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A.O. DE LA SERNA INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
OCTOBER 1, 2010
ABSTRACT This affirms the importance of the employment of ion exchange chromatography, including itsconcept of isocracy and electroneutrality, resin polymerization and sulfonation, stoichiometric ratio, hydration and particulates, in chemical analysis and determination of total ion concentration of Cu II in samples provided by instructor. This report discusses basic mechanisms and materials of specifically cation exchange columnar chromatography. Dowex 50 cation exchange resin was the stationary phase and the solvent containing the analyte ion was the mobile phase. IC conditions were kept paramount during the duration of the experiment. 10 mL of the analyte sample was then eluted to the preconditioned column for three trials. Per trial, the eluate was allowed to flow to a fresh Erlenmeyer flask until its pH = 5. This fresh pool was then titrated with previously standardized sodium hydroxide NaOH against a primary standard KHP. Cu2+ concentration in ppm was then calculated using the titrimetric data. The actual concentration was 1250 ppm Cu2+,the entire class reported a substantially accurate experimental value ² 1260 ppm Cu2+ of 0.8% error. The highly accurate value affirms the feasibility of IC as a means of determining total ion concentration.
INTRODUCTION The classical titrimetric and gravimetric methods have long been solely tantamount to analytical chemistry until the early Twentieth century. Chemical analysis is such a trending pursuit that analytical methodologies have been advancing exponentially. Hence, instrumental methods for analysis were developed. This report features ion exchange chromatography as a chromatographic instrumental method for analytical chemistry and as a separation science. Chromatography, as an instrumental method, separates, identifies, determines and quantifies the chemical components of a mixture. Methodologically, it can be planar using porous paper support or columnar using narrow tube support. It is composed of a stationary phase that is fixed in the support and the mobile phase that moves through the stationary phase.
Elution chromatography is one columnar chromatography technique involving washing the solute through a stationary phase by quantitative additions of the mobile phase. In 1850, forty years prior to Arrhenius· proposal of the ionization theory, a primordial notion about ion exchange was discovered by two Englishmen, J.T. Way and H.S. Thompson. The concept was described by the liberation of Calcium and Magnesium ions by treating earths with ammonium sulfate. Ion exchange is a meristem henceforth. The impeccable promise for analysis of the ion exchange concept underwent further harnessing. It was inculcated and formally tagged in chromatography in 1905 by M. Tswett. The term ´ion chromatographyµ has then been shortened by the common usage of the acronym IC. It has become a formidable advancement after its formalization as a novel analytical method by
Be guided that the discussions give more emphasis on cation exchange columnar chromatography as it has been employed throughout the course of the experiment. An intent discussion about IC. Dwelling on the stoichiometry of the equation. The experiment aimed to determine the concentration in ppm of Cu2+ in a given sample using IC as a separation technique. stoichiometric calculations for analysis. Separation is made possible by the adsorption of charged analyte molecules to immobilized resin ion exchange function group of opposite charge. 2 moles of H+ are displaced. RESULTS AND DISCUSSION As its name suggests. Therefore. Dowex 50 cation exchange resin was the stationary phase and the solvent containing the analyte ion was the mobile phase. to maintain the ionic integrity of the system. Equation (b) is the particular reaction in the experiment. separation phases and other particulates are found in the remainder of this report. limitations. These displaced H+ are then titrated with any strong base. 2 moles of the cation exchanger reacts. A flow rate of 15 drops per minute was maintained by precise manipulation of the stopcock. Hence. its processes. 10 mL of the analyte sample was then eluted to the preconditioned column for three trials. A column previously inserted with a wad of absorbent cotton for resin support and packed with sulfonated resin was kept hydrated with distilled water washings in an improvised IC burette tube. the displaced ion will be titrated and the calculated amount multiplied by the said propagated ratio or factor will be the amount of analyte constituents. look intently to these chemical equations (a) nrSO3 ² H+ + Mn+ (rSO3)nM + nH+ (b) 2rSO3 ² H+ + Cu2+ (rSO3)2Cu + 2H+ (c) 2H+ + 2OH. chemical concepts. ion exchange chromatography is a chromatographic science concerned with the separation of various type of charged species in a system.species are involved.Since it explicitly meddles with ion exchange.Small. This fresh pool was then titrated with previously standardized sodium hydroxide NaOH against a primary standard KHP. conditions. Per trial. Mn+refers to the metal / cationanalyte species. hence the name. not H+). The mobile phase was allowed to flow until the pH of the eluate = pH distilled water = pH of 5. In the experiment. To further substantiate and affirm the importance of this stoichiometric ionic reaction. and both species react with each other in one-to-one correspondence. There is an exchange of ions. is equal to one amount of Cu 2+ . The copper cation was separated from the sample at par with the displacement of hydrogen protons from the column. therefore. nrSO3 ² H+ refers to the sulfonatedcation exchanger resin. Stevens and Bauman of the Dow Chemical Company. The displaced ions from the column exist in a stoichiometric ratio or factor with the analyte ion.and transitively twice the amount of H+ . The technique was then commercialized in 1975 by the Dionex Corporation. These particulates are discussed intently in the remainder of this report. Cu2+ concentration in ppm was then calculated using the titrimetric data. Most importantly. the defining number in our calculation. NaOH for example. This system is usually comprised of separate phases. the leader of ion-exchange equipment today. twice the amount of OH.2H2O Equation (a) shows the general chemical reaction in cationic exchange. the eluate was allowed to flow to a fresh Erlenmeyer flask until its pH = 5. and H+ refers to the displaced proton ion. a stoichiometric reaction must be paramount at all analyses. n refers to that stoichiometric factor. for every 1 mole of copper II species. ´ion exchange chromatographyµ. (Anionic exchange works analogously except that OH.
The cross linkages with the copolymer give the resin physical strength to withstand subsequent ion reactions. The polymerization yields inactive resins and must be activated.Flow rate is crucial for the ion exchange to take place.The stationary adsorbent phase or the site of exchange. The resins are also perforated with microporesfor liquid pathways to increase surface area of adsorption. we are now ready to look intently on the explanations of the materials and mechanism of IC at par with the experiment performed (cationic exchange columnar chromatography). Transition ions from the previous usage of the resin might still be left in the column. Now we have a stoichiometric foothold for the ion exchange process. That is why a pH of 5 (the pH of distilled water must be observed. Their stronger cohesion prevents the resin ions from approaching the ion exchange sites.  Sulfonation by nrSO3². A pH of 5 means that the system is isocratic and therefore is highly deprotonated from H+ after the cation exchanger has fully reacted with the cationanalyte (all H+ have been displaced and are now ready for titration with strong base). All of which can be explained by the interplay of ionic charges during the stoichiometric reaction. Divalent and Trivalent organic and carboxylic are more strongly held making them a less activator for the resins. a set of parameters must be paramount and maintained throughout the duration of the experiment. As the resins react with the acid. Rapid flow will never assure the optimum completion of the reaction and the total .  Ultrapure Reagents should be used in cleaning the IC tube.  Isocracy or electroneutrality. must be solvated with deionized and distilled water. This shows that the resin is activated and the H+ are now ready to be exchanged with another cation species.Cation exchanger contain sulfonic acid groups nSO3 ² H+ attached / chelated to the aromatic ring of insoluble inorganic molecule nR.  Notice that a resin functional group is written with H+ written posteriorly (nrSO3 ² H+). Water is the medium for reaction.The resin used is Dowex ² 50. this working equation for determination of the amount of Cu2+ concentration in a given sample is derived: (d)Ppm Cu2+ = liberation of H+.  Flow rate should occur between 0.Inactive resins have hydrophobic spheres and must be introduced to sulfonic acid nrSO3 ² to expose the functional hydrophilic sites for exchange. Standard Conditions.Analogously. Regenration of cationic resin exchangers by 2M H2SO4. the column of resins. A modest rate of flow neutralizes the turbulence and high fluid pressure at the narrow end of the tube. Prior to conducting the IC. Resins.Sulfuric acid is such a strong acid that it prolongs the activity of the cation exchanger.7 and 4.Gel-based resins are produced by polymerizing with usually styrene-divinylbenzene S-DVB copolymer.5 mL or 15 drops per minute. The spherical shape narrows particle size allotment. thrice of an amount of H+ is equal to one amount of Aluminum 3+. water forms and swells the beads making it a suitable medium for reaction. Sulfuric acid displaces these cations as explained by IC mechanism making the column isocratic and ready for another usage. Other acids like carboxylic acid and other bases like quaternary ammonium can functionalize resins. Now grounded to the notion that the calculations are dependent on that stoichiometric ratio. These pores are generated by poragens like toluene. Impurities can accumulate on the column which reduce the ion exchange capacity and reacts drastically with the system chemicals.
The resin must be hydrated at all times. IC. Table 4. . Table 1 shows the standardization data of titrant NaOH of all the groups. Titration. This further affirms the feasibility and accuracy of IC in total ion concentration determination. using the working equation (d). The class improvised a burette type IC tube. Therefore.Addition of water. It also displaces entrapped gases. Water level should not fall below the resin level.Transition metals like Cu2+ has greater ionic affinity with the sulfonic acidic functional group of the cation exchanger than H+. IC is assailed with a few limitations.  The air pockets cause pulsations in the flow and may react with the resins forming altered canals. 2 and 3 per group. the ionic interactions are functions of ionic strength.As mentioned. Appendix C shows detailed data of statistics per group. See appendix B. H+ is eluted first. the liberated H+ are titrated with a strong base. These canals cause apparent loss in column capacity and adsorptive power. therefore. NaOH to determine the concentration of Cu 2+. It is grounded on the stoichiometric ratio that 1 mole Cu2+ = 2 moles H+. Each group has less than 10% error. Limitations of IC. Amidst the greater accuracy than that of classical methods. Table 4 shows the percent error of the experimental ppm value per group. Liberation of H+. Table 5 lists ions yet analyzable by IC Table 5. like any other instrumental titration.the percent error of the experimental ppm value per group.Cu 2+ppm per group Statistics. table 2 for detailed titration data of trials 1. the concentration of Cu 2+ in ppm was determined per sample. therefore. Separation is possible due to the differences in ionic strength.Ions yet analyzable by IC Not Yet Analyzable Isocyanite derivatives Silicate Large Phosphonates Nitrilotriacetic acid EDTA Ethylenediamine Toluenediamine One notable disadvantage is that IC is costly. Table 3. has many demands and conditions to be observed. The actual concentration per 10 mL sample was 1250. water solvates the system and serves as a suitable medium for reaction to take place.Aside from maintaining the isocracy of the system.Like any other instrumental method and as a still growing chromatographic science.Since the aforementioned discussion states that ion exchange explicitly depends on the ionic interactions.
Impurities may also affect the data. It can be induced that the interval in which. 7th Editionµ.. The standard deviations were pooled and the average ppm was computed. The actual concentration of the Cu2+ lies in the interval 1260±7.CarilloKJ. Table 6 shows the overall class statistics. ´Analytical Chemistry Laboratory Manualµ. Appendix C shows more statistical data including standard and relative standard deviations and confidence intervals. 1976.. Harold. the class garnered a very precise result.8% with the reported class value of 1260 ppm.Wiley-Interscience Publications The class got a low percent error with respect to the actual concentration of 1250 ppm. .59 ppm.. the value of the Cu 2+ concentration from finite number of sources lies is in 1260±7. 2009 ed.  Skoog D. CalejaHJ. 1983. it can be concluded that since the class has a very small amount of pooled standard deviation (9. and that the mechanism of isocracy of ionic charges and stoichiometric ratio are of vital importance for calculations involving IC. Hudson MJ.59 ppm. West D.. otherwise known as carbonate water dip. taking into account the confidence level. REFERENCES  Dyer A.University of the Philippines ² Diliman. meaning. The highly accurate value affirms the feasibility of IC as a means of determining total ion concentration. because the ion-exchange equilibrium is always determined by the balance between the H+ and analyte ion interaction with active sites of a resin. the class got precise measurements. The veracity and feasibility of IC can be affirmed basing from the experiment results. Frank. These limitations may have lead to these statistical deviations.86ppm).´Fundamentals of Analytical Chemistry. buffer may react with the resin or even the solvent containing the analyte. Inc. The class garnered a value of 1260 ppm (0.. ´Ion Exchange Chromatographyµ.et al. 1993.Saunders College Publishing  Walton. The pooled sd is also substantially low. ´The Practice of Ion Chromatographyµ. 1996. The class got an accurate result basing on the substantially low percent error of 0. Themethod provides no direct information on events occurring at the surface of the stationary phase. Table 6 shows the overall class statistics. However.An IC setup may encounter chromatographic anomalies..  Smith. ´Ion Exchange Processes: Advances and Applicationsµ. Institute of Chemistry.8% error).Dowen.. a buffer is needed.  Ballesteros J. There are also minor shifts in retention and calibration curves. Hutchinson & Ross.The Royal Society of Chemistry. An example is water dip. There are times that to maintain the isocracy. et al. However.et al. It can be concluded that the total ion concentration can be accurately determined via IC. Temperature must also be kept constant since minor fluctuations can alter the ionic kinetic energy. the standard deviations per group are very minimal and can still substantiate the feasibility of IC. SUMMARY AND CONCLUSION Upon intent analysis of the data.
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