Name: Juvinch R.

Vicente December 06, 2010

Partner: Cliff Jeffersonn Escobar Chemistry 126 Laboratory

Experiment No. 1

PROPERTIES OF ION-EXCHANGE RESINS

I. INTRODUCTION

Ion exchange is a stoichiometric and reversible interchange of ions between a solid (ion
exchange material) and a liquid in which there is no permanent change in the structure of the
solid. These ion exchange materials are in the form of resins. Conventional ion exchange resins
which are consist of a cross-linked polymer matrix with a relatively uniform distribution of ion-
active sites throughout the structure. These active ion-exchange sites are insoluble acids or
bases which have salts which are also insoluble, and this enables them to exchange either
positively charged ions (cation exchangers) or negatively charged ones (anion exchangers).

Resins are also broadly classified as strong or weak acid cation exchanger or strong or
weak base anion exchanger depending on their behavior. Strong acid cation resins are highly
ionized in both the acid (R-SO3H) and the salt (R-SO3Na). In a weak acid resin, the ionizable
group is a carboxylic acid (COOH) as opposed to the sulfonic acid group of strong acid resins,
upon which the resins behave similarly to weak organic acids that are weakly dissociated.
Strong base resins are highly ionized and can be used over the entire pH range. Weak base
resins are like weak acid resins in such a way that the degree of ionization is strongly influenced
by pH.

The main objective of the experiment is to determine the exchange capacity or in this
case the acid capacity of the ion exchange resin used. The exchange capacity of an ion exchange
resin is defined as the total number of chemical equivalents available for exchange per some
unit weight or unit volume of resin. The capacity may be expressed in terms of milliequivalents
per dry gram of resin or in terms of milliequivalents per dry gram of resin or in terms of
millequivalents per milliliter of wet resin. In this experiment, the acid capacity will be measured
in terms of milliequivalents of exchangeable anion per gram of dry resin. Since ion-exchange is
an stoichiometric reaction, it should follow the equation below (for strong acid cation
exchanger):
x+ ¿ ↔¿¿ ¿
+¿+ M ¿
H
xRSO−¿ ¿
3

Where R is the organic unit of the resin where the sulfonic group is attached, M is the
metal ion species which exchanges with the H+ ions from the resin.
 The determination will be done by allowing two different cations Na + and Fe3+ to
exchange ions with the H+ saturated resin. Titration analysis will then follow to quantify the
total amount of H+ ions replaced by each test cations, using standardized NaOH. In theory, the
amount of the H+ ions replaced by the two cations will just be equal since the stoichiometric
ratio of the two process will just be the same. Hence, the acid capacity that will be calculated
for both of the tests will also be the same.

II. MATERIALS AND METHODS

0.3 M NaCl Freshly distilled water

1.0 M/3.0 M HCl 0.1 M Fe(NO3)3

Cation Exchange Resin (Dowex 50) 25 mL Burette

Phenolphthalein Solution Glass Wool

Standard 0.1 N NaOH

The resin column was prepared first by mixing about 10.0 grams of the Dowex 50 resin
in 50.0 mL of freshly distilled water. It was then allowed to stand for around 15 minutes. A roll
of glass wool was then carefully plugged into the bottom of a 25-mL burette. The prepared resin
was then poured into the burette properly so as to avoid hollow portions along the column. All
throughout the preparation, the water level was controlled for it not to go below the level of
the resin.

The resin was then saturated with H+ by passing about 100 mL of 1.0 M HCl through the
column. The rate of flow of the acid was maintained very slow (around 15 mL per minute) to
allow a complete generation of H + saturated resin. During addition, the acid solution was
applied through the glass wall of the burette so as not to disturb the resin. The resin was then
washed using freshly distilled water. The first few milliliters of water was used to wash the glass
walls and then allowed to soak into the resin before continuing. The washing was continued
until the resin gives a nearly neutral eluate. The neutrality of the eluate was monitored using a
pH paper.

(Test 1) The resin was allowed to exchange cation with NaCl. This was done by pouring
in 10.0 mL of 0.3001 M NaCl. It was poured in the resin at a very slow rate (around 3 mL per
minute) and was allowed to stand for a few minutes to let the cations exchange completely.
The resin was then washed with 100 mL of freshly distilled water, collecting all the eluate from
the addition of NaCl solution. The eluate was then added with 3 drops of phenolphthalein
indicator and titrated with the standardized NaOH solution.

(Test 2) The previous analysis using NaCl was repeated, but the resin this time was
allowed to exchange cation with Fe(NO 3)3 instead of NaCl. Theoretical volumes of NaOH for
each analysis were then calculated and we’ve found out that the results obtained from the
experiment were very far from the theoretical values. So we repeated the experiment but this
time the analysis was done using NaCl solution alone as in Test 1. Also, we increased the
concentration of HCl used from 1.0 M to 3.0 M to make sure that the resin will be completely
saturated with H+ ions. We also tried to further make the flow rates in each soaking slower to
allow a more efficient exchange of the ions. After all the analysis using NaCl, the analysis was
done again but this time about 10.0 mL of NaOH was used instead of the previous solution.

The previous results for the analysis using NaCl were replaced by the new more accurate
results obtained upon the repetition of the analysis. Yet, the results for the analysis using
Fe(NO3)3 were retained due to lack of time, but we tried to investigate the possible sources of
the discrepancy. Results were then recorded and tabulated accordingly.

III. EXPERIMENTAL RESULTS

TABLE 1. Amount and Concentration of Reagents used

Mass of Resin used 10.0412 g

Molarity of Standardized NaOH 0.09276 M
Molarity NaCl 0.3001 M
Volume NaCl used 10.00 mL
Molarity Fe(NO3)3 0.1001 M
Volume Fe(NO3)3 used 10.00 mL

TABLE 2. Titration of Eluate after passing 10.0mL 0.3M NaCl (Test 1)

Volume in mL
Initial Volume NaOH 0.00
Final Volume NaOH 31.50
Volume NaOH used 31.50

TABLE 3. Titration of Eluate after passing 10.0mL 0.1M Fe(NO3)3 (Test 2)

Volume in mL
Initial Volume NaOH 0.00
Final Volume NaOH 1.70
Volume NaOH used 1.70

TABLE 4. Observations after passing 10.0mL 0.1M NaOH through the column

Volume in mL
Initial Volume NaOH 0.00
Final Volume NaOH 0.10
 Volume NaOH used 0.10

TABLE 5. Summarized Results:

Mas Acid
VNaO VNaOH Acid
s of VNaOH Capaci
TRI H NaO Capaci
Resi Fe(NO ty
AL NaCl H ty
n 3)3 (mL) Fe(NO3
(mL) (mL) NaOH
(g) )3
10.0 31.5
1 1.70 0.10
412 0 0.2910 0.0157
10.0 32.4
2 3.50 0.10
087 0 0.3003 0.0324
10.0 32.4
3 2.30 0.20
048 0 0.3004 0.0213
10.0 33.4
4 2.70 0.05
451 0 0.3084 0.0249
10.0 32.1
5 2.10 0.10
610 0 0.2960 0.0194
10.0 31.4
6 2.90 0.05
029 0 0.2912 0.0269
Ave
10.0 32.2
rag 2.53 0.10
273 0
e 0.2979 0.0234

IV. DISCUSSIONS AND CONCLUSIONS

In the experiment, the resin used was the cation exchange resin Dowex 50. Dowex 50 is
one of a strong acid cation exchanger. The resins are prepared as spherical beads 0.5 to 1.0mm
in diameter. These appear solid even under the microscope, but on a molecular scale the
structure is quite open. This means that a solution passed down a resin bed can flow through
the crosslinked polymer, bringing it into the intimate contact with the exchange sites.

Table 1 show all the amounts and concentrations of the reagents used in this
experiment. Each reagent was prepared by the class monitors for the whole duration of the
experiment. There were a total of 6 groups. Each group is tasked to perform the experiment
independently, thus each represented a replicate of the experiment. The experiment was
divided into two main parts, the preparation of the ion exchange resin and the analysis part. For
the analysis, two salts were used as tests, these were NaCl and Fe(NO 3)3.

In test 1, the resin was allowed to exchange ions with Na + from NaCl. Na+ replaces the H+
ions from the resin; forming a resin in which Na now is the one attached on the Sulfonic group.
Consequently, H+ ions are released which reacts with Cl - ions left by the Na + ions, forming HCl.
The HCl now then is the one eluted and collected. Moreover, HCl is then titrated with NaOH.
The overall process are summarized by the equations below:

(Ion Exchange) R-SO3H + NaCl ↔ R-SO3Na + HCl Eq.1

(Titration) HCl + NaOH → NaCl + H2O Eq.2

The R indicates the organic portion of the resin and SO 3- (Sulfonic group) is the immobile
portion of the exchange site. As we can see, the ion exchange process is just a double
replacement reation between the resin and the NaCl. From the equation above, we could see
that only one resin site is needed for each Na+1 with a +1 valence.

Table 2 shows the volume of NaOH consumed during the titration of the eluate of NaCl
for our group. The average amount of NaOH consumed was 32.20 mL (see Table 5), which has a
percent error of 0.4637% (see Cal. 5) from the theoretical 32.35 mL (see Cal. 1). From the
volume of NaOH consumed in each replicate, the acid capacity of the resin in each replicate was
calculated (see Cal. 3). The average acid capacity is 0.2979 meq/g resin (see Table 5).

In test 2, the resin this time was allowed to exchange ions with Fe 3+ from Fe(NO3)3. Fe3+
replaces the H+ ions from the resin; forming a resin in which Fe now is the one attached on the
Sulfonic groups. Consequently, H+ ions are released same as that of test 1, but this time the ions
react with NO3- ions left by the Fe3+ ions, forming HNO3. The HNO3 now then is the one eluted
and collected. Furthermore, HNO3 is then titrated with NaOH. The equations are shown below:

(Ion Exchange) 3R-SO3H + Fe(NO3)3 ↔ 3R-SO3Fe + 3HNO3 Eq.3

(Titration) HNO3 + NaOH → NaNO3 + H2O Eq.4

Unlike Na+, Fe3+ trivalent ferric ions need three active sites as shown by Eq. 3. During the
addition of the Fe(NO3)3 solution, there was a change in the color of the upper part of the resin
column.

Table 3 shows the volume of NaOH consumed during the titration of the eluent of
Fe(NO3)3 for our group. The average amount of NaOH consumed was 2.53 mL (see Table 5),
quiet far from the theoretical value which is 32.37 mL (see Cal. 2). It has a very large percent
error of 92.18% (see Cal. 6). From the volume of NaOH consumed in each replicate, the acid
capacity of the resin in each replicate was calculated (see Cal. 4). The average acid capacity is
0.0157 meq/g resin (see Table 5).

There is a very large discrepancy on the result of the test 2. There should have been a
great source of error on this part. To find this out, the class checked for the all the preparation
of the reagents used. After backtracking all the procedures done, we found no significant
mistake committed during the preparation of the reagents, so I made my own apprehensions
regarding to the problem.
 My first suspicion is that the concentration of the acid used to generate H + ions was not
strong enough to completely saturate the resin column, since when we changed the
concentration of HCl used for the analysis using NaCl from 1.0 M to 3.0 M the problem was
fixed. It could also be that the rate flow in which the acid was introduced to the resin was quiet
fast. Another possible problem could also be that the rate of flow in which the Fe(NO 3)3 solution
was introduced to the resin was not slow enough to allow complete exchange of ions between
the solution and the resin. Moreover, as far as I can remember, we did not allow the solution to
stand within the resin for several minutes. These apprehensions could have been the possible
sources of the discrepancy on the results of Test 2 which is with the Fe(NO 3)3 solution.

Table 4 shows the result for the titration of the eluate collected from passing NaOH
through the solution. This step is simply a neutralization reaction between the OH - ions from
NaOH and H+ of the resin (Eq. 5). The eluate is then expected to be neutral. Thus, during
titration only the least amount of the titrant should be added to the eluate to indicate
equivalence point. Our group consumed 0.10 mL (see Table 4) of the titrant and the average
amount titrant consumed was also 0.10 mL (see Table 5).

OH- + H+ → H2O Eq. 5

Based on the data gathered and calculations done, we have concluded that the
reactions in ion exchange are stoichiometric and reversible. Thus, the number of active sites of
the resin, and the theoretical volumes of NaOH for titration and all depend only the cation
exchange equilibrium reaction. For the case of Na +, it requires only 1 ion exchange site, while 3
ion exchange sites for Fe3+. Theoretically, the volume of the NaOH consumed and the acid
capacity should be the same for the two tests. This is because the concentration of NaCl
solution used was three times higher that of the Fe(NO 3)3, and that Fe3+ requires three times ion
exchange sites than that of Na+. Hence, the stoichiometric relationships are just equal.

V. REFERENCES

 http://www.scribd.com/doc/23177334/Principle-of-Ion-Exchange-and-Resin-Beads

 http://nzic.org.nz/ChemProcesses/Ion-exchange

 http://www.dow.com/

 Fundamentals of Analytical Chemistry 8th edition

VI. COMMENTS
 Generally, the experiment done was quite hard for us both, and had a lot of things to be
done. So what we did with my partner is to divide the duty fairly. Fortunately, we have agreed
to the plan, so we didn’t have problems with regards to the fairness of the work load. We did
our assigned tasks very well and that we were able to accomplish the target goals in each
meeting of the experiment. So to sum it all, I really have no problem with my partner. Our
tandem for the first experiment was just perfect, and I hope the same thing for the other
experiments.

VII. CALCULATIONS

Cal. 1. Calculation for the theoretical volume of NaOH (NaCl – Test 1)

mmol NaCl 1 mmol HCl 1 mmol NaOH

10.00mL NaCl × 0.3001 × ×
mL NaCl 1mmol NaCl 1 mmol HCl
V NaOH =
mmol NaOH
0.09276
mL NaOH

V NaOH =32.35 mL NaOH

Cal. 2. Calculation for the theoretical volume of NaOH (Fe(NO3)3– Test 2)

V NaOH =10.00 mL Fe ¿ ¿

V NaOH =32.37 mL NaOH

Cal. 3 Sample Calculation for Acid Capacity (NaCl – Test 1, Trial 1)

 1 meq anion
+¿
H 1meq H +¿
Exchange Capacity=V NaOH × N NaOH × 1 meq × ¿¿
1 meqOH dry mass resin
¿

−¿
OH
−¿×0.09276 1 meq ¿¿
−¿ H +¿
mLs OH ×1 meq ¿¿
1 meq anion
+¿
−¿ 1 meq H
1 meq OH × ¿
10.0412g resins
Exchange Capacity=31.50 mL OH ¿

meq anion
Exchange Capacity=0.2910
g resins

Cal. 4 Sample Calculation for Acid Capacity (Fe(NO3)3– Test 2, Trial 1)

1 meq anion
+¿
H 1meq H +¿
Exchange Capacity=V NaOH × N NaOH × 1 meq × ¿¿
1 meqOH dry mass resin
¿

−¿
OH
−¿×0.09276 1 meq ¿¿
−¿ H +¿
mLOH ×1 meq ¿¿
1 meq anion
+¿
−¿ 1 meq H
1 meq OH × ¿
10.0412 g resins
Exchange Capacity=1.70 mLOH ¿

meq anion
Exchange Capacity=0.0157
g resins

Cal. 5 Percent error for Average Volume NaOH (NaCl—Test 1):

Percent error=| Actual value−Theoretical

Theoretical value
value
|× 100 %
32.20 mL−32.35 mL
Percent error=| |×100 %
32.35 mL

Percent error=0.4637 %
Cal. 6 Percent error for Average Volume NaOH NaOH (Fe(NO3)3– Test 2):

Percent error=| Actual value−Theoretical

Theoretical value
value
|× 100 %
2.53 mL−32.37 mL
Percent error=| |×100 %
32.37 mL

Percent error=92.18 %