<'

Contents

Foreword ......... ' . ' ' ' ' ' ' . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Techniques of Ion Exchange
Batch vs. Column Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Selection of Laboratory Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Preparation of Laboratory Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Operation of the Column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Where Ion Exchange Resins are Useful
Types of Appl ications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Types of Ion Exchange Resins and Their Reactions .......................................... 10
Selection of Correct Ion Exchange Resin .......................................... . . . .. . .. 12
Rules of Ion Exchange Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

Demonstration Experiments
Concentration by Ion Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Conversion by Ion Exchange . ........................... . ............................... 15
Purification by Ion Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
De ionization
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Deionizatlon by Monobed Resins .. . ................................. . ... .. .............. 18
Preparation of Deionized Water for the Laboratory .. .. ........................ . ............ 19

Determining Ion Exchange Capacity

Introduction ... . .. . ................................................................... . 22
Co ndition ing ............................................................. . ... : . ........ 22
Solids (or Moisture) Content Determination ................................................ 22
Cation Exchange Capacity (CEC) .. ... . . ............................................ . .... 23
Salt-Splitting Cation Capacity (SSCC) ............... . ...... . .............................. 23
Weak Base, Strong Base. and
Total An ion Exchange Capacity (TAEC) ............................................... . . . 23
Anion Exchange Capacity (AEC) .......................... . .............................. 24
Appendix
Larger-Scale Column Testing .................................................... . ........ 26
Ion Exchange Constants and Conversions ............................ . .................... 27
Screen Equivalents .................. .. ................ . ...................... .. .... .. . . 28
Electrical Resistance of Dilute Electrolytes ................................................. 29
Foreword ~
The development of ion exchange tech-
nology and the availability of ion exchange
resins possessing a wide array of properties
have resulted in the widespread use of these
materials in commercial processes and in
laborato..cies throughout the world. Primarily,
this laboratory guide is designed to help lab-
oratory personnel use ion exchange resins
easily and effectively. Its secondary purpose
is to review the ways in which ion exchange
resins will be helpful in the laboratory for
preparative and analytical work and to sug-
gest the utility of ion exchange resins for
commercial chemical processes. Therefore,
emphasis is placed on the actual tech-
niques involved and ion exchange funda-
mentals are mentioned only where they will
help explain these techniques.

1
-> attached to the top of the column with a suit-
Figure 2 Buretta Ion Exchange Resin Column able delivery tube provided with a flow control
device such as a screw clamp. Reservoirs
should always be placed higher than the top of
TO WATER INLET
the column and the attachment to the column
t should be airtight. Separatory funnels are very
RUBBER TUBING
useful and convenient since they contain a
stopcock which can be used to start and stop
SCREW CLAMP the flow, and they can be seated into the top of
-
GLASS TUBING the column by means of a rubber stopper. Flow
rate should be controlled at the bottom of the
column to ensure that the column Is always
flooded .

Preparation of
Laboratory Columns
Safe Handling Information
NOTE: Some precautions should be kept in
mind whenever on ion exchange column is to
ION EXCHANGE RESIN be used. Always fully hydrate on ion exchange
resin sample before charging It to a column
and make certain the column already con-
tains some water, Never allow a column to
become dry, since rehydration of the resin will
cause it to swell, possibly shattering the gloss
column. During the course of on experiment,
be sure to maintain a constant liquid head over
the top of the bed. Add the next solution to the
reservoir In time to prevent such loss or be sure
to stop flow through the column while switching
to another solution. If it is necessary to interrupt
GLASS WOOL PLUG a column run, be sure to shut off both influent
and effluent valves and keep the resin com-
pletely submerged in liquid.

Material Safety Data Sheets

Material Safety Data Sheets are available for
all Rohm and Haas products. To obtain Material
down the tube at the bottom as shown. For ion
Safety Data Sheets, contact your local Rohm
exchange resins of chromatographic size (100
and Haas representative.
mesh or smaller) smaller columns (less than
½ inch (12.7 mm]) are employed, and the Ion CAUTION: Acidic and basic regenerant solutions
exchange resins are usually supported by fine are corrosive and should be handled In a man-
porosity sintered glass discs. Chromatographic ner that will prevent eye and skin contact.
effects can be facilitated by using long col- Nitric acid and other strong oxidizing agents
umns with very small diameters, and many of can cause explosive-type reactions when
the columns normally used in adsorption chro- mixed with ion exchange resins. Proper design
matography may also be employed for ion of process equipment to prevent rapid buildup
exchange chromatography. of pressure Is necessary if use of an oxidizing
Almost any convenient vessel can be used to agent such as nitric acid Is contemplated .
hold the stock or regenerant solutions if it Is Before using strong oxidizing agents in contact

3
with ion exchange resins, consult sources 6. Adjust the liquid level to within 1-2 centi-
knowledgeable In the handling of these meters above the top of the bed.
materials. NOTE: Operation of mixed bed systems re-
quires special techniques. See section entitled
Charging Ion Exchange Resins "Design of Large Laboratory Unit."
Into Columns
Deionized water should be used to transfer ion Conditioning of Ion Exchange Resins
exchange resins to the column. The column If the ion exchange resin is in the proper ionic
itself should contain some water at the start of form the only conditioning step necessary is a
the operation, and the ion exchange resin brief rinse with deionized water to remove
should be poured into the column as a water materials that may have formed or leached
slurry, using a beaker or other vessel. Dry ion from the resin during storage.
exchange resins should always be fully Occasionally it may be desirable to condi-
hydrated before introduction into the column, tion further. For example, when trace metals in
since the swelling pressures created when the the parts-per-billion (ppb) range are to be
resin imbibes water may burstthe glass column. determined, plastic columns can be employed
The following steps, then, should be followed in and the resins treated with reagent-grade
charging resins properly: hydrochloric acid before being rinsed with
1. Add resin-water slurry as described above deionized water.
to a column containing some water. If the ion exchange resin is not in the re-
2. Occasionally drain excess water through quired ionic form, a regeneration step can be
the bottom of the column. included as part of the conditioning. This Is
3. Do not permit the liquid level to fall below discussed in a later section .
the resin level. If the ion exchange resin is to be used to treat
4. Continue adding In this manner until all a solvent other than water, it should be rinsed
resin Is transferred. with that particular solvent. If the solvent is not
5. Do not load columns to more than about water-miscible, some mutually miscible solvent
half their height. should be passed through the resin first, fol-
lowed by the solvent Itself.
Backwashing
The following procedure frees the bed of
Operation of the Column
entrapped air pockets, classifies the resin parti- Before proceeding to actually use an ion
cles, and rids the bed of debris and resin fines: exchange column for a laboratory applica-
1. Attach a water line to the bottom of the tion, consideration should be given to the flow
column . rates to be employed, concentrations of the
2. Introduce deionized water upflow very solutions that will contact the resin, and the
slowly. volume of these solutions required. Although
3. Increase the flow until the bed of resin the following recommendations need not be
expands to near the top end of the adhered to exactly, their practice will help
column. ensure that efficient ion exchange will occur.
4. Maintain this flow until all air pockets are In column technique the actual exchange
removed and all the particles have of ions is usually termed the "exhaustion" or
achieved mobility. (Extremely small parti- "adsorption" step. If the resin is to be reused
cles may be allowed to pass out of the after exhaustion takes place, a "regeneration"
column.) This step is most important and, step is necessary. This should always be pre-
if performed correctly, will result in good ceded by backwashing to remove particulate
particle size classification with the smaller material that may have been in the solution
particles at the top and the larger ones at < during the previous exhaustion step. Following
the bottom portion of the column. regeneration the ion exchange resin must be
5. Stop the flow of water and permit the resin rinsed free of excess regenerant before pro-
to settle by gravity. ceeding to the next cycle.

4
Assuming that the resin has been charged > Rinse Step - use enough to rinse excess
to the column, backwashed and settled cor- regenerant from the column. Usually 10 bed
rectly, the liquid level adjusted, and the resin volumes of deionized water are adequate.
itself in the proper ionic form, a measurement Rinse can be checked chem ically to insure
should be made of the resin volume in place in completeness.
the column. It is most convenient to use pre- NOTE: About 30 to 40% of the total volume
calibrated columns or burette-type columns occupied by an Ion exchange resin in a col-
because the volume can be read directly. umn is void space. The exhausting solution will
Otherwise the top of the bed can be marked displace the water or other solvent filling this
and the volume determined later."'The volume space, so it is usually desirable to discard the
of resin under these conditions is termed a first bed volume before collecting the treated
"bed volume." It includes the void spaces solution unless a quantitative expe riment is
between particles. being performed.
Flow Rates Typically Employed
Exhaustion Step - 0.1 to 0.2 bed volumes Regeneration
(BV)/minute. Note- 0.133 ml / ml /min = 8
BV/hr = 1 gpm/ft3. To reuse an ion exchange resin after an
Backwash Step- see "Backwashing," exhaustion step, or to convert it to another
Regeneration Step-0.05 to 0.1 BV/mlnute. ionic form for a different e xperiment, a proper
Rinse Step-same as regeneration for first BV;
same as exhaustion for remainder. TABLE 1
NOTE: These suggested flow rates are adequate Suggested Regeneratio n Levels
for most laboratory investigations Involving 16 to Ion Requirement
50 mesh (U.S. Standard Screens) material. They Exchange Ionic Regen- (Meq. Regen)
should be decreased when working with finer Resin Form eront Meq. Resin
particle size resins. A simple way to measure flow Strongly
rate Is to periodically collect some of the effluent Acidic H+ { HCI } 3-5
in a graduated cylinder while checking the time H2 SO 4
Cation Na + 3-5
with a stop watch. For permanent columns Exchanger NaCl
ftowmeters can be fitted Into the effluent line.
Weakly
Concentrations of Solutions Acidic H+ { HHCI} 1.5-2
Exhaustion Step - less than 0.1 Normal for 2 SO 4
Cation Na + 1.5-2
quantitative exchange; somewhat higher Exchanger NaOH
concentrations can be tolerated if quan-
titative removal is not necessary. Strongly
Backwash Step- use deionized water for ana - OH - NaOH 4-5
Basic
lytical experiments. Anion {NaCl}
Regeneration Step- about 1,0 Normal in gen- Cl - 4-5
Exchanger HCI
eral; 4 to 10% usually acceptable. Type 1·
Rinse Step - deionized water. If exhaustion SO 4 = {Na 2 S0 4 } 4-5
H2 SO 4
Involves other solvent. displace water with
solvent; if not water-miscible use mutually Type 11· OH - NaOH 3-4

l
miscible solvent as intermediate rinse,
Weakly
Volumes of Solutions Basic
Free Base NaOH
NH (
Exhaustion Step-for quantitative exchange use Anion 4 OH 1.5-2
an amount of solution that contains Ions Na 2 CO 3
Exchanger
equivalent to a half of the ion exchange
capacity of the resin as measured in the Cl - HCI 1.5-2
column. SO 4 = H2 SO 4 1.5-2
Backwash Step- use as much as is required to
achieve desired results discussed In back- *Type I resins are benzyl-trimethylamine functionality.
wash section, page 4. Type II resins are benzyl-dimethylethanolamine functionality which
are of slightly lower basicity than Type I anion resins. This results ,n
Regeneration Step- use amounts calculated to better regeneration efficiency, but lower effectiveness in removal of
provide from 150 to 500% In excess of the- the anions associated with weak acids, such as silica (siliceous
oretical capacity of resin In column. acid).

5
Ion exchange resin is Resin / water slurry is
hydrated In a beaker poured Into column con-
while column Is flushed taining some water. Do not
with deionized water and load column to more than
prepared for use. half Its height.
Ion exchange resin Is Eluate Is collected In a
rinsed with an appropri- volumetric flask. Its capa-
ate solution. city Is then measured
with a known quantity of
reagent.
regeneration technique must be used. Column The "Regenerant Requlremenf' can be deter-
operation allows for a high level of regenera- mined from the previous table for various resin
tion and the same column used In the exhaus- types and ionic forms. The volume capacity of
tion cycle can be used for regeneration. The the particular Ion exchange resin must be
Ion exchange resin may require a thorough expressed as milliequivalents per milliliter of
backwash before the regenerant is applied resin or some other equivalent term.
and adequate rinsing should follow applica- Laboratory work of an analytical nature
tion of the regenerant. Suitable flow rates were requires as high a degree of regeneration as
given in the previous section . Note that the first possible. Levels of regeneration calculated in
bed volume of rinse water should be applied at the above manner are designed to Insure that
the regeneration flow rate since this actually regeneration will accomplish this. It should be
represents the completion of regeneration . noted that more moderate levels are called for
Suggested concentrations of regenerants In commercial operations or when quantitative
were also given In the previous section . In gen- removal Is not necessary.
eral. concentrations of about 1to 2 Normal are For the same reasons it is suggested that
used (about 4 to 10%). Applied at the suggested regenerants for laboratory work be formu-
flow rates, such concentrations will allow for lated using reagent-grade chemicals and
adequate contact time if the correct volumes deionized water. This can be especially impor-
of regenerant are used. tant for the regeneration of strongly basic
anion exchange resins because they have
high affinities for substances like carbonates,
CAUTION: Most regenerants are solutions of cor-
frequently present in impure caustic soda.
rosive acids or bases. Eye and skin protection
Special mention should be made of the
adequate to prevent contact should be used
regeneration technique for weakly dissociated
when handling these solutions and column ion exchange resins. Appropriate acids should
effluents during regeneration.
be used to convert weakly basic anion
The appropriate volume of a regenerant
exchange resins from the free-base form to a
depends upon the Ion exchange resin in ques-
salt form, and appropriate bases should be
tion. It Is convenient to express such volume in
used to regenerate weakly acidic cation
terms of bed volumes of resin. This can be cal-
exchange resins from the hydrogen form to a
culated from the following :
salt form. An advantage may be found in the
use of ammonium hydroxide for the regenera-
Bed Volumes of Regenerant = tion of weakly basic anion exchange resins to
Vol. Capacity of Res in x Regenerant Requirement the free-base form because the excess Is usu-
ally easier to remove by rinsing than is the case
Normality of Regenerant with sodium hydroxide.
Photomic rograph of cation exchange resin beads, magnified approximately 50 times.

8
Where Ion Exchange Resins Are Useful
Types of Applications > techniques. In the nuclear industry, ion
exchange resins are used to concentrate
Where Ion Exchange Resins Are Useful radioactive elements. Small volumes of con-
centrated resin or regenerant are easier to
When equipped with the fundamental types of store during decay than tremendous volumes
ion exchange materials, the laboratory worker of radioactive solutions.
can perform a wide variety of tasks. Many of
these reactions will be specialized, but, in gen- Purification and Deionization-Nearly com-
eral, there are five major categories of appli- plete removal of ions from solution can be
cations for ion exchange resins. Ttiese are: achieved with ion exchange by using the
hydrogen form of a cation exchange resin and
Conversion - One of the major applications the hydroxide form of an anion exchange resin.
of ion exchange resins is the transformation of In this way, many substances can be conve-
ionic species or the replacement of one ion by niently purified. By using both cation and anion
another. Often the aim of this technique is to exchange in this manner, solutions can be
replace a deleterious ion with an innocuous completely deionized In either a two-step
one. ion exchange methods can often help manner, by using the resins in a series-column
avoid lengthy precipitation techniques . In arrangement, or In a mixed bed process In
some cases, the desired product may not be which the resins are intimately mixed. Such
stable and preparation Just before use may be arrangements have made possible the Impor-
performed simply by ion exchange. One of the tant commercial application of deionizing
notable examples of conversion by ion water supplies for Industry. Delonlzation has
exchange is the softening of water (during become increasingly important for the deash-
which calcium, magnesium and other divalent ing of a wide variety of process liquors; treat-
cations are replaced by sodium) by using a ment of sugar solutions is a notable example.
strongly acidic cation exchange resin. In this Ion exchange purification may often be
case, the scale-forming ions are removed and accomplished more simply where undesirable
replaced by non-scale-forming sodium. components exist as acids or bases, therefore
Potassium salts can easily by converted to requiring treatment with only a single ion
sodium salts by the same techniques since the exchange resin . Examples of this are the
resin will exert a higher affinity for potassium. removal of formic acid from formaldehyde
This operation is used to convert the slightly and iron from hydrochloric acid.
soluble potassium bitartrate in wines to the
more soluble sodium salts. Other applications Fractionation-Ion Exchange Chromatog-
of this technique include the analytical raphy-Ion exchange fractionation can be
method used for the determination of total salt used to separate ionic mixtures where even
concentration . By converting ail cations to slight differences in selectivity of the ion
hydrogen ions a simple titration permits easy exchange resins may exist. Fractionation is pos-
evaluation of total concentration. sible on ion exchange res ins because of
molecular size or extent of ionization dif-
Concentration - Ionic materials that exist at ferences of the ionic species . For example,
low concentration can be adsorbed on an ion large ionic species such as sulfonic acid dyes
exchange column and then be eluted in a can be separated from smaller-sized species
much more concentrated form . This technique like mineral acids on anion exchange resins
is useful for the recovery of valuable ionic con - because of the preferential removal of the
stituents or as a means of pollution reduction. In mineral acid. Similarly, weakly and strongly dis-
many analytical schemes preconcentration of sociated acids can be separated using weakly
solutions containing very low levels of specific basic anion exchange resins which react pref-
ions is a convenient first step. Among the many erentially with the strong acids. In this way,
applications utilizing Ion exchange resins for hydrochloric acid can be separated from
concentration, metal recovery Is an outstand- acetic acid since the latter travels through the
ing one. Recovery of copper, chromium, ura- ion exchange column more freely. Two general
nium, gold, and many other metals can be methods useful for separations involve adsorp-
accomplished with suitable ion exchange tion and elution chromatography. Adsorption

9
chromatography generally applies to the sep- there is sufficient water present to swell the gel
aration of solutes that exhibit reasonably differ- structure and thus permit the reactants to dif-
ent selectivities for a resin, such as the fuse to the acidic or basic sites. Macroretlcular
separation of divalent and monovalent ions. ion exchange resins with physical porosity built
More closely related ionic species can often into the matrix are particularly useful for cata-
be separated by elution chomatography in lysis in non-aqueous solutions. More details on
which an elution agent is used to selectively both aqueous and non-aqueous catalysis with
strip several adsorbed species. Gradient elu- ion exchange resins are available from the
tion Is often used and consists of progressively Fluid Process Chemicals Department of Rohm
increasing the concentration of the eluting and Haas Company.
agent. By these various techniques many diffi- PRECAUTIONARY NOTE: While in the foregoing
cult separations have been made possible. applications the ion exchange resins them-
These include the fractionation of amino acids selves present no significant toxic hazard, the
and the separation of rare earths. In the latter laboratory worker should be alert to the haz-
case, small differences in selectivity can be ards of the various reagents or solvents intro-
enhanced by the use of complexing agents. duced to the column and the hazards of the
effluent from the column . Adequate safety
Catalysis-Many organic reactions are cata-
measures should be taken to protect oneself
lyzed by mineral acids or strong bases. It is not
from exposure by using suitable eye and skin
surprising that many organic chemists have
protection in addition to providing for proper
used or considered the use of Ion exchange
ventilation .
resins as catalysts. The advantages of resin cat-
alysts over various homogeneous catalysts are
apparent:
Types of Ion Exchange Resins
1. The resin can be removed from the reaction and Their Reactions
mixture by a simple filtration step.
2. The resin may be placed in reactors through There are four fundamental types of synthetic
which the reaction mixture is passed in a ion exchange resins available. Each type is
continuous process. essentially analogous to common acids or
3. Corrosion problems arising from the use of bases and undergoes similar reactions. The pri-
homogenous catalysts can be greatly mary difference, however, is that the ion
reduced through the use of resin catalysts. exchange materials are insoluble and actually
4. The production of unwanted by-products of remove constituents from solution by the for-
reactions peculiar to the use or removal of mation of a resin salt while the common acids
homogenous catalysts can be avoided. and bases form water-soluble salts with the
5. Neutralization, precipitation, distillation and constituents present in solution . These four
extraction steps, which usually accompany types and their typical reactions are listed
the use of homogeneous catalysts, can be below. Note that R2 represents the polymer
eliminated. matrix of the ion exchange resin.
6. The direct recovery of the catalyst permits its
reuse. Strongly Acidic Cation Exchange Resin-
Companies producing oil-epoxide plas- Analogous to sulfuric acid.
ticizers now use ion exchange resin-catalyzed R,SO 3 H + NaOH :;::: R,SOaNa (1)
processes. The production of invert sugar from
sucrose is commercially accomplished R,SO 3 H + NaCl :;::: R,SO 3 Na (2)
through use of strongly acidic cation exchange 2R,SO 3 Na + CaCl 2 :;::: (R,SO 3 ) 2 Ca + 2NaCI (3)
resin catalysts. Other processes in which ion
exchange resin catalysis has been studied
include olefin hydration, ester formation and Weakly Acidic Cation Exchange Resin-
ester hydrolysis, acetal formation, a Idol con-< Analogous to acetic acid .
densation and many others.
Conventional gel-type ion exchange resins
R,C0 2 H + NaOH :;::: R.C0 2 Na + H20 (4)
are useful chiefly in aqueous systems where 2R,C0 2 Na + CaCl:i :;::: (R,C0 2 )~Ca + 2NaCI (5)

10
Strongly Basic Anion Exchange Resin- Reactions (2) and (7) represent the salt-
Analogous to sodium hydroxide. splitting properties of strongly acidic cation ex-
changers and strongly basic anion exchangers.
R.N R8 0H + HCI .= R. N R3 CI + H2 0 (6) The weakly acidic and weakly basic exchangers
R.N R3 0H + NaCl .= R. N R3 CI + NaOH (7) do not undergo these rsactions nor will they re-
2R,N R3 CI + H~S0.1 .= (R . N R3 ) 2 S0 4 + 2HCI (8) move extremely weak bases and acids. Data
plotted In Figures 3 and 4 show the titration
curves for each of the four fundamental types
Weakly Basic Anion Exchange Resin-
of ion exchange resins. They are most useful for
Analogous to ammonium hydroxide.
studying the behavior of the various exchangers
R,NH 2 + HCI .= R,NH 3 CI and can be helpful In choosing the correct resin
or
for any given application . Other tips on ion
exchange resin selection are given in the next
R.NH 3 0H + HCI .= R,N H3CI + H2 0 (9) section.
2R,NH 3 CI + H2 S0 4 .= (R,NH 3 ) 2 S04 + 2HCI (10)

Figure 3. Titration curves of cation exchange resins

14
L- I
l ~
12
f'strongly Ai:ldlc I~
10
/
pH
8

4
,
,
_1....,.. Weakly Acidic

2 ~"
2 4 6 8 10
MILLIEQUIVALENTS ALKALI ADDED PER GRAM

Figure 4. Titration curves of anion exchange resins

14
12
- ~

10

8
~
Weakly
ic
" Strongly
Basic

' ~,
pH
6

4
r-,-......._
-
2

2 ' 4
MILLIEQUIVALENTS ACID ADDED PER GRAM
6 8 10

11
Cycling test apparatus for ion exchange process.

Selection of Correct Ion Exchange preferred. With anion exchange resins, operat-
ing temperature can be a deciding factor in
Resin choosing between the weakly and strongly
In selecting the proper ion exchange resin for a basic types.
particular laboratory application, the investi-
gator must decide upon the following: (1) func-
tionality required, (2) proper porosity or degree Porosity-Crosslinker Level
of crosslinkage and (3) particle size. In general. ion exchange resins with lower lev-
els of crosslir\'kers in the copolymer matrix are
Ionic Functionality capable of Imbibing greater amounts of water
when they are hydrated. Such resins are said to
Selection of the proper functionality depends have higher porosity, but it must be empha-
primarily upon the nature of the system. Most sized that this refers to the gel phase porosity,
often strongly acidic cation exchange resins or and is independent of any physical porosity
strongly basic anion exchange resins can be resulting from the presence of discrete pores
employed for sorblng or separating practically in the resin . High gel phase porosity (low
all ionic species. This is so because they are .:
crosslinker) will normally result in more rapid
the most strongly dissociated types. However, diffusion of ions into and out of the gel phase,
when regeneration efficiency or the stability of a distinction that is more important when
materials of a biological nature are involved, the adsorbate is a large, complex ion or mole-
weakly dissociated exchangers are usually cu Ie. Resins with low gel phase porosity

12
(high crosslinker level - low moisture-holding .. separations, such as those between ions of like
capacity) will be more capable of excluding and similar charge, are frequently made using
larger molecules and are likely to exhibit slower chromatographic techniques. These latter
gel phase kinetics than are resins with low lev- applications frequently require resin particles
els of crosslinker. This will have an effect upon of much smaller particle size and narrower size
selectivity of the resin for various solute ions, distribution . Chromatographic-grade Ion
and Ion exchange resins with higher crosslinker exchange resins are available from laboratory
levels usually display higher degrees of selec- supply houses with particles sizes as small as
tivity, following the order presented in the next - 325 mesh, or about 45 microns. In general,
section. , columnar operations not involving a chro-
The presence of physical porosity, as in matographic separation are carried out using
Amberlite macroreticular resins, will have an normal size Ion exchange resins [or perhaps
effect upon adsorption and elution kinetics screen cuts from within this range) to avoid the
apart from the considerations of gel phase very large pressure drops which unavoidably
porosity described above. The diffusion path accompany the use of very small particles.
length of adsorbate ions or molecules is short-
ened by the presence of pores in the resin
matrix. This results in higher rates of loading and
elution In those cases where gel phase diffu-
Rules of Ion Exchange Selectivity
sion is the rate-limiting step. The following are empirical rules, intended as a
Another consideration in this regard applies guide to help understand relative selectivity
to the use of ion exchange resins in non-aque- patterns, but they cannot be interpreted strictly
ous solutions, where macroretlcular resins are for all cases.
normally much more effective than gel resins
with no physical porosity. When the gel phase 1. At low aqueous concentrations and ordi -
of any ion exchange resin is hydrated as a nary temperatures, the extent of ex -
change or exchange potential increases
consequence of the resin having imbibed
water, the polymer chains are opened or with increasing valence of the
forced apart, thereby making the lonlcally exchanging ion.
functional sites accessible to the sorbate ion or (Na +< Ca ++< La +++ < Th++++)
molecule. In the absence of water, as, for
example, in non-polar media, the polymer 2. At low aqueous concentrations, ordinary
chains return to their original, unhydrated con - temperatures, and constant valence, the
dition in which they are more tightly "packed," exchange potential Increases w ith in-
thereby reducing the accessibility of the func- creasing atomic number.
tional sites. A resin with high physical porosity
will be less dependent upon matrix hydration
(Li < Na < K < Rb < Cs; Mg < Ca < Sr < Ba;
owing to the decreased diffusion path length
F < Cl < Br < I)
mentioned above, and will thus be more useful 3. At high concentrations, the differences in
in anhydrous conditions as compared to a exchange potentials of ions of different
resin with no physical porosity. valence diminish and, in some cases, the
ion of lower valence has the higher
exchange potential.
Typical Particle Size (Na + vs Ca ++ )
Ion exchange resins have a particle size dis- 4. At high temperatures, or in non-aqueous
tribution ranging between a #16 sieve (U .S. media, or at high concentrations, the
Standard Sieve) and a #50 sieve. The particle exchange potentials of Ions of similar val-
diameter range is thus from 0.3 mm to 1.2 mm. ence do not increase with increasing
Resins with this particle size are typically used in atomic number but are very similar, and
columns in the majority of applications which level off or even decrease.
are based upon separation, isolation or 5. The exchange potentials of various ions
exchange of cations or anions. Certain difficult may be approximated from their activity

13
coefficient; the higher the activity coeffi- TABLE 2
cient, the greater is the potential.
6, The exchange potential of the hydrogen Relative Selectivity Coefficients of
ion or the hydroxide ion depends upon Strongly Acidic Cation Exchange Resins
the strength of the acid or base formed
between the functional group and the % Divinylbenzene (crosslinker)
hydrogen or hydroxide ion. The stronger
the acid or base formed, the lower is the Cation 4 8 10
protential. Li 1.00 1.00 1.00
7. Organic ions of high molecular weight H 1.30 1.26 1.45
and metallic anionic complexes exhibit
Na 1.49 1.88 2.23
unusually high exchange potentials.
8. As the degree of crossllnking or the fixed NH 4 1.75 2.22 3.07
ion concentration of any ion exchanger is K 2.09 2,63 4.15
lowered, the exchange equilibrium or Rb 2.22 2.89 4.19
selectivity coefficient approaches unity. Cs 2.37 2.91 4.15
Ag 4.00 7.36 19.4
Tl 5.20 9.66 22.2

TABLE 3

Relative Selectivity Coefficients of

Strongly Basic Anion Exchange Resins

Anion Coefficient

OH 0.09
Cl 1,0
Br 2.8
N0 3 3,8
I 8.7
C10 4 10,0

14
Demonstration Experiments
>
Experiment I- ately. If boron, silica, and carbon dioxide are to
be determined, Amberlite IRA-400, hydroxide
Concentration by Ion Exchange form, can be substituted for the Amberl lte
Purpose: Concentration of all cations and min- IRA-93 or added in a series as a third column
eral acid anions in a water supply whose total following the Amberl ite IRA-93. Elution of the
dissolved solids content is less than 500 ppm strongly basic resin should be accomplished
(as calcium carbonate). with 50 ml of warm (40°C.) 2N NaOH. Although
ammonium hydroxide is adequate to regene r-
Materials: Amberl ite IR-120 Plus (H), hydrogen ate the weakly basic anion excha nge resin, It is
form . , not a strong enough base for regeneration of
Amberl ite IRA-93, free-base form . the strongly basic a nion exc hange res in.
Two ion exchange columns. Sodium hydroxide is required for the latter.
Separatory funnel. Other weakly basic anion exchanges, such as
Hydrochloric acid. Amberllte IRA-68 or Amberllte IRA-94 may be
Ammonium hydroxide. used in place of Amberlite IRA-93.
Deionized water.
Procedure: Prepare one column charged with
about 20 ml of Amberl ite IR-120 Plus (H), and the
other with about 20 ml of Amberlite IRA-93, Experiment II-
free-base form . Connect the columns in series Conversion by Ion Exchange
with small-diameter rubber tubing leading
from the bottom of the cation exchange resin Purpose:To determine the total salt concentra-
column to the top of the anion exchange resin tion of a solution by exchanging hydrogen Ions
column. The second column should be about 4 for existing cations.
to 6 Inches (10.2 to 15.2 cm) below that of the Materials: Amberlite IR-120 Plus (H), hydrogen
first. Place one liter of the water sample in a form.
separatory funnel connected to the top of the Ion exchange column.
cation exchange resin column . Pass the water Separatory funnel.
sample through the two columns at recom- Erlenmeyer flask.
mended exhaustion flow rate (0.1 to 0.2 bed Standardized sodium hydroxide.
volumes per minute). Just as the last of the Deionized water.
sample leaves the separatory funnel add 200
ml of deionized water to the funnel and flush Procedure: Prepare an Ion exchange column
this through both columns. Do not allow either with 10 to 20 ml of Amberlite IR-120 Plus (H). The
column to run dry. Stop the columns In time to sample to be analyzed should contain 1 to 4
maintain the usual liquid level over the resins. meq of electrolyte and the concentration
Disconnect the columns. Elute adsorbed ca- should be adjusted with deionized water so
tions from the first column with 50 ml of 2N HCI that it is below 0.1 N. Pass the sqmple through
followed by 50 ml of deionized water. Elute the ion exchange column at the recom -
anions from the second column with 25 ml of 1N mended exhaustion flow rate (0 .1 to 0.2
NH 4 OH followed by 50 ml of deionized water. BV/ min.), collecting the effluent in an Erlen -
Use regeneration flow rates of 0.05 bed vol - meyer flask. When the last of the sample just
umes per minute and collect solutions in sepa- enters the ion exchange column, 80 to 100 ml of
rate vessels. deionized water should be passed through the
bed in 4 increments of 20 to 25 ml each, col-
Discussion: This procedure results in a tenfold lecting all in the same flask. Titrate the contents
concentration of cations and mineral acid of the flask with standardized sodium hydroxide
anions. Furthermore, it results in a separation of to phenolphthalein endpoint. If bicarbonates
the anions from the cations, eliminating some are present, methyl orange should be used as
interference which may occur during analysis. the indicator. Do a separate titration to the
For waters containing less than 50 ppm total same endpoint on a sample of the unknown
dissolved sol ids, two liters of sample can be which has not been treated by ion exchange.
taken and the flow rate increased proportion- Subtract th is titre from the first titre. If the sample

15
treated by Ion exchange is colored so that column, the first bed volume of effluent may be
these titrations cannot be performed, determi- discarded. As the acid is treated, the exhaus-
nations can be done potentlometrically. tion of the anion exchange resin may be fol-
lowed by noting the color change taking place
Discussion : This procedure can be used for in the resin bed. As the ferric chloride complex,
analyzing water samples, soil extracts, plant which Is usually present as a contaminant, is
extracts, fertilizer solutions, serum samples, etc. adsorbed, the Amberllte IRA-400 darkens .
An anion exchange resin can be used to Regeneration can be accomplished by simply
accomplish these determinations, too, but the washing the column with approximately 300 to
metal hydroxides that are formed must not be 500 ml of deionized water. The course of
insoluble or else they will precipitate on the regeneration can be followed by noting the
resin. If an anion exchange resin (Amberlite color change as the resin becomes lighter.
IRA-400, hydroxide form) Is used, titration should
be with standardized acid. Discussion: This Is an example of purification
using a single ion exchange resin in an ionic
form compatible with the liquid being treated .
Good absorption of the ferric chloride com-
Experiment Ill- plex occurs at a high concentration of hydro-
Purification by Ion Exchange chloric acid which favors formation of the
complex anion; very poor adsorption would
Purpose: To remove contaminants that are take place at low concentrations. Advantage
anionic complexes of trace metals from con- is taken of this phenomenon to achieve a
centrated hydrochloric acid. straightforward purification step and regen-
Materials: Amberlite IRA-400, chloride form. eration is thus easily accomplished with
Ion exchange column. deionized water. If only traces (10 to 100 ppm) of
Separatory funnel. iron are present in the original acid, many liters
Collection vessel. of acid can be treated by the column
Deionized water. described in the procedure. If ferrous ion is
present, It must be oxidized to the ferric state to
Procedure: Prepare the ion exchange column ensure complete removal. Certain metals may
with a charge of 75 to 100 ml of Amberlite form chloride anionic complexes which will be
IRA-400, chloride form. The concentrated adsorbed but not conveniently eluted. Exam-
hydrochloric acid Is placed in the separatory ples are mercury, iridium and platinum. Special
funnel and permitted to flow through the col- rejuvenation techniques will then be required
umn at the exhaustion flow rate [0.066 BV /min .). or the resin can simply be replaced with a new
Because of the water originally present In the charge.

16
Automated Industrial water treatment pilot plant for scaled-up laboratory experiments.
Deionization*
Introduction 2. The existence of an unfavorable ex-
c hange equilibrium during the first stage
of the deionlzatlon leading to Incomplete
One of the most Imp ortant develop ments in
ion removal.
Ion exchange t e chnology has been the
removal of cationic and anionic impurities For many applications, a transient acidic or
from water and other solutions by d e ionization. basic condition can drastically alter the prop-
There are three basic methods for employing erties of a substance. This can be particularly
ion exchange resins for deionizing solutions. critical for the delonlzation of biochemical
The first, conventional deionizati o n, involves solutions containing sugars, protein, etc .
passage of the solution through a column of a Because of the reversible nature of the
cation exchanger In the hydrogen cycle to exchange equilibria Involved, it can be difficult
form the free acids of the e lectrolytes p resent to achieve complete deionization with a single
and then th rough the basic form of an anion pass through the two columns of exchangers
exchanger to remove this acidity. The second, In series. This may make necessary the use of
reverse deionization, is similar to the first, except a series of alternating cation and anion
that the solution is first passed through the exchange columns.
anion exchanger to form the hydroxides of the
salts present and then through the cation Deionization by Monobed Resins
exchanger to convert the cations to hydrogen.
The third, mixed-bed deionizatlon involves Reali zation of these deficiencies led to the
contacting the solution with a mixture of cation development of the mixed-bed technique in
and anion exchangers in the hydrog en and which Monobed resins both maintain a neutral
hydroxide forms, res p ectively. medi um a t all times and give the solute
These schemes can employ various com- re mova l typical of an irreversible reaction,
binations of weakly or strongly acidic and basic a llowing complete delonlzatlon. Combina-
ion exchange resins. In conventional and tions involving strongly acidic cation exchange
reverse deionlzation systems, two undesirable resins with strongly basic anion exchange res-
effects can arise: Ins are ro utinely used to produce water of
1. The formation of a temporarily acidic or extremely high quality. Mixed-bed operations
basic medium. are not limited to the use of strong electrolyte
TABLE 4
Properties of Various Monobed Resins
Cation Exchange Resin Anion Exchange Resin
Amberllte Amberllte Amberlite Typical
Monobed Type Designation Type Designation Application
MB-1 Strongly Acidic IR-120 Strongly Basic IRA-400 Highest purity water
MB-2 Strongly Acidic IR-120 Strongly Basic IRA-410 High quality process water
MB-3 Strongly Acidic IR-120 Strongly Basic IRA-410 Cartridge deionizers
(dyed) L (throwaway)
MB-4 Strongly Acidic IR-120 Weakly Basic IRA-93, IRA-94 Separation of weak and
strong acids
MB-5 Weakly Acidic IRC-50S Strongly Basic IRA-410 Sugar treatment
MB-6 Weakly Acidic IRC-50 Weakly Basic IRA-93 Deashing of pharmaceuticals

NOTE: The cation and anion exchange resin components are suggested prototypes. They can be substituted to achieve specific effects. For
example, more-porous anion exchange resins like Amberlite IRA-402 can be used in Amberlite MB-5. Other weakly basic anion exchange
resins may be used to advantage in Amberlite MB-4 and in Amberlite MB-6. Contact the Fluid Process Chemicals Department of Rohm and
Haas Company for further details. ~
'The American Society For Testing Materials (ASTM) (1916 Race St.. Philadelphia, PA) has developed standardized
test methods for the operating performance of ion exchange resins. These methods are under the jurisdiction
of ASTM Committee D-19 and the procedures are listed under the ASTM Designation: D1782-72.

18
resins such as Amberlite IR-120 Plus and > preference to the other depending upon the
Amberlite IRA-400 or Amberlite IRA-410 . circumstances involved. In some instances, the
Although Amberllte MB-1 and Amberlite MB-3 two methods are complementary.
are the only pre-mixed Monobed resins avail- In any discussion of the laboratory prepara-
able, other combinations can be formulated tion of pure water by Ion exchange, the basic
by the end user to achieve tailor-made differences between this technique and dis-
requirements. Table 4 lists other Monobed resin tillation must be considered. Ion exchange can
combinations. The degree of deionizatlon or be used to completely remove all dissolved
the resistivity of the effluent obtainable is high- electrolytes, Including such weak electro-
est for Amberlite MB-1 and lowest for Amberlite lytes as silicic acid, boric acid, phenols, carbon
MB-6. However, the regeneration efficiencies dioxide and even humic acids. True non-
are In the reverse order, Amberlite MB-6 pos- electrolytes, however, cannot be removed .
sessing the highest. Furthermore, although colloids and bacteria
Monobed resin systems such as Amberlite are adsorbed by Ion exchange resins, one can-
MB-1 and Amberlite MB-3 will be of interest to not assure sterility and freedom from pyrogens
the laboratory worker for producing high qual- by ion exchange treatment of water. On the
ity water to be used for preparing reagents other hand, although distillation can be
and conducting ion exchange experiments . employed to prepare sterile and pyrogen-free
This is discussed in the next section. Amberlite water, many stages of distillation and elabo-
MB-6 can be quite useful for the gross deioniza- rate pretreatment steps are required before
tion of a variety of solutions. Such weak-elec- one can obtain distilled water having the free-
trolyte Monobed resins possess high regenera- dom from ionic impurities that is achieved by
tion efficiencies and they are relatively inert ion exchange. Therefore, many laboratories
with respect to pH-sensitive substances such as requiring sterile, pyrogen-free water of a high
enzymes, sucrose, drugs, and fine organic degree of purity use a combination of ion
chemicals. Another very Important advantage exchange and distillation.
of the Amberllte MB-6 type Is that it can be used
at temperatures as high as 100°C., since it incor- Ion Exchange Now Standard Method
porates a weakly basic rather than a strongly
basic anion exchange resin. For most laboratory functions, ion exchange
The mechanisms of Monobed resin opera- has become the standard method for prepar-
tion can best be understood by reviewing the ing low conductivity water. In many instances,
next section which discusses the production of Ion exchange is preferred over distillation
laboratory water of high quality. because of convenience, modest space
requirements, low capital Investments, and the
high degree of purity achieved. Water freed of
Preparation of Deionized Water Ionic impurities by means of Ion exchange res-
for the Laboratory Ins Is generally called "deionized" water and
the operation employed is termed "deion-
Ion exchange work in the laboratory almost ization." Other terms such as "demineralized
always requires distilled or deionized water for (demineralization)" and "desalted (desalina-
preparing reagents and regenerants, and for tion)" are sometimes used to describe water
rinsing and conditioning steps. Even where ion that is purified by means of ion exchange.
exchange is not involved, routine laboratory Although large commercial ion exchange
work frequently demands high quality water. units have been installed as central facilities for
Although water Is not normally considered as a supplying ion-free water to laboratory build-
reagent, the availability of water of extremely ings and large groups of laboratories, it is not
low conductivity In large or even small quan- the purpose of this article to review such oper-
tities in the laboratory poses various problems. ations since In such a case the water problem
Two methods are commonly used in the labo- has already been solved for the laboratory
ratory for preparing such water-distillation worker. The purpose of this discussion Is to
and ion exchange. Each method has Its advan- describe how laboratory personnel can solve
tages and disadvantages and may be used in their own water problems.

19
Laboratory Water Problems yellow-brown]. This Monobed resin is used
widely when small quantities of deionized
Laboratory investigators are frequently faced water ore required only occasionally. Maintain-
with one of several water problems. (1) They ing a pound jar of Amberlite MB-1 or Amberlite
may have continual demands for modest or MB-3 on the reagent shelf assures one of an
even large quantities of low conductivity water emergency supply of many gallons of
with tap water as the only water source. (2) In deionized water on short notice. The jar should
situations where a central distillation or de- be kept tightly capped to prevent drying of the
Ionization system supplies water for a labo- resin and adsorption of CO 2 .
ratory installation, the purity of the water when
delivered over long distances or when stored In
tanks is not adequate for certain laboratory Contamination of Central Supply
studies. (3) On occasion, certain laboratory In many large research facilities, distilled or
operations merely require small quantities of deionized water Is prepared in a centrally
Ion-free water which do not Justify elaborate located installation and the water distributed
installations. Each of these three situations Is a through a piping system to various locations. In
common occurrence which can readily be order to maintain adequate supplies, a stor-
solved by ion exchange techniques. age tank is employed. Distilled or deionized
Although there are several ways in which one water stored and transported in this manner
can deionize water using ion exchange resins, deteriorates in quality due to Impurities picked
the most commonly used laboratory tech- up from the atmosphere. piping. and micro-
nique is the use of a mixed-bed resi~ ~ystem biological growth. Although such water is more
consisting of a mixture of a strongly ac1d1c cat- than adequate for most laboratory uses. the
ion exchange resin, such as Amberlite IR-120 purity is not adequate for various analytical
Plus, and a strongly basic anion exchange and research purposes. In such cases, small
resin, such as Amberlite IRA-400 or Amberllte cartridges of Amberlite MB-1 or Amberlite MB-3
IRA-402. The Monobed resin system may be may be employed for polishing such water.
employed on a one-use basis or in a more Because the feed to the Monobed resins is
elaborate device which permits regeneration quite pure, the quantity of water that can be
of the resins. treated (polished) is very great.
In some instances, large quantities of ion-
Preparation of Small Quantities free water must be supplied for laboratory use.
In a case such as this, one cannot eco-
In the case where the laboratory worker
nomically use a Monobed resin unit on a throw-
requires but a small quantity of ion-free water away basis. It therefore becomes necessary to
on occasion, the problem can be solved by
consider apparatus in which the resins can be
means of a regenerated Monobed resin mix- regenerated. In many such instances. com-
ture, such as Amberllte MB-1 or Amberlite MB-3.
mercial "package" units can be purchased
When a small quantit y of deionized water is
and readily installed. In fact, most people find
required, some of the Monobed resin mixture is
that it is more economical to purchase or rent
placed In the column as shown in Figure 1 an_d
one than to c;onstruct their own. However, it is
the raw water is then passed through the resin occasionally of educational value to construct
and collected in a clean container. Various one's own unit.
columnar devices may be employed; however,
a bed depth of at least 18 inches of resins
should be used. Under average conditions, 100
ml of resin will treat 12,000 ml of water at flow
rates of about 25 to 50 ml per minute. The
quality of such water is equivalent to_that
of carefully distilled water. If the capacity of c:
the resin is not exhausted, the column may
be clamped at both ends and used again.
Amberlite MB-3 is self-i ndicating, changing
color when exhausted (from blue-green to

20
1! -kl-.:'

Apparatus for testing the kinetic performance of Ion exchange resins.

Determining Ion Exchange Capacity*
Introduction erably 3 to 5 grams for solids). In each case
about 10 bed volumes of regenerant should be
The following section describes methods of passed through the column at a rate of 0.05 ml
testing for one of the most important charac- per ml of resin per minute, followed by a rinse
teristics of ion exchange resins-total capac- with deionized water to the prescribed
ity. Such total capacity Is a constant for any endpoint.
given resin and must be distinguished from
column capacities which define the potential Type of Regenerant Rinse
Exchanger Solution Requirement
of a resin to remove specified ions under actual
conditions of use to a target leakage value. Strongly acidic 10% NaCl Free of Cl -
The techniques described here express total cation (SSCC)
4% HCI Neutral to methyl
capacities in terms of milliequivalents per (CEC) orange
gram of dry resin. In order to obtain these val- Weakly acidic 4% HCI Neutral to methyl
ues, It is necessary to know the solids content of cation orange
each resin being tested . This procedure is Strongly basic 10% NaCl Free of Cl -
described below. In order to achieve some anion
degree of standardization, capacity determi- Weakly basic 4% NaOH Until 1 drop of
nations are usually run on specific ionic forms anion 0. l N H2 SO~
for each type of exchanger. Thus, the capacity neutra Iizes 12
ml of effluent
procedures speak of "conditioned" resin. Listed
below are suggested conditioning steps for As with all column operations, this regenera-
each exchanger. tion technique should be preceded by a
Although these determinations will yield only thorough backwashing. If the resin sample Is
weight capacities, volume capacities can be dirty, backwashing should be continued until
determined where desirable by determining the overflow runs clear.
the density of the conditioned resin. This can After rinsing, the sample should be trans-
be done by measuring a known weight of the ferred from the column to a Buchner funnel
conditioned resin in a graduated cylinder, but where excess moisture should be removed by
most workers find it more convenient and drawing air through the tunnel for 5 minutes
accurate to employ cali brated Ion exchange using a water suction pump. The drained sam-
columns in which the actual capacity will be ple is now in the proper form for determining
determined. A buret-type column, therefore, is solids content and capacity.
extremely useful. The volume capacity of any
resin can be found by the following equation:
Solids (or Moisture)
.
Capac1tyml
meq
= C .
apac1ty-g-
meq Content Determination
All samples for this determination should be
. g % Solids
x Density ml x weighed at the same time as the sample for
100
capacity determination. It is suggested that no
less than 1 gram of sample be used for this
Conditioning determination (3 to 5 grams being preferable).
Before capacities can be determined, each Accurately weigh the sample on an analytical
ion exchange resin should be conditioned with balance in a dry, tared weighing pan. Oven dry
an appropriate regenerant as listed below. at 110°C. for at least 8 hours. Cool in a desic-
Enough resin should be placed into a condi- cator and weigh. The calculation is:
tioning column to allow both a capacity deter- Wt. oven dried resin x 100 _ o/c S I'd
mination and a separate amount for a solids ' bef ore d'
Wt. resin rymg -oOIS
determination (e.g., about 5 grams hydrated 100-% Solids =
resin for capacity plus at least 1gram and pref- < % Moisture Holding Capacity (MHC)

!The American Society For Testing Materials [ASTM) (1916 Race St.. Philadelphia, PA) has developed standardized
test methods for the physical and chemical properties of ion exchange resins. These methods are under the
Jurisdiction of ASTM Committee D-19 and the procedures are listed under the ASTM Designation: D2187-77.

22
Cation Exchange Capacity (CEC) > Reagents: 4% HCI
1 N NaN0 3
Type of Exchanger: Both weakly acidic cation Methyl orange indicator
exchange resins, such as Amberlite IRC-50, and Phenolphthalein indicator
strongly acidic cation exchange resins such as Deionized water
Amberlite IR-120 Plus.
Procedure:
Principle: To neutralize the acid form of a cation 1. Weigh out accurately 5 grams of the NaCl
exchange resin by contacting it with a known conditioned cations exchange resin along
excess of a standard alkali. The residual alkali Is with a sample for solids determination.
titrated with standard acid. 2. Quantitatively transfer the 5-gram sample
Reagents: 0.1 N NaOH prepared in 5% NaCl to an ion exchange column (a wash bottle with
0.1 N HCI deionized water is handy).
Phenolphthalein indicator 3, Pass through the column 1 liter of 4% HCI,
Deionized water followed by 1 liter of deionized water. If the
effluent is not neutral to methyl orange at this
Procedure: point, continue rinsing until It is. These effluents
1. Weigh accurately a 1 gram sample of can be discharged to waste, Flow rate should
conditioned cation exchange resin and be such that 1 liter of solution is passed through
another sample for solids determination. NoTE: the resin in 30 to 45 minutes.
If sample is a strongly acidic cation exchange 4, Place the exit end of the ion exchange
resin it should be conditioned with HCI rather column into the neck of a 1-liter volumetric flask
than NaCl. and pass through the resin exactly 1 liter of 4%
2. Place the capacity sample into a dry 250- sodium nitrate. Use the same flow rate.
ml Erlenmeyer flask and pipette in exactly 200 5, Mix the solution well and titrate 100-ml ali-
ml of standardized 0.1 N NaOH which has been quots with standardized sodium hydroxide
prepared in 5% sodium chloride. using phenolphthalein as the indicator,
3. Stopper the flask and allow to stand 6. Capacity calculation :
overnight.
4. Back-titrate 50-ml aliquots of the superna- ml NnOB X 10 -
NNaOH X
tant liquid with standardized 0.1 N HCI using a % Solids -
Sample wt. x
phenolphthalein endpoint. Be sure not to draw 100
off any ion exchange resin beads. Meq of strong acid capacity
5. Calculate capacity: Gram of dry Na-form resin

(200 x NNaOH) - 4(ml acid x Nacld)

% Solids Weak Base, Strong Base, and Total
Sample wt. x Anion Exchange Capacity (TAEC)
100
Meq cation exchange capacity Type of Exchanger: Strongly basic anion
Gram of dry H-form resin exchange resins only, either Type I or Type II
such as Amberlite IRA-402 and IRA-410,
respectively.
Salt-Splitting Cation Capacity
(SSCC) Principle: The total anion exchange capacity
of strongly basic anion exchange resins in the
Type of Exchanger: Strongly acidic cation chloride form is found by determining two
exchange resins such as Amberlite IR-120 Plus. component capacities: weak-base capacity
upon elution with ammonium hydroxide and
Principle: This type of exchanger is most often
strong-base capacity (or salt-splitting anion
characterized for its ability to split neutral salts.
exchange capacity) upon subsequent elution
The resin in a column is converted to the acid
with sodium nitrate. Practically all of total
form then treated with a large excess of a neu-
capacity in unused Type I anion exchange res-
tral salt, sodium nitrate. The effluent Is titrated
ins will be salt-splitting anion exchange
with standardized sodium hydroxide.
capacity,

23
Reagents: 4% HCI 10. Calculate weak-base capacity for the
Ethyl alcohol NH 4 OH fraction and strong-base capacity for
1% NH 4 OH the NaNO 3 fraction. In each case use the fol-
1 N NaNO 3 lowing equation:
Methyl orange indicator
Cone. HNO 3 ml X NAgNu., x 10 _
AgNU J

0.1 N NaOH % Solids -

Sample wt. x
5% K2 CrO 4 100
0.05 N AgNO 3 Meq anion exchange capacity
Deionized water Gram of dry Cl-form resin
Procedure:
1. The conditioned anion exchange resin, 11. The sum of the weak-base capacity and
already in the chloride form, must be further the strong-base capacity is the total anion
conditioned by passing through about 1 liter of exchange capacity of the sample.
4% HCI. Rinse with about 1 liter of ethyl alcohol.
Flow rate should be such that 1 liter of solution is
passed through the resin in 30 to 45 minutes. Anion Exchange Capacity (AEC)
2. Remove the sample from the column, Type of Exchanger: Weakly basic anion
and drain on a Buchner funnel for 25 minutes. exchange resins only, such as Amberlite IRA-68
3. Weigh, accurately, about 5 grams for or Amberllte IRA-93.
capacity determination and at the same time
weigh the remaining sample for solids Principle: Anion exchange capacity Is deter-
determination. mined by first converting the anion exchange
4. Transfer the capacity sample quan- resins to the hydrochloride salt form and then
titatively to an ion exchange column. eluting it with sodium nitrate.
5. Pass exactly 1 liter of 0.15 M aqueous
ammonia* through the column, collecting the Reagents: 4% HCI
effluent in a 1-liter volumetric flask. Flow rate Ethyl Alcohol
should be such that 1 liter of solution is passed 1 N NaNO 3
through the resin in 30 to 45 minutes. Save the Methyl orange indicator
solution. 0.1 N NaOH
6. Pass exactly 1 liter of 1 N NaNO 3 through 5% K2 CrO 4
the column at a flow rate such that 1 liter of 0.05 N AgNO 3
solution is passed through the resin in 30 to 45 Procedure:
minutes, collecting the effluent in another 1. Weigh out accurately 5 grams of the con-
1-liter volumetric flask. ditioned sample along with another sample for
7. Shake both solutions thoroughly. Take solids determination
100-ml aliquots from each and treat both as 2. Quantitatively transfer the capacity sam-
follows: ple to an ion exchange column.
8. To the aliquots in a wide mouth Erlen- 3. Pass through the column 1 liter of 4% HCI.
meyer flask add 2 drops of methyl orange con- Rinse with about 1 liter of alcohol. Flow rate
centrated HNO 3 drop-wise until solution turns should be such that 1 liter of solution is passed
red or pink. Carefully add 0.1 N NaOH until color through the resin in 30 to 45 minutes.
Just returns to yellow.
9. Add 1 ml of 5% K2 CrO 4 and titrate with
0.05 N AgNO 3 until color changes from pale
yellow to yellow-orange.

.-
*Ammonia is prepared by diluting 10 ml of 28% reagent grade ammon ia solution to 1 liter with DI water.

24
4. Pass through the column exactly 1 liter of 1 .,.
N NaNO 3 , collecting the effluent in a 1-liter vol -
umetric flask. Use the same flow rate.
5. Shake the flask well and transfer 100-ml
aliquots to an Erlenmeyer flask.
6. Add 2 drops of methyl orange and, If pink,
just enough 0.1 N NoOH to change the color
bock to yellow.
7. Add 1 mi of 5% K2 CrO 4 and titrate with 0.05
N AgNO 3 until color changes tram yellow to
yellow-orange.
8. Calculate the onion exchange capacity
using the following equation :

ml x NAgNo3 x 10 _
Ag NUJ
% Solids -
Sample wt. x
100
Meq anion exchange capacity
Gram of dry free-base-fonn resin

25
Appendix
Larger-Scale Column Testing into the column which should already contain
some water. Bed depth should be at least 24
This laboratory guide has discussed ion inches (0.61 m), but there should be enough
exchange column technique only with refer- space above the top of the resin to allow for
ence to small laboratory columns. In cases expansion during backwashing as noted
where it is desirable to scale up data obtained below. Insert the inlet stopper and, with the inlet
from very small column studies it is necessary to tube closed but the overflow open, backwash
gain some operational experience in some- the ion exchange resin at a rate sufficient to
what larger columns. Very small columns do expand the bed to 75 to 100% of its original
not demonstrate realistically the hydraulic volume for about 10 minutes. Shut off the back-
operational factors which will be experienced wash water and allow the bed to settle. Draw
in commercial units, nor do they usually facili- off excess water slowly until the water level is
tate evaluation of the long-term behavior of about 1to 2 inches (2.5 to 5.1 cm) above the top
the ion exchange material. of the bed. Read and record the volume of the
The bed depths in such "pilot" columns ion exchange resin.
should be at least 24 Inches (0.61 m). Although Regeneration or other pretreatment of the
various diameter columns can be used, a sample should be done at this point and the
1-inch (2.5 cm) internal diameter column about volume of the treated, rinsed bed should be
4 feet (1.2 m) long is frequently chosen because read again since it may be different than that
it represents a good compromise between measured before pretreatment. Regenerants
size and expense. Meaningful data can be should be applied at a flow rate of about 0.5
obtained from such a column and the amount gpm/ft3 (4.0 LIL/hr) (.06 bed volumes per min-
of ion exchange material required is not overly ute). Rinsing should start at this flow rate and,
large. The following procedure is a general after about 1 bed volume has passed through,
one that can be applied to most larger scale the rate can be increased to 1.5 gpm /ft 3 (12.0
column studies. (See photograph on page 17). UL/hr) (0 .2 bed volumes per minute) , The
Materials: Glass column, 1-inch (2.5 cm) inter- exhaustant or test solution is usually passed
nal diameter by 4 or 5 feet (1.2 to through the column at a rate of 1 to 2 gpm /f t3
1.5 m) long (8.0 to 16.0 LIL/hr) (0.13 to 0.27 bed volumes per
Rubber stoppers minute).
Glass T-tubes During the course of the exhaustion run the
Clamps effluent can be collected in calibrated receiv-
Rubber tubing ers and periodically analyzed . Actual column
capacities can be determined by plotting a
Bed support material (can be 80- graph showing the volume of loading solution
mesh screen of stainless steel or passed through the resin as a function of leak-
plastic) age appearing in the effluent.
It should be recognized that the first such
Mount the column in an exactly vertical posi-
column run may yield a higher capacity than
tion. Fit rubber stoppers at the top and bottom
will be found in subsequent runs. This is particu-
and insert glass T-tubes in each. The bottom
larly true when starting with new resin.
stopper should be modified to accommodate
Repeated cycling, therefore, will help deter-
the bed support screen, and care should be
mine the real operating capacity under the
taken to insure that a collection space is pro-
conditions of the test. It will also be most helpful
vided below the screen itself. A backwash
in predicting the behavior of the ion exchange
water supply should be connected to the side
resin in an actual plant unit.
arm of the outlet tube. All inlets and outlets
should be provided with rubber or plastic tub- The hydraulic characteristics provided by the
ing and screw clamps and other rate-regulat- type of column described above approach
ing devices should be attached. Calibrate the r
those of a plant size unit much more real-
column using water at 25°C. istically than does an analytical-type column
study. As a matter of fact, testing in small ana-
Column Operation: Slurry the ion exchange lytical columns may be discouraging because
resin in a separate vessel, then pour the slurry

26
excessive pressure drop may be experienced. believe. Thus, laboratory personnel should use
This may be due merely to the packing of the small-column techniques to see if a particular
ion exchange beads or to the small size of the application is feasible by ion exchange. They
column itself or to the bed support material. should be careful not to draw misleading con-
Performing the same study in a 1-inch column, clusions, however, about flow rates, pressure
as described previously, often shows that the drop, bed expansion, etc ., and should resort to
hydraulic factors are not the problem that larger column testing for a study of these
smaller column studies would lead one to factors.

ION EXCHANGE RESIN CONVERSION TABLES

VOLUME

Cub ic Feet Gallons (U.S.) Gallons (Imp.) Liters Cubic meters

1 Cubic ft. 1 7.48 6.23 28.3 0.0283

1 Gallon (U .S.) 0.134 1 0.833 3.785 0.003785
1 Gallon (Imp.) 0.161 1.2 1 4.55 0.00455
1 Liter 0.0353 0.264 0.220 1 0.001
1 Cubic meter 35.3 264 220 1000 1

MASS

Pounds Grams Kilograms Grains Kllogralns

1 Pound 1 453.6 0.4536 7000 7

1Grom 0.0022 1 0.001 15.43 0.01543
1 Kilogram 2.205 1000 1 15430 15.43
1 Groin 0.000143 0.0648 0.0000648 1 0.001
1 Kilogroln 0.143 64.8 0.0648 1000 1

DENSITY

Pounds/ Cubic ft. Grams/Liter Pounds/Gal. (U.S.) Pounds/ Gal. (Imp.)

1 Pound /Cu. ft. 1 16 0.134 0.160

1 Grom / Liter 0.0624 1 0.00834 0.010
1 Pound / Gal. (U.S.) 7.48 120 1 1.2
1 Pound / Gal. (Imp.) 6.24 100 0.834 1

CONCENTRATION (Expressed as CaCO 3 )

German
Grains/ Gal. Grains/Gal. French Degree Degree
ppm Meq./Liter (U.S.) (Imp.) of Hardness of Hardness

1 ppm 1 0.02 0.0585 0.0704 0.1 0.056

1 Meq./Liter 50 1 2.9 3.48 5.0 2.8
1 Groin /Gal. (U.S.) 17.1 0.34 1 1.20 1.71 0.96
1 Groin / Gal. (Imp.) 14.2 0,28 0.833 1 1.42 0.80
1 French Degree 10 0.20 0.585 0.704 1 0.56
1 Germon Degree 17,9 0.36 1.05 1.26 1.78 1

27
FLOW RATE*

bed volumes/min. gpm (U.S.)/ft3 gpm (IMP) /ftJ lbs H2 O/ mln/ft3

1 bed volume/min. 1 7.48 6.24 62.4

1 gpm (U.S.)/ft3 0.134 1 0.833 8.33
1 gpm (IMP)/ft3 0.161 1.20 1 10
1 lb H2 O/min./f t3 0.016 0.12 0.10 1

· To convert flow rote per volume to flow rote per unit area, multiply flow rote per unit volume by resin volume and d ivide by cross-
sectional area.

CAPACITY* AND REGENERATION LEVEL

meq. lb-eq/ft3 kgr g CaCO/ 1 g CaCO 3 / I

---mr (as CaCO 3 ) ft3

1 meq./ml 1 0.0624 21.8 28 50

1 lb-eq/ft3 16.0 1 349 449 801
1 kgr (CaCO 3)/ft3 0.0459 0.00286 1 1.28 2.29
1 g CaO/1 0.0357 0.00223 0.779 1 1.79
1 g CaCO 3/I 0.0200 0.00125 0.436 0.560 1
· Capacity on a dry weight basis may be calculated as follows:
g-meq /ml
G-meq/g of dry resin = 6,240 x - - - - - - - - - - -
Wet density In lbs./cu. ft. x % Solids

SCREEN EQUIVALENTS

U.S. Standard Tyler Standard British Standard

Sieve Opening Meshes per Opening Meshes per Opening

No. Inch Inch
mm Inches mm Inches mm Inches

12 1.68 0.0661 10 1.65 0.065 10 1.68 0.0660

14 1.41 0.0555 12 1.40 0.055 12 1.40 0.0553
16 1.19 0.0469 14 1.17 0.046 14 1.20 0.0474
18 1.00 0.0394 16 0.991 0.039 16 1.00 0.0395
20 0.84 0.0331 20 0.833 0.0328 18 0.853 0.0336
25 0.71 0.0280 24 0.701 0.0276 . 22 0.699 0.0275
30 0.59 0.0232 28 0.589 0.0232 25 0.599 0.0236
35 0.50 0.0197 32 0.495 0.0195 30 0.500 0.0197
40 0.42 0.0165 35 0.417 0.0164 36 0.422 0.0166
45 0.35 0.0138 42 0.351 0.0138 44 0.353 0.0139
50 0.297 0.0117 48 0.295 0.0116 52 0.295 0.0116
60 0.250 0.0098 60 0.246 0.0097 60 0.251 0.0099
70 0.210 0.0083 65 0.208 0.0082 72 0.211 0.0083
80 0.177 0.0070 80 0.175 0.0069 85 0.178 0.007
100 0.149 0.0059 100 0.147 0.0058 100 0.152 0.006
200 0.074 0.0029 200 0.074 0.0029 200 0.076 0.003
325 0.044 0.0017 325 0.043 0.0017 240 0.066 0.0026

28
Figure 6. Electrical Resistance of Dilute Electrolytes (Deionized Water at 25°C)

10
~
9
8

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---3, ---"' ....::! _.
X 8 :"'II ~~ ~ • ~ ...::::"!
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7
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,I'-.""~ I" ~ , 1""""1"'11,
a5
u
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·.;; 0

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& '~1..:: ""
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09 -.A 31
08 ~ _,., 1311
07 I ~~---" •

06
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05
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04 ~ · ~ ""~ C'I

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I' rL"-."-. I '-
rl"~ ~ i\ J'- r"'r i·
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3 4 5 6 7 8910 3 4 5 6 7 8 9 10 20 30 40 50 60 70 80 90 100

Concentration, ppm

29
ROHMD
IHAAS~
PHILADELPHIA, PA . 19105

ACRYSOL, AMBER LITE, AMBERLYST, DUOLITE, LYKOPON, MONOBED and STRATABED are registered trademarks of
Rohm and Haas Company, or of its subsidiaries or attiliates . The Company's policy 1s to register its trademarks where
products designated thereby are marke ed by the company, its subsidiaries or affiliates .

These suggestions and data are based on information we believe to be reliable . They are offered in good faith , but with-
out guarantee, as cond1t1ons and methods of use of our products are beyond our control We recommend that the
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Suggestions for uses of our products or the inclusion of of descriptive material from patents and the c1tat1on ~f spec1f1c
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lulu 1QQ":l 0 ... i nt.nrl i n 11 C: Ii