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EXPERIMENT 1

Properties of Ion-Exchange Resins

Submitted by:

Cahilig, Guen Gian D.

Seduco, Rhett Adrian C.

Ubas, Johnziel G.

Submitted to:

Prof. Jay O. Martizano

Chem 126 – Laboratory

23 February 2018

University of the Philippines Visayas

Miagao, Iloilo
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I. Abstract

The experiment was conducted to demonstrate both cation and anion exchanges, as

well as to quantify the concentrations of the given samples: sodium chloride (NaCl), ferric

nitrate (Fe(NO3)3) and sodium hydroxide (NaOH) using strong acid cation exchange resins,

and to determine the independent masses of the Ni2+ and Zn2+ in the nickel- and zinc-

containing sample using strong base anion exchange resins. The said resins acted as the

stationary phase and the solutions passing through the column were the mobile phase in the

entire ion-exchange chromatography. Four generic steps were performed: conditioning

solvent addition, loading of sample solution, washing solvent addition and finally elution.

The eluents were collected as the final analytes to be titrated with their respective

standardized titrants in order to quantitatively analyze the samples and unknown.

Moreover, ion-exchange chromatography was found to be effective in the separation of

interferences from the desired analyte such as water softening and protein purification.

II. Introduction

Ion exchange is the 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. It

is a process in which ions attached to a high molecular weight polymer are exchanged for

other ions in a solution that is in contact with the polymer (Skoog et al, 2014). Ion exchange

is used in water treatment and also provides a method of separation in many non-water

processes. Impurities found in water can be removed by use of this, with the process of

water softening and demineralization (Skoog et al. 2014). It has special utility in chemical

synthesis, medical research, food processing, mining, agriculture and a variety of other areas
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(Wheaton et al. 2000). Ion exchange is also important in many chromatographic techniques

(Harris 2010).

Ion exchange occurs in a variety of substances and it has been used on an industrial

basis since circa 1910 with the introduction of water softening using natural and later,

synthetic zeolites. Sulfonated coal, developed for industrial water treatment, was the first

ion exchange material that was stable at low pH. The introduction of synthetic organic ion

exchange resins in 1935 resulted from the synthesis of phenolic condensation products

containing either sulfonic or amine groups which could be used for the reversible exchange

of cations or anions (Wheaton et al. 2000).

In this experiment, determination of the properties of ion-exchange resins for cations

and anions were performed. The experiment is separated into two parts. The first part aims

to illustrate cation exchange and determine the molarities of the given sample solutions

through cation exchange resin. The second part aims to illustrate cation separation by ion-

exchange method using a strong-base exchanger and determine the molarities of the given

sample solutions through anion exchange resin. Preparations for the experiment included a

sequence of washing, pouring and mixing of needed chemicals, titration, and heating

process in order for the experimenters to gather a collection of data for the needed

calculations and analyses.

III. Materials and Methods

To execute the experiment, an ion-exchange column was used. Composition of the

column includes a pipette with a 3-inch long rubber tubing attached to its tip. A 5-mL

medicine dropper was used by removing the rubber handle and attaching the remaining part

to the lower part of the rubber tubing. To regulate the flow of the fluid, a pinchcock was
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fastened to the rubber tubing. And a small piece of cotton was placed at the very bottom of

the column.

A. Cation Exchange Resin

Column preparation

In this part of the experiment, around 10.0 g of cation-exchange resin (Dowex 50)

was weighed in a beaker, and was washed three times using distilled water. The washed

resin was then added with 50.0 mL of distilled water, and was slowly poured into the

column. The transferring of resin was executed with care to avoid bubble formation inside

the column. To prevent channeling of beads inside the column, the water level was strictly

allowed to fall only above the surface of the resin bed. A parafilm was used to store the

column by sealing tightly the top part.

For the activation of resin, 100 mL of 1 M HCl was poured and moved through the

resin column. Adjustment of the pinchcock was made in order for the solution to move

through the column at a rate of 15 mL/min. Thereafter, 150 mL of distilled water was added

for washing process.

Analysis

For the analysis part, 10 mL of 0.3 M NaCl was poured and moved through the

column, followed by 100 mL of distilled water for washing, at a rate of 3 mL/min. The height

of the liquid inside the column was strictly allowed and maintained only to fall above the

surface of the resin bed at all times. The collected eluate was placed inside a 250-mL

Erlenmeyer flask. Three drops of phenolphthalein indicator were added to the eluate. The

eluate was titrated with a standard 0.1016 M NaOH solution. This procedure was performed
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three times (3 trials). After the three trials, the H+ in the column was regenerated by pouring

and moving through 100 mL of 1 M HCl into the column, followed by 150 mL of distilled

water for washing.

Repetition of the procedure above was performed but instead of NaCl, 10 mL of 0.1

M Fe(NO3)3 was poured and moved through the column. The eluate was also titrated against

the same standard NaOH solution to a phenolphthalein endpoint. The procedure was also

done three times (3 trials).

The H+ in the column was regenerated, followed by washing with distilled water. This

time, 10.0 mL of 0.10 M NaOH was allowed to move through the column. The collected

eluate was also titrated using the same standard NaOH solution to a phenolphthalein

endpoint. This procedure was also done three times (3 trials). Recording of the volume of

the titrant used and observations was done by the experimenters before and after the

process.

B. Ion Exchange Separation and Titrimetric Determination of Nickel (II) and Zinc (II)

Column Preparation

By using a strong-base anion exchange resin, a new resin column was prepared. The

methods used in preparing the ion-exchange column in the first part of the experiment were

done. The resin column was then washed with 50 mL of 6 M NH3, followed by 100 mL of

distilled water, and 100 mL of 2 M HCl. The height of the liquid inside the column was strictly

allowed and maintained only to fall above the surface of the resin bed at all times.
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Generation of the Unknown

For the generation of the unknown, 1.3687g of ZnCl2 and 1.2952g of NiCl2 were

transferred to a 250-mL volumetric flask. Forty milliliters of 12 M HCl was added into the

flask, and then diluted to the mark using distilled water, generating 0.04 M unknown

solution.

Separation of Nickel (II) and Zinc (II)

10 mL of the unknown solution was poured and moved through the column. The

solution was moved through the column in a slow rate until the level of the liquid was nearly

above the surface of the resin bed.

To wash the inner wall of the column, two 3 mL portions of 2 M HCl were used,

allowing the liquid level to reach the surface of the resin bed before the addition of another

portion. To eluate nickel, the column was washed with 50 mL of 2 M HCl solution at a rate of

3 mL/min. To eluate zinc, 100 mL of distilled water was passed through the column at the

same rate. Collection of three trials per analyte was done.

Titration of Nickel and Zinc with EDTA

a.) Titration of Nickel

To evaporate the excess HCl, the collected eluate was placed on a hotplate until only

about 4-5 mL of the solution was left. To dissolve the residue, 100 mL of distilled water

followed with 15 mL of NH3/NH4Cl (pH 10) buffer were used. A pinch of murexide was

added to serve as the indicator. Lastly, the resulting solution was titrated with standard

0.01000 M EDTA solution. The volume of the titrant at which the solution turned from
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yellow to blue was recorded. The same procedure was also done for the 2 two remaining

trials. The weight in milligrams (mg) of nickel (Ni2+) in the unknown was calculated.

b.) Titration of Zinc

15-mL of pH 10 buffer and five drops of Eriochrome Black T (a complexometric

indicator) were added to the obtained eluate. The final solution was also titrated against the

same standard EDTA solution. The volume of EDTA required for a color change from wine

red to blue was recorded. Three trials were also performed. The weight in milligrams (mg) of

zinc (Zn2+) in the unknown was also calculated.

IV. Results

Table 1.1. Standardization of NaOH with KHP

Primary Standard Used Potassium hydrogen phthalate (KHP)

Formula Mass of KHP (g/mol) 204.22

% Purity of KHP 99.9%

TRIALS 1 2 3

weight of KHP (g) 0.7654 0.7659 0.7656

corr. weight of KHP (g) 0.7646346 0.7651341 0.7648344

Final Reading of NaOH (mL) 38.6 39.6 38.7

Initial Reading of NaOH (mL) 0.1 0 0

Volume of NaOH used (mL) 38.5 39.6 38.7

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MNaOH 0.097251195 0.094611537 0.096773885

average MNaOH 0.096212206

standard deviation 0.001406613

Table 1.2. Determination of the Exchange or Acid Capacity of Cation Exchange Resin

B.1. +10mL 0.3M NaCl

TRIALS 1 2 3

Final Reading of NaOH (mL) 27.3 29 29.8

Initial Reading of NaOH (mL) 0 0 0

Volume of NaOH used (mL) 27.3 29 29.8

MNaCl 0.262659 0.279015 0.286712

average MNaCl 0.27612903

standard deviation 0.012283552

B.2. +10mL 0.1M Fe(NO3)3

TRIALS 1 2 3

Final Reading of NaOH (mL) 27.6 27.4 28.2

Initial Reading of NaOH (mL) 0 0 0

Volume of NaOH used (mL) 27.6 27.4 28.2

MFe(NO3)3 0.265546 0.263621 0.271318

average MFe(NO3)3 0.266828517

standard deviation 0.004005634

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B.3. +10mL 0.1M NaOH

TRIALS 1 2 3

Final Reading of NaOH (mL) 27.5 27.6 27.7

Initial Reading of NaOH (mL) 27.4 27.5 27.6

Volume of NaOH used (mL) 0.1 0.1 0.1

MNaOH 0.000962 0.000962 0.000962

average MNaOH 0.000962122

standard deviation 1.97807E-17

Table 1.3. Standardization of EDTA against CaCO3

Primary Standard Used Sodium Carbonate (CaCO3)

Formula Mass of CaCO3 (g/mol) 100.09

Mass of CaCO3 (g) 0.2636

Mass of EDTA (g) 11.178

Volume of Water (mL) 250

TRIALS 1 2 3

Volume of CaCO3 (mL) 50 50 50

Volume of EDTA (mL) 52 52 51

Average Volume of EDTA (mL) 51.66666667

MCaCO3 0.010534519
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MEDTA 0.010129 0.010129 0.01032796

Average MEDTA 0.01019555

Standard Deviation 0.00011467

Titer EDTA (mg/mL) 5.018538 5.018538 5.116941176

Average Titer EDTA (mg/mL) 5.051339367

Table 1.4. Determination of Nickel (II) and Zinc (II)

D.1. Nickel

TRIALS 1 2 3

Final Reading of EDTA (mL) 61.6 62.2 62.5

Initial Reading of EDTA (mL) 0 0 0

Volume of EDTA used (mL) 61.6 62.2 62.5

mNi (mg) 311.1625 314.1933 315.7087

average mNi (mg) 313.6881747

standard deviation 2.314814501

D.2. Zinc

TRIALS 1 2 3

Final Reading of EDTA (mL) 38.8 38.3 38.1

Initial Reading of EDTA (mL) 0 0 0

Volume of EDTA used (mL) 38.8 38.3 38.1

mZn (mg) 195.992 193.4663 192.456

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average mZn (mg) 193.9714317

standard deviation 1.82128631

V. Discussion

Ion-exchange resin made a great contribution to the chromatographic separation

techniques. In fact, ion-exchange chromatography refers to modern, efficient methods for

separating and determining ions on columns with relatively low ion-exchange capacity

(Skoog, et. al., 2007). The main principle of this method based on the positive and negative

charge interaction between specific molecules with matrix which is in the column of

chromatography. This method is used to separate mixtures of ions (organic or inorganic),

and finds its application mostly in protein separations. The stationary phase consists of very

small polymer resin beads which have many ionic bonding sites on their surface, termed as

ion-exchange resins. This resin can be either an anion exchange resin, which possesses

positively charged sites to attract negative ions, or a cation exchange resin, which possesses

negatively charge sites to attract positive ions.

In the cation exchange resin, acidic condition had been introduced first to the resin

by adding HCl, generating H+. This means that the H+ was attracted by the negative charge

sites of the resin. Meanwhile, Cl- was the first ion to be dislodged by washing the resin with

water. In the addition of the sample solutions, NaCl, Fe(NO3)3, and NaOH, separately and

respectively, the negative ion of the added solution was attached with the H+ while the

negative ion of the same solution was first to be eluted. Finally, the negative ion was next to

be eluted by washing again the resin with water. In the analysis part, the samples that were

collected after the ion-exchange chromatography were titrated against the standardized
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NaOH with the aide of phenolphthalein indicator. Final volumes used to achieve end point of

each sample (3 trials to each sample) were presented in Table 1.2. The molarities of the

sample solutions were calculated (some were presented in the Sample Calculations section)

and presented in the said table.

In the anion exchange resin, the basic condition had been introduced first to the resin

by adding NH3, generating NH2-. This means that the NH2- was attracted by the positive

charge sites of the resin. Meanwhile, H+ was the first ion to be dislodged by washing the

resin with water. In the washing of HCl, the Cl- was attracted to the NH2-, forming chloramine

(NH2Cl). By adding the unknown solution, the first elution of Ni2+ had been made by

removing the H+ from added HCl. Addition of more amount of HCl triggered the Ni2+ with

excess amounts of H+ and Cl- to be eluted. Nickel was first to be separated since it did not

form a significant complex in HCl and it passed rapidly through a column. Stable

chlorozincate(II) complexes (such as ZnCl42-) were formed in such medium. Thus, after

separation was completed, elution with water effectively decomposed the chloro complexes

and permitted the removal of the zinc. In the analysis part, the samples that were collected

after the ion-exchange chromatography were titrated against the standardized EDTA with

the aide of the following indicators: EBT (for zinc) and Murexide (for nickel). To nickel

sample, water was added after it was heated to dissolve the residue. Ammonia-Ammonium

chloride (NH3-NH4Cl) buffer (pH-10) was also added before the EBT indicator in order to

control pH change. Final volumes used to achieve end point of each sample (3 trials to each

sample) were presented in Table 1.4. The molarities of the sample solutions were calculated

(some were presented in the Sample Calculations section) and presented in the said table.
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VI. Conclusions

Ion-exchange chromatography is indeed useful in determining some properties of a

certain sample solution such as its concentration and weight. Through this experiment, four

generic steps were realized: 1) addition of conditioning solvent; 2) loading of sample

solution; 3) addition of washing solvent; and, 4) elution to obtain the final analyte solution to

be titrated.

VII. Literature Cited

Skoog, D., Holler, F.J., and Crouch, S. (2007). Principles of Instrumental Analysis, 6th edition.

Canada: Thomson Corporation. p. 839.

Harris, D. (2010). Quantitative Chemical Analysis, Eighth Edition. New York, NY: W.H.

Freeman and Co. pp. 635 – 636.

Skoog D., Crouch S., Holler F., and West D. (2014). Fundamentals of Analytical Chemistry, 9th

Edition. Cengage Learning Asia Pte Ltd. pp. 857 – 861.

Wheaton, R. Lefevre, LJ. (2000). DOWEX Ion Exchange Resins: Fundamentals of Ion

Exchange. Retrieved on February 19, 2018 from

http://msdssearch.dow.com/PublishedLiteratureDOWCOM/dh_0032/0901b8038003

26ca.pdf
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VIII. Sample Calculations

A. Standardization of NaOH with KHP

Molarity of NaOH:

1𝑚𝑜𝑙 𝐾𝐻𝑃 1𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

0.99 × 0.7654𝑔 𝐾𝐻𝑃 × 204.22𝑔 𝐾𝐻𝑃 ×
1𝑚𝑜𝑙 𝐾𝐻𝑃
𝑀𝑁𝑎𝑂𝐻 = = 0.0973𝑀 𝑁𝑎𝑂𝐻
1𝐿 𝑁𝑎𝑂𝐻
38.5𝑚𝐿 𝑁𝑎𝑂𝐻 × 1000𝑚𝐿 𝑁𝑎𝑂𝐻

B. Determination of the Exchange or Acid Capacity of Cation Exchange Resin

Molarity of NaCl:

1𝐿 𝑁𝑎𝑂𝐻
0.096212206𝑀 𝑁𝑎𝑂𝐻 × (27.3𝑚𝐿 𝑁𝑎𝑂𝐻 × 1000𝑚𝐿 𝑁𝑎𝑂𝐻 )
𝑀𝑁𝑎𝐶𝑙 =
1𝐿 𝑁𝑎𝐶𝑙
10𝑚𝐿 𝑁𝑎𝐶𝑙 ×
1000𝑚𝐿 𝑁𝑎𝐶𝑙

= 0.263𝑀 𝑁𝑎𝐶𝑙

Molarity of Fe(NO3)3:

1𝐿 𝑁𝑎𝑂𝐻
0.096212206𝑀 𝑁𝑎𝑂𝐻 × (27.6𝑚𝐿 𝑁𝑎𝑂𝐻 × 1000𝑚𝐿 𝑁𝑎𝑂𝐻 )
𝑀𝐹𝑒(𝑁𝑂3 )3 =
1𝐿 𝐹𝑒(𝑁𝑂3 )3
10𝑚𝐿 𝐹𝑒(𝑁𝑂3 )3 ×
1000𝑚𝐿 𝐹𝑒(𝑁𝑂3 )3

= 0.266𝑀 𝐹𝑒(𝑁𝑂3 )3

Molarity of NaOH:

1𝐿 𝑁𝑎𝑂𝐻
0.096212206𝑀 𝑁𝑎𝑂𝐻 × (0.1𝑚𝐿 𝑁𝑎𝑂𝐻 × 1000𝑚𝐿 𝑁𝑎𝑂𝐻 )
𝑀𝑁𝑎𝑂𝐻 =
1𝐿 𝑁𝑎𝑂𝐻
10𝑚𝐿 𝑁𝑎𝑂𝐻 × 1000𝑚𝐿 𝑁𝑎𝑂𝐻

= 0.000962𝑀 𝑁𝑎𝑂𝐻

C. Standardization of EDTA against CaCO3

Molarity of CaCO3:

1𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3
0.2636𝑔 𝐶𝑎𝐶𝑂3 × 100.09𝑔 𝐶𝑎𝐶𝑂
3
𝑀𝐶𝑎𝐶𝑂3 = = 0.01053𝑀 𝐶𝑎𝐶𝑂3
1𝐿 𝐻 𝑂
250𝑚𝐿 𝐻2 𝑂 × 1000𝑚𝐿2 𝐻 𝑂
2
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Molarity of EDTA:

1𝐿 𝐶𝑎𝐶𝑂3
0.01053𝑀 𝐶𝑎𝐶𝑂3 × (50𝑚𝐿 𝐶𝑎𝐶𝑂3 × 1000𝑚𝐿 𝐶𝑎𝐶𝑂 )
3
𝑀𝐸𝐷𝑇𝐴 =
1𝐿 𝐸𝐷𝑇𝐴
52𝑚𝐿 𝐸𝐷𝑇𝐴 × 1000𝑚𝐿 𝐸𝐷𝑇𝐴

= 0.01013𝑀 𝐸𝐷𝑇𝐴

Titer EDTA (mg/mL):

1000𝑚𝑔 𝐶𝑎𝐶𝑂3
0.99 × 0.2636𝑔 𝐶𝑎𝐶𝑂3 × 𝑚𝑔 𝐶𝑎𝐶𝑂3
1𝑔 𝐶𝑎𝐶𝑂3
𝑡𝑖𝑡𝑒𝑟𝐸𝐷𝑇𝐴 = = 5.019
52𝑚𝐿 𝐸𝐷𝑇𝐴 𝑚𝐿 𝐸𝐷𝑇𝐴

D. Determination of Nickel (II) and Zinc (II)

Mass of Ni2+ (in mg):

𝑚𝑔
𝑚𝑁𝑖 2+ = 5.051339367 × 61.6𝑚𝐿 𝐸𝐷𝑇𝐴 = 311.1625𝑚𝑔 𝑁𝑖 2+
𝑚𝐿 𝐸𝐷𝑇𝐴

Mass of Zn2+ (in mg):

𝑚𝑔
𝑚𝑍𝑛2+ = 5.051339367 × 38.8𝑚𝐿 𝐸𝐷𝑇𝐴 = 195.992𝑚𝑔 𝑍𝑛2+
𝑚𝐿 𝐸𝐷𝑇𝐴