24, 117
Absorption of uranium, 32
Acetone, 55 Aqueous media
acid type, 49
Acid aqueous solutions, 49
Acid concentrations, see also specific acids chlorine type, 98
collection from, 15—17, 92—104
extraction efficiency and, 29
Acidic halides, 24—32 nitrate type, 32—33
retention from, 15—17
Acidic thiocyanate, 33—34, 36—47
Acidic thiourea, 49 sorption from, 23, 55—70
chlorinated organic compounds, 56—59
Active carbon, 97
other organic compounds, 65—70
Active hydrogens, 160
polynuclear aromatic hydrocarbons, 60—65
Adsorption mechanisms, 179
Arsenic, 12, 13
Aerodynamic behavior, 2
heteropolymolybdates of, 53
Air sampling, 4, 17, 18, 21, 22
Alamine-foam columns, 143 Arzenoazo, 131
A shore hardness of OPP, 162, 166
Alcohols, 182
Aldrin, 100 Automatic squeezing, 15, 32, 120
Aliphatic hydrocarbons, see also specific types
separation of, 180 B
Aliquat foam, 130—131
Alkali-metal chlorides, phosphomolybdate sorp-
tion and, 54 Band broadening, 184
Alkali metal picrates, sorption of, 49 BaP, see Benzo(a)pyrene
Alkali metals, see also specific metals Barium, sorption of, 51
sorption of, 51 Batch methods, 15, 24, 65, 69, 117
Alkaline cyanide, 47—48 Batch shaking, 15
Alkylbenzene sulfonate (ABS), 128 Batch squeezing, 3,4, 15, 28, 29, 120
detection of, 66 Battery powered low-volume air sampling system,
extraction of, 65 22
Allophanate linkages, 10 Benzene, 24
Alumina, 183 o-Benzildioxime foam, 116
Aluminum, 12, 13, 28 Benzo(a)anthracene, 88
separation of gallium and iron from, 27 Benzo(a)pyrene (BaP), 63, 88, 102
Aluminum nitrate, 32 desorption of, 61
Amines, 126, 159, 160 recovery of, 60, 61
Analytical chemistry, open-pore polyurethane sorption of, 60
(OPP)in, 173, 176—195 Benzo(ghi)perylene, 88
collection, concentration, and other methods, Benzo(j)fluoranthene (BjF), 62
190—191, 193—195 recovery of, 61
gas-liquid chromatography, 179—186 Benzo(k)fluoranthene (BkF), 62
gas-solid chromatography, 176—180 recovery of, 61
liquid chromatography, 183—185, 187—192 Benzoylacetone foam, 113
Analytical methods for characterization of foams, Biacetylmonoxime benzoylhydrazone foam, 122
13—14 Bismuth
Analytical use of foams, 14—22 gold separation from, 97, 98
Anchored functional groups, 133—135 palladium separation from, 94
Anchoring of chelating groups to foam matrix, 92 separation of, 93, 95
Aniline, 160 Bismuth-thiourea complex, 95
Anion exchange, 23, 45, 128—130 Biurett, 10
open-pore polyurethane (OPP) and, 173 BjF, see Benzo(j)fluoranthene
weak-base, 43 BkF, see Benzo(k)fluoranthene
Anthracene, 88 Blowing
Antimony, 12, 13 by in situ chemical reaction, 7—8
distribution ratios for, 24 by vapor from volatile liquid, 8
extraction of, 29, 30 Breakthrough capacity of foams, 94
gold separation from, 97, 98 Bromine, 12, 13, 152
Bromoxynil oxtanoate, 90 Chlorinated hydrocarbons, see also specific types,

Bulk density, 13, 102, 162, 177, 184 157
sorption from aqueous media, 55—59
c sorption from gaseous media, 70—83
Chlorine, 12, 13, 152
ff-Chloro acrylic esters, 8
Cadmium Chlorofluorocarbons, see also specific types, 8
cation exchange distribution ratios of, 133 Chloroform, 24
collection of, 110, 120 Cholinesterase, 155
detection of, 126 immobilized, 156
extraction of, 45, 113, 117 inhibition of, 155, 157
qualitative determinations of, 122 sorbed, 156
semiquantitative determinations of, 122, 126 Chromatography, 3, 15
separation of, 113, 117, 130, 131 gas-liquid, 179—182
Cadmium-zinc, separation of, 130 gas-solid, 176—177
Calcium, cation exchange distribution ratios of, liquid, 183—190
133 preparative, 191 — 192
Camptothecin, 191 thin-layer, 191
Capacity, 29, 30, 176 Chromium, determinations of, 122
for copper, 120 Chromofoams, 122
sample, 179 Chrysene, 88
Carbamate compounds, see also specific types, 88 Cigarette filters, 91
collection of, 89 Cleaning of foams, 15
Carbamic acid anhydride, 9 Closed-cell (rigid) foams, 7, 10, 11
Carbon, 148 Coated glass beads, 17
active, 97 Cobalt
total organic (TOC), 191, 193, 194 carrier-free, 129
Carbon dioxide, 9 coextraction of other metals with, 37
Carrier-free cobalt, 129 collection of, 110, 113, 120
Catalysis, reaction rate and, 10 extraction of, 33, 34, 41, 45, 117, 131
Catalysts, 161, 162, 166 gold separation from, 97, 98
Cation-chelation mechanism, 45 iron separation from, 98
Cation exchange, 131, 133 preconcentration of, 34, 119
distribution ratios for, 133 qualitative determinations of, 122
heterogeneous, 152 retention of, 98
Cells semiquantitative determinations of, 122
immunoadsorption of, 3, 155—157 separation of, 33, 117, 131
quasi-spherical, 4 from manganese, 119
structure of, 7 from nickel, 128, 129
Cerium sorption of, 118
pulsated columns for, 137 Cobalt-thiocyanate complex, extraction of, 37
reduction efficiency of, 136 Collection, 176, 190—191
in aqueous media, 15—17, 92—102
Characterization of foams, 13—14
of cadmium, 110, 120
Charcoal-foam mixture, 58, 59
of carbamate compounds, 89
Chelates, metal, 176, 179
of chlordane, 77
Chelating groups, anchoring of to foam matrix, of cobalt, 110, 113, 120
92 of copper, 120
Chelating reagents, hydrophobic, 102—121 flow rate and efficiency of, 57
Chelation-cation mechanism, 45 in gaseous media, 17—22, 102
Chemically bonding functional groups, 159 of hexachlorobenzene (HCB), 77
Chemical methods of foam preparation, 7—8 of inorganic species, 23—55
Chemical properties of polyurethane foams, 11 — of lead, 110
13 of manganese, 118
for open-pore (OPP) types, 162—173, 183 of mercury, 105, 108, 110, 120
Chemical resistance of polyurethane foams, 11 of metal ion traces, 122
Chloranil, 136 of methylmercury chloride, 108
Chlordane, collection of, 77 of oil, 69
Chlorides, see also specific types of organic species, 22, 55—92
extraction efficiency and, 29 sorption from aqueous media, 55—70
ionic strength effect of, 41 sorption from gaseous media, 70—92
211
of organochlorine pesticide mixtures, 72 Desorption, of benzo(a)pyrene (BaP), 61

of phenol, 69 Detection
of phthalate ester, 66 of alkylbenzene sulfonate (ABS), 66, 128
of polychlorinated biphenyls (PCBs), 71, 77, of cadmium, 126
102 of iron, 126
of polynuclear aromatic hydrocarbons (PAH), of mercury, 126
190 of phosphate, 126
of radioiodide, 143 of tin, 126
of silver, 105 Diameter
of toxaphene, 77 of column, 60
of trace elements, 2 of open-pore polyurethane (OPP), 162
of zinc, 120 Dichloroanilines, separation of, 185
Column redox reactions, 135—137 Di-n-dibutylphthalate, 88
Columns, see also specific types, 15—16, 117 Dieldrin, 100
diameter of, 60 extraction of, 57
EPON-type, 189 Diethyldithiocarbamate foam, 110—113
pulsating, see Pulsating columns Diethyl ether, 32, 98
Combustion Diethylhexylphthalate, 88
dry, 149 Di(2-ethylhexyl) phthalate, 88
of iodoorganic compounds, 148 Diethylphthalate, 88
Compatibility of open-pore polyurethane (OPP), Diffusion, of gallium, 29
173 Diheptylphthalate, 88
Composition of foams, 13 Dilute bases, 173
Concentration, 176, 190—191 p-Dimethylaminobenzaldehyde, 13
of monomers, 162 Dimethylglyoxime (DMG) foam, 113—116
Continuous Aqueous Monitor System, 157 o-Dinonylphthalate, 122
Copper o-Dinonylphthalate-plasticized PAN, 120
capacity for, 120 1,5-Diphenylcarbazide foam, 122
coextraction of with cobalt, 37 Diphenylmethane diisocyanate, 11
collection of, 120 Dissolved gas, low pressure release of, 8
elution of, 133 Distribution coefficient of silver, 53
extraction of, 113, 117 Distribution ratios of inorganic species, 23
gold separation from, 97, 98 Dithizone foams, 105—110, 122
iron separation from, 98 in ff-dinonylphthalate, 122
polyurethane foam immobilizing, 140 plasticized, 105
qualitative determinations of, 122 unplasticized, 105
retention of, 98 DMG, see Dimethylglyoxime
semiquantitative determinations of, 122 Dodecane, 177
separation of, 113, 117, 130 Dry combustion, 149
silver separation from, 105 Drying of foams, 15
sorption of, 121, 132
Copper-foam, 140
Cresols, sorption of, 69 E
Crude MDI, 160
Crystal violet, 65 Eldrin, 100
Cyanide, 47—48 Elemental microanalysis, 3
1,2-Cyclohexanedione dioxime foam, 116 Elution, of copper, 133
Enzyme inhibitors, 3
trapping of, 155—157
D Enzymes, see also specific enzymes
immobilization of, 155
DDT, 100 inhibition of, 3, 155—157
extraction of, 57 starch containing, 3
Decachlorobiphenyl (DCB), 82 Enzymic-inhibiting atmospheric pollutants, 3
Decomposition EPON-based open-pore polyurethane (OPP), 190
of organobromine compounds, 155 EPON-type columns, 189
of organochlorine compounds, 155 Equilibrium, 177
of organomercury compounds, 149 Erythrocytes, immunospecific binding of, 157
Density, 11, 159, 162, 166, 184, 196 1,2-Ethanedithiol foam, 116—117
bulk, see Bulk density Ethanol, 55
particle, 185 hydrochloric acid mixtures with, 133
Ethers, 29 analytical use, 14—22

Ethy! acetate, 55, 98 Formaldehyde, 160
Ethyl-hexyl phosphoric acid, 131 Fungicides, see also specific types
Experimental techniques for analytical use of chlorinated hydrocarbon, 157
foams, 14—22
Extraction
of alkylbenzene sulfonate, 65 G
of antimony, 29, 30
of cadmium, 45, 113, 117 Gallium
of cobalt, 33, 34, 41, 45, 117, 131 diffusion of, 29
of cobalt-thiocyanate complex, 37 extraction of, 27, 28
of copper, 113, 117 extraction efficiency and, 29
of DDT, 57 polymeric extractor for, 28
of dieldrin, 57 recovery of, 27
efficiency of, 27—29 separation of from aluminum, 27
of gallium, 27, 28 sorption of, 29
of gold, 117 Gas chromatography, 3
of gold-thiourea complexes, 97, 98 Gaseous media, see also specific types
hydrochloric acid and efficiency of, 27, 37 collection from, 17—22, 102
of indium, 33, 117 polychlorinated biphenyls in, 102
of iridium, 33, 54 retention of, 17—22
of iron, 29, 31, 33, 34, 45, 117 sorption from, 70—92
of manganese, 45, 117 Gaseous phase, 1
of mercury, 33, 117 Gas flow rates, 159
of nickel, 114, 116, 131 Gas-liquid chromatography, 179—182
of organochlorine compounds, 100, 102 Gas samplers, 21, 73
of palladium, 33, 39—40, 98 Gas-solid chromatography, 176—177
of palladium-thiocyanate complexes, 41 Gas-solid membranes, 1
of platinum, 54 Geometrical isomers, 176
of polychlorinated biphenyls (PCBs), 57, 102 Geometry of foams, 4—7
of rhodium, 33 Germanium heteropolymolybdates, 53
solution temperature and efficiency of, 37 Glass beads, 17
solvent, 43, 45 Glass fiber filters, 21
thiocyanate concentration and efficiency of, 37 Glycols, 160
of tin, 31, 32 Gold
of uranyl nitrate, 33 distribution ratios for, 24
of zinc, 33, 45, 117 extraction of, 117
nondestructive determination of, 25
retention of, 98
F separation of, 96—98, 117
from cyanide, 47
Factual membranes, 4 from ore, 26
Filler, 8 sorption of, 24, 38, 120
Filtration applications of open-pore polyurethane sorption isotherms of, 24
(OPP), 196 Gold chloride, separation of, 25
Finely divided precipitate, 139—141 Gold-thiourea complexes
FL, see Fluoranthene extraction of, 97, 98
Flexible foams, see Open-pore polyurethane retention of, 49
(OPP) sorption of, 92—93, 97
Flow operations, 65, 69 Granular sorbents, 17
Flow rates, 2, 4, 177 Greases, 100
cerium reduction efficiency and, 136 Guinea pig erythrocytes, 157
collection efficiency and, 57
gallium extraction and, 27
gas, 159 H
HETP and, 94
solvent, 159 Halides
Fluoranthene (FL), recovery of, 61 acidic, 24—32
l-Fluoro-2,4-dinitrobenzene, 90 metal, 32
Foams Halogens, 149
analytical methods for characterization, 13—14 HCB, see Hexachlorobenzene
213
Height equivalent to a theoretical plate (HETP), extraction of, 33, 117

93,94, 177, 180, 189 preconcentration of, 112
Heptachlor, 100 separation of, 33, 117
Heptafluorbutyric anhydrides, 90 sorption of, 38, 120
Heptane, separation of, 192 Inhibition of cholinesterase, 155, 157
Heptens, 157 Inorganic species, see also specific types
Herbicides, see also specific types collection of, 23—55
chlorinated hydrocarbon, 157 sorption from aqueous media, 23—54
Heterocyclics, 159 sorption from nonaqueous media, 54—55
Heterogeneous cation exchange, 152 distribution ratios of, 23
Heterogeneous ion exchange, 132—133, 152 retention of, 22
Heteropolymolybdates, 53 separation of, 23
HETP, see Height equivalent to a theoretical Inorganic trace impurities in polyurethane foams,
plate 11
Hexachlorobenzene (HCB), 75 Insecticides, see also specific types
collection of, 77 chlorinated hydrocarbon, 157
Hexachloroiridate, sorption of, 54 organochlorine, see Organochlorine com-
Hexachloroplatinate, sorption of, 55 pounds
High-density foams, 4 In situ chemical reaction, 7—8
High-volume air samplers, 17 In situ polymerization, 184, 185
High-volume gas samplers, 73 Interference, 28
History, 2—4 Iodine, 12, 13, 148
Horse-serum cholinesterase, 155 distribution ratios for, 24
Hydrobromic acid, 131 radioactive, 140—144
tin extraction from, 32 retention of, 148
Hydrocarbons, see also specific types, 176 separation of, 144, 146
aliphatic, 180 sorption of, 24
chlorinated, see Chlorinated hydrocarbons sorption isotherms of, 24
polynuclear aromatic, see Polynuclear aromatic TBP-pIasticized, 143
hydrocarbons lodoorganic compounds, combustion of, 148
Hydrochloric acid, 30, 98, 128—131 Ion exchange, 25, 45
ethanol mixtures with, 133 heterogeneous, 132—133
extraction efficiency and, 27, 37, 39—40 liquid, 92
tin extraction and, 31, 32 pellicular, 132
Hydrodynamic behavior, 2 selectivity of, 133
Hydrofluoric acid, tin extraction from, 32 Ionic strength effect of chlorides, 41
Hydrogens, 148 IP, see Indeno(l,2,3-cd)pyrene
active, 160 Iridium
Hydrophobic organic phases, 141 —148 extraction of, 33, 54
Hydrophobic organic reagents, 138 preconcentration of, 37
Hydrophobic reagents, 102, 104—121 separation of, 33, 37, 130
o-benzildioxime foam, 116 Iron
benzoylacetone foam, 113—114 cation exchange distribution ratios of, 133
diethyldithiocarbamate foam, 110—113 coextraction of with cobalt, 37
dimethylglyoxime foam, 113—116 detection of, 126
dithizone foam, 105—111 distribution ratios for, 24
1,2-ethanediol foam, 116—118 extraction of, 29, 31, 33, 34, 45, 117
l-nitroso-2-naphthol foam, 113—114 gold separation from, 97, 98
pyridylazo-naphthol foam, 117—120 preconcentration of, 34
Hydroxyl surface, 189 pulsated columns for, 137
qualitative determinations of, 122
reduction of, 136, 137
I retention of, 98
semiquantitative determinations of, 122
Immobilization separation of, 33, 98, 117, 130
of cholinesterase, 155, 156 from aluminum, 27
of enzymes, 155 sorption of, 24, 121
Immunoadsorption of cells, 3, 155—157 sorption isotherms of, 24
Immunospecific binding of erythrocytes, 157 Iron hydroxide, 3
Indeno(l,2,3-cd)pyrene (IP), recovery of, 61 Isocyanate, 9, 159, 160, 166, 180
Indium, 12, 13 Isopropyl ether, 98
Isotope exchange, 3, 92, 138—148 distribution ratios for, 24

extraction of, 33, 117
in natural samples, 108
K preconcentration of, 105, 112
Ketosteroids, separation of, 190 recovery of, 134
semiquantitative determinations of, 122, 126
separation of, 33, 117
L sorption of, 24, 38, 120
vapor of, 149
LAS, see Linear alkylate sulfonate Mercury chloride, sorption of, 134
LC, see Liquid chromatography Metal chelates, 176, 179
Leaching, of PAN, 119 Metal halides, 32
Lead Metal ions, see also specific metals, 3
collection of, 110 collection of, 122
qualitative determinations of, 122 sorption of, 105
semiquantitative determinations of, 122 Methylene blue, 65, 66
silver separation from, 105 sorption efficiency of, 57
sorption of, 51 Methylisobutyl ketone, 98
Linear alkylate sulfonate (LAS), 190, 191, 193 Methylmercury, preconcentration of, 112
Liquid cation, 131 Methylmercury chloride
Liquid chromatography (LC), 183—190 collection of, 108
Liquid ion exchangers, 92, 128—131 sorption of, 134
Liquid phase, 1 Methyltricaprylyl ammonium chloride, 130
Liquid-solid membranes, 1 Microspheres, 8
Lithium chloride, and tin extraction, 31 Mixed cresols, sorption of, 69
Loading, 92 Molybdenum, 24
hydrophobic chelating reagents, 102—121 Monomer concentration, 162
liquid ion exchangers, 128—131 Multiple in situ polymerization, 184, 185
liquid phase open-pore polyurethane (OPP),
180
silicone oils, 102 N
solvent extractants, 92—102
Load resilient polyurethane foams, 135—157 Natural sponge, 2
column redox reactions, 135—139 Neutral cyanide, 47—48
isotope- and redox-exchange separations, 138— Nickel
148 cobalt separation from, 128, 129
trapping enzyme inhibitors and the immunoad- extraction of, 114, 116, 131
sorption of cells, 155—157 gold separation from, 97, 98
trapping volatile combustion products in or- iron separation from, 98
ganic microanalysis, 148—155 palladium separation from, 94
Low-density foams, 4 qualitative determinations of, 122
Low pressure release of dissolved gas, 8 reaction of with DMG, 115
Low-volume sampling, 21, 22 semiquantitative determinations of, 122
separation of, 93, 95, 115, 116, 131
Nitrate ion concentration, 33
M Nitrite functional groups, 189
Nitrile surface, 189
Magnesium, 12, 13 Nitrogen heterocyclics, 159
Manganese, 12, 13 l-Nitroso-2-naphthol foam, 113
cobalt separation from, 119 Nonane, separation of, 192
collection of, 118 Nonaqueous media, see also specific types, 69
extraction of, 45, 117 sorption from, 54—55
separation of, 117 Nondestructive determination of gold, 25
Manufacturers of polyurethane foams, 10
Matrix, 184
Mechanical methods of foam preparation, 8 o
Medium-density foams, 4
Mercury Oil collection, 69
collection of, 105, 108, 110, 120 Open-cell foams, see Open-pore polyurethane
detection of, 126 (OPP)
215
Open-pore polyurethane (OPP) columns, 161— p

162
Open-pore polyurethane (OPP) sorbents, 14—15, PAH, see Polynuclear aromatic hydrocarbons
22, 159 Palladium
analytical chemistry applications of, 173, 176— extraction of, 33, 39—40, 98
195 gold separation from, 97, 98
collection, concentration, and other meth- separation of, 33, 93, 95
ods, 190—191, 193—195 from bismuth, 94
gas-liquid chromatography, 179—186 from nickel, 94
gas-solid chromatography, 176—180 Palladium-thiocyanate complexes, extraction of,
liquid chromatography, 183—185, 187—192 41
cell structure, 7 Palladium-thiourea complexes
chemical properties of, 11, 162—177 retention of, 93
collection, 29, 30 sorption of, 49
column redox reactions, 135—139 PAN, see l-(2-Pyridylazo)-2-naphthol
compatibility of, 173 Particle density, 185
Particle size, 162, 196
formation of, 160
of open-pore polyurethane (OPP), 183
historical overview, 3—4
Particle sphericity, 162
isotope- and redox-exchange separations, 138— PCBs, see Polychlorinated biphenyls
148 Peak shapes, 177
permeability of, 177 Peak tailing, 182
physical properties of, 11, 162—177 Pellicular ion exchangers, 132
polarity of, 182 Pentafluoropropionic anhydride, 90
polyether type, 78—79 Pentane, separation of, 192
preparation of, 159—162 Perchloric acid-thiourea system, 93—95
properties of, 28, 159, 162—173 sorption from, 97
reagents of, 159—161 Permeability, 105, 176, 180
stability of, 161 of open-pore polyurethane (OPP), 162, 177,
structure of, 159 183
synthesis of, 10, 159—161, 185 Pesticides, see also specific types
thermodynamic properties of, 28 carbamate, 88
trapping enzyme inhibitors and the immunoad- organochlorine, see Organochlorine com-
sorption of cells, 155—157 pounds
trapping volatile combustion products in or- pH, extraction efficiency and, 39—40
ganic microanalysis, 148—155 Phenanthrene, 88
Phenolic resins, 7
OPP, see Open-pore polyurethane
Phenols, 159, 189
Organic acids, 160
collection of, 69
Organic compounds, see also specific types
distribution ratios for, 24
chlorinated, see Chlorinated hydrocarbons sorption of, 24, 69
Organic extractable compounds, 12
total, 193
Organic microanalysis, 148—155 o-Phenylenopyrene, 88
Organic reagents, hydrophobic, 138 Phenylmercury, preconcentration of, 112
Organic species, see also specific types Phosphate, 126
collection of, 55—92 Phosphomolybdate, sorption of, 47, 54
sorption from aqueous media, 55—70 Phosphoric acid, 131
sorption from gaseous media, 70—92 Phosphorus, heteropolymolybdates of, 53
Organobromine compounds, decomposition of, Phthalate esters, 88, 102
155 collection of, 66
Organochlorine compounds, 79, 102 recovery of, 66
collection of, 72 Physical methods of foam preparation, 8
decomposition of, 155 Physical properties of polyurethane foams, 11 —
extraction of, 100, 102 13
recovery of, 100 for open-pore polyurethane (OPP), 162—173,
sorption of, 83, 102 183
Organomercury compounds, decomposition of, Plasticized amine foams, 126
149 Plasticized biacetylmonoxime benzoylhydrazone
Organophosphorus compounds, see also specific foam, 122
types, 55, 83—85, 156 Plasticized diethylammonium DDC foam, 112
Plasticized dithizone foams, 105 breakthrough capacities of, 137

Plasticized l-nitroso-2-naphthol foam, 113 l-(2-Pyridylazo)-2-naphthol (PAN), 117—120
Plasticized l-(2-pyridylazo)-2-naphthol (PAN)
foams, 117, 118
Plasticizers, 105, 109 Q
Plate numbers, 177, 179, 180, 185
efficiencies of for open-pore polyurethane Qualitative determination, 121 —128
(OPP), 184 Qualitative spot reaction, 14
theoretical, see Theoretical plate numbers Quantitative elution of antimony, 30
Platinum, extraction of, 54 Quantitative separation
Polar compounds, separation of, 190 of cadmium-zinc, 130
Polarity of open-pore polyurethane (OPP), 182 of copper, 130
Polychlorinated biphenyls (PCBs), 21, 70, 81, 82 Quasi-spherical cells, 4
collection of, 71, 77, 102 Quasi-spherical solid membranes, 1—2
PCN mixture with, 72
sorption of, 56, 75, 102 R
Polyester polyurethane foams, 11, 31, 38, 47
unloaded, 34 Radiochemical separation, 138
Polyether polyurethane foams, 11, 30—32, 37, Radioiodine, 140, 141
38,41, 55—56, 136 collection of, 143
open-cell, 78—79 separation of, 142—144, 146
surface area for, 12 Radiosilver, 139, 140
unloaded, 34, 49 separation of, 147
untreated, 148 Reactants, 162
Polyisocyanate, 160 Reaction conditions, 159, 162
Polymeric extractor for gallium, 28 Reaction rate, catalysis and, 10
Polymerization, 161, 162 Reaction time, 161, 162
multiple in situ, 184, 185 Reagents
Polymerization time, 161 of open-pore polyurethane (OPP), 159—161
Polynuclear aromatic hydrocarbons (PAH), 21, in qualitative analysis, 121 —128
159 in semiquantitative analysis, 121 —128
collection of, 190 Recovery, 176
sorption from aqueous media, 55, 56, 60—65 of benzo(a)pyrene (BaP), 60, 61
sorption from gaseous media, 86—88 of benzo(j)fluoranthene (BjF), 61
preconcentration of, 190 of benzo(k)fluoranthene (BkF), 61
volatile, 88 of fluoranthene (FL), 61
Polyols, 10, 173, 189 of gallium, 27
Polypropylene glycol, 160 of indeno(l,2,3-cd)pyrene (IP), 61
Polyurethane foams, defined, 4 of mercury, 134
Polyurethane polymers, 4 of organochlorine pesticides, 100
Porosity, 159, 161, 162, 166, 177, 185, 196 of phthalate ester, 66
Potassium, 12, 13 of tetrachlorobiphenyl (TCB), 77
Potassium thiocyanate, 45 Redox-exchange separations, 92, 135—148
Precipitate-exchange separations, 139—141 column, 135—139
Preconcentration, 92 Reduction
of antimony, 112, 116 of cerium, 136
of cobalt, 34, 119 of iron, 137
of indium, 112 of vanadium, 137
of iridium, 37 Resilient foams, see Open-pore polyurethane
of iron, 34 (OPP)
of mercury, 105, 112 Resins
of methylmercury, 112 ion exchange, 25
of phenylmercury, 112 phenolic, 7
of polynuclear aromatic hydrocarbons (PAH) superficially sulfonated, 132
of rhodium, 37 Resolution, 179, 180
of silver, 105 Retention
Preparation of foam, 7—8 in aqueous media, 15—17
Preparative chromatography, 191 —192 of cobalt, 98
Propan-2-ol, 55 of copper, 98
Pulsating columns, 4, 16—17, 122, 146 of gaseous media, 17—22
217
of gold, 98 of iridium, 33, 37, 130

of gold-thiourea complexes, 49 of iron, 33,98, 117, 130
of inorganic species, 22 from aluminum, 27
of iodine, 148 isotope-exchange, 138—148
of iron, 98 of ketosteroids, 190
of open-pore polyurethane (OPP), 189 of manganese, 117
of organic species, 22 of mercury, 33, 117
of palladium-thiourea complex, 93 of nickel, 93, 95, 115, 116, 131
times for, 177 of nonane, 192
Reticulated foam, 7 of palladium, 33, 93, 95
Rhenium, 24 from bismuth, 94
Rhodium from nickel, 94
extraction of, 33 of pentane, 192
preconcentration of, 37 of polar compounds, 190
separation of, 33, 37, 130 precipitate-exchange, 139—141
Rigid (closed-cell) foams, 7, 10, 11 radiochemical, 138
Rodenticides, see also specific types of radioiodide, 142—144, 146
chlorinated hydrocarbon, 157 of radiosilver, 147
redox-exchange, 92, 135—148
column, 135—139
s of rhodium, 33, 37, 130
of silver, 105, 140, 147
Sample capacity, 179 of thorium, 131
Sample loading range, 183 of zinc, 33, 117
Sample sizes, 177, 180 Shore A hardness of OPP, 162, 166
Selectivity Silica, 177, 183—185, 189
of ion exchange, 133 Silicon, heteropolymolybdates of, 53
of open-pore polyurethane (OPP), 189 Silicone oil-loaded foams, 102
Semiquantitative determination Silicone rubber, 130
of alkylbenzenesulfonate (ABS), 128 Silver, 152
of cadmium, 122, 126 collection of, 105
of chromium, 122 distribution coefficient of, 53
of cobalt, 122 isotope exchange separation of, 140
of copper, 122 preconcentration of, 105
of iron, 122 radioactive, 139, 140, 147
of lead, 122 separation of, 105, 140
of mercury, 122, 126 sorption of, 51
of nickel, 122 Silver sulfide, 139
of phosphate, 126 Silver-thiourea complexes, 97
reagent foams in, 121 —128 Sodium, 12, 13
of tin, 122, 126 Solution process, 179
of zinc, 122 Solution temperature, extraction efficiency and,
Separation, see also specific types, 92 37
of aliphatic hydrocarbons, 180 Solvents, see also specific types, 162
of antimony, 110, 116 extraction, 43, 45, 92
of bismuth, 93, 95 flow rates for, 159
of cadmium, 113, 117, 130, 131 Sorbed cholinesterase, 156
of cadmium-zinc, 130 Sorption, 41
of cobalt, 33, 117, 131 of alkali metal picrates, 49
from manganese, 119 of alkali metals, 51
from nickel, 128, 129 of antimony, 117
of copper, 113, 117, 130 from aqueous media, 23—70
of dichloroanilines, 185 inorganic species, 23—55
of gallium from aluminum, 27 organic species, 55—70
of gold, 96—117 of barium, 51
from ore, 26 of benzo(a)pyrene, 60
of gold chloride, 25 capacities for, 23, 24
of heptane, 192 of chlorinated hydrocarbons, 59
of indium, 33, 117 of cobalt, 118
of inorganic species, 23 of copper, 121, 132
of iodine, 144, 146 of gallium, 29
from gaseous media, 70—92 TCB, see Tetrachlorobiphenyl

of gold, 24, 38, 120 Temperature
of gold-thiourea complex, 92—93, 97 BaP recovery and, 60
of hexachloroiridate, 54 cerium reduction efficiency and, 136
of hexachloroplatinate, 55 extraction efficiency and, 37
of indium, 38, 120 gallium extraction and, 27
of iron, 121 HETP and, 94
isotherms of, 24 open-pore polyurethane (OPP) diameter and,
of lead, 51 162
of mercury, 24, 38, 120 polymerization and, 162
of mercury chloride, 134 stability of, 11, 180
of metal ions, 105 of water, 60
methylene blue and, 57 Temporary filler, 8
of methylmercury chloride, 134 Tetrachlorobiphenyl (TCB), recovery of, 77
of mixed cresols, 69 Tetrachlorohydrobenzoquinone, 136
from nonaqueous media, 54—55 Tetrachlorohydroquinone, 135
of organochlorine insecticides, 83, 102 Thallium
of palladium-thiourea complex, 49 distribution ratios for, 24
of phenol, 69 sorption of, 24, 51
of phosphomolybdate, 54 Theoretical plate numbers, 179, 185
of phosphomolybdate anion, 47 height equivalent to a (HETP), 93, 94, 177,
of polychlorinated biphenyls (PCBs), 56, 75, 180, 189
102 for open-pore polyurethane (OPP), 177
of silver, 51 Thermal decomposition of chemical blowing
of thallium, 51 agents, 7
from thiourea-perchloric acid solution, 97 Thermodynamic properties of open-cell foams, 28
of zinc, 38, 120 Thermogravimetric analysis, 173
Soxhlet extractors, 86, 88, 90, 134 Thin-layer chromatography, 191
Spot tests, 14 Thiocyanate, extraction efficiency and, 37
Squeezing, 122 Thiocyanate-cobalt complexes, extraction of, 37
automatic, 15, 32, 120 Thiocyanate-palladium complexes, extraction of,
batch, 120 41
Stability Thiourea, 49
of open-pore polyurethane (OPP), 161, 183 Thiourea-bismuth complexes, 95
temperature, 180 Thiourea complexes, see also specific types
Storage of foams, 15 extraction of, 97
Stress-strain compressing strength of open-pore Thiourea-gold complexes
polyurethane (OPP), 173 extraction of, 98
Styrene-polyurethane copolymer, 134—135 retention of, 49
Sulfhydril groups, 134 sorption of, 92—93, 97
Superficially sulfonated resins, 132 Thiourea-palladium complexes
Surface, 162 retention of, 93
Surface area, 12, 102, 161, 190 sorption of, 49
Surface characteristics, 159 Thiourea-perchloric acid systems, 93—95
Surface hydroxyls, 189 sorption from, 97
Surfactants, 159 Thiourea-silver complexes, 97
Synthesis of polyurethane foam, 8—11 Thorium, separation of, 131
for open-pore polyurethane (OPP), 159—161, Tin, 12, 13
185 detection of, 126
T semiquantitative determinations of, 122, 126
TOA, see Tri-n-octylamine
TBP, 109, 128, 140, J42 TOC, see Total organic carbon
TBP-HC1 system, 98 p-Toluenesulfonyl semicarbazide, 7
TBP-loaded foam, 92, 94, 98 Total organic carbon (TOC), 191, 193, 194
TBP-perchloric acid-thiourea system, 98 Total phenol, 193
TBP-plasticized o-benzildioxime, 116 Toxaphene, collection of, 77
TBP-plasticized diethylammonium DDC foam, Trace elements, see also specific elements, 12, 13
110 collection of, 2
TBP-plasticized iodine foam, 141, 143 Trace organic contaminants, 67
219
Trapping Uranyl nitrate, extraction of, 33

of enzyme inhibitors, 155—157 Urea, 9
of volatile combustion products, 148—155
Triallate, 90
Tri-n-butyl phosphate, see TBP
V
Triethylamine, 161
Trifluoracetic anhydride, 90 Vanadium, 12, 13
Trifluralin, 90 pulsated columns for, 137
Tri-n-octylamine (TOA) foams, 128—130 reduction of, 136, 137
silicon rubber loaded with, 130 Van IJeemter equation, 180
Triphenylene, 88 Van Deemter plot, 177
Volatile combustion products, 148—155
Volatile PAHs, 88
U
Unloaded polyurethane foams, 22, 49, 55, 135—

w
157
column redox reactions, 135—139 Water temperature, 60
isotope- and redox-exchange separations, 138— Weak-base anion exchange, 43, 173
148
polyester type, 34
polyether type, 34, 49
z
trapping enzyme inhibitors and the immunoad-
sorption of cells, 155—157 Zinc
trapping volatile combustion products in or- cation exchange distribution ratios of, 133
ganic microanalysis, 148—155 coextraction of with cobalt, 37
Unplasticized dithizone foams, 105 collection of, 120
Unplasticized l-(2-pyridylazo)-2-naphthol (PAN) extraction of, 33, 45, 117
foams, 117, 118, 120 gold separation from, 97, 98
Untreated polyurethane foams, 47, 54 qualitative determinations of, 122
polyether type, 148 semiquantitative determinations of, 122
Uranium separation of, 33, 117
absorption of, 32 sorption of, 38, 120
distribution ratios for, 24 Zinc diethyldithiocarbamate-foam (ZnDDC), 110
sorption capacities for, 24 Zinc dithizonate, 108, 109

,!7IB3B5-ijgibg!: Polyurethane Foam Sorbents in Separation Science

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,!7IB3B5-ijgibg!: Polyurethane Foam Sorbents in Separation Science

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CRC REVIVALS CRC REVIVALS

Tibor Braun, James D. Navratil, A. B. Farag

Tibor Braun, James D. Navratil, A. B. Farag

Tibor Braun, Ph.D.

James D. Navratil, Ph.D.

Boca Raton London New York

CRC Press CRC Press,

Reissued 2018 by CRC Press

© 1985 by CRC Press, Inc.

No claim to original U.S. Government works

Library of Congress Cataloging in Publication Data

A Library of Congress record exists under LC control number: 84007701

ISBN 13: 978-1-315-89681-6 (hbk)

POLYURETHANE FOAM SORBENTS

I. QUASI-SPHERICAL SOLID MEMBRANES IN SEPARATIONS

In a great majority of separation and/or preconcentration processes a solid sorbent

Planar Cylindrical Spherical

FIGURE 1. Equivalent sections of three membrane geometries.

FIGURE 2. Geometrical relationship for three membrane configu-

II. HISTORICAL OVERVIEW

water employing natural sponge supporting iron(III) hydroxide precipitate. By towing

III. FOAMED POLYURETHANE POLYMERS

IV. FUNDAMENTAL KNOWLEDGE OF FOAMED POLYURETHANES

FIGURE 3. Growth curve of publications dealing with po-

FIGURE 4. Growth curve of world polyurethane foam consump-

FIGURE 5. Scanning electron micrographs of a typical polyurethane foam struc-

D. General Methods of Foam Preparation

b. Blowing by In Situ Chemical Reaction

b. Blowing by Vapor from a Volatile Liquid

b. The Use of Microspheres

E. Polyurethane Foam Synthesis

R-N=C=O + R'-OH -> R-NH-C-0-R' (1)

The isocyanate group is considered to exist in the following resonance forms: 9

R_N-C=0 •«• R-N=C=0 <-> R-N-C-0: (2)

Electron-withdrawing substituents on the isocyanate molecule should move negative

R_N=C=O + H 2 0 •[R-NH-C-OH]-" R-NH2 + C02

[R_NH-C-OH]+ R-N=C=0 ->[R-NH-C-0-C-NHR] (4)

R_NH-CO-NHR + CO, < 1

thane reaction producing allophanate linkages (Equation 5) and the isocyanate-urea

R _N=C=0 + R-NH-C-OR' R -NH-C-N-C-0-i-R'

R_N=C=O + R-NH-C-NHR' R-j_N-CO-NH R' (6)

V. PHYSICAL AND CHEMICAL PROPERTIES OF POLYURETHANE

Generally, the physical properties of polyurethane foams depend on the method by

Tin 850 1110

Note: Each result is an average of three determinations; the relative

Element Ether-type Ester-type

Note: Each result is an average of three de-

From Braun, T., Abbas, M. N., Elek, A.,

VI. ANALYTICAL METHODS FOR THE CHARACTERIZATION OF

A. Differentiation of Polyurethane Foams from Other Plastic Foams

B. Qualitative Spot Reaction for Polyester- or Polyether-Based Polyurethane Foam

1. 2 M solution of KOH in methanol plus phenolphthalein to a dark pink color.

Procedure — Approximately 50 mg of small pieces of foam are treated with a few

VII. EXPERIMENTAL TECHNIQUES IN THE ANALYTICAL USE OF

A. Preparation of Resilient Polyurethane Foam Sorbents for Analytical Use

B. Collection and Retention Techniques in Aqueous Media

FIGURE 6. Chromatograms of petroleum ether extracts of foam

3. Pulsating Column Methods

FIGURE 7. Cell used in foam squeezing. From

C. Collection and Retention Techniques in Gaseous Media

FIGURE 8. Foam chromatographic column in

the cartridge receptacle. A combination of polyurethane foam and granular sorbents

FIGURE 13. High-volume sampling apparatus for polynu-