WHERE DID THAT WATER COME FROM?

Analysis of Salt Content in a Water Sample by IonExchange Chromatography, High-Pressure Ion Chromatography (HPIC) and Gravimetric Analysis

Michelle Likhtshteyn

Carnegie Mellon University Chemistry Lab, Section B

November 3, 2011

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This experiment gave students the opportunity to learn about three experimental approaches that can be used to determine salt content in a sample, traditional ion-exchange chromatography, the instrumental technique high-pressure ion chromatography (HPIC), and gravimetric analysis. The objective of this experiment was to determine the % chloride in an unknown sample using ionexchange chromatography and gravimetric analysis. Another objective was to determine the % chloride, and maybe nitrate, in a water sample by ion-exchange chromatography and HPIC to identify the source of water found as evidence at Henrys crime scene. The efficacy of those three methods were them compared with each other on the basis of accuracy, time required, expertise required, cost of chemicals and equipment and cost of waste disposal. For ionexchange, the resin used was IONAC Anion Exchange Resin. The average chloride content in unknown #786, using ion-exchange analysis, was 59.85% 0.05 (N=3). The average chloride content in the unknown, using gravimetric analysis, was 59.05% (N=2). For the water sample, the average mg of chloride per mL water in sample D, using ion-exchange, was 0.078 mg/mL. According to the HPIC data, sample D contained both chloride and nitrate. The results from HPIC yielded .0798mg/mL of chloride and .008150mg/mL of nitrate in the water sample. The remainder of this paper will offer details regarding the data analysis and conclusions that can be drawn regarding the soundness of the data. A method used to determine chloride content in the unknown was Ion-Exchange chromatography. Chromatography can be used for the separation, identification and quantitative determination of chemical components in a mixture. All types of chromatography involve the use of two phases, a stationary and a mobile phase. The various components of the liquid distribute themselves between the two phases by different chemical interactions. Specifically, in ionexchange chromatography, ions of like charge are separated by the ability of the analyte (resin) to displace an ion of like charge from the stationary phase. In this experiment, the negatively charged chloride/other anions from either the unknown or evidence sample were exchanged with the hydroxide ions associated with the resin. After the resin was added to the column as a slurry, the sample was applied to the top of the resin bed; the mobile phase was then applied to the column and collected. The analysis was completed by titrating the displaced OH- eluted from the column. A flaw with this method is that chloride may not be the only anion exchanged by the column. However, this is not a problem for the unknown because only the chloride anion was

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present. The average chloride content determined is based on three precise trials using ion exchange. Three titrations were done in order to obtain a standard deviation, minimize error, and be more accurate. The sample was titrated using 0.0500 M HCl solution using phenolphthalein as the indicator; the solution was titrated until the pink color disappeared, and remained colorless for 30 seconds. The average chloride content in the unknown was 59.85% 0.05 (N=3). The small standard deviation proposes that the three trials were extremely similar in their %Cl- yield, and therefore quite precise. Due to the precision of data, none of the determinations were discarded in calculating average. Moreover, the results were accurate based on the range provided (45% to 70%). Precision also lends confidence in the assessment of accuracy; due to a small standard deviation, the %Cl- is believed to be more accurate. Despite confidence in the accuracy of the results, sources of error must be considered in discussion, and are as follows. The incorrect packing of column, such as incorrect installment of the kim wipes and poorly packed resin; this could have allowed some of the resin to pass through into the eluate which would have yielded incorrect %Cl-. Additionally, the resin might not have been completely converted to the basic form, which would have also yielded an incorrect %Cl- . Similarly, if the eluate was at a higher flow rate, the exchange of OH- ions could have been limited which would have affected the %Clas well. Another source of error could have been the titration of the eluate; over or under titration, and endpoint determination are always errors associated with titrations. Another method used to determine the %Cl- in the unknown was gravimetric analysis. Using this method, the compound analyzed (analyte) is separated as an insoluble compound from the other components of that sample, including any solvent present. The insoluble compound produced is then dried and weighed as precipitate. The criteria for a successful analysis are that the separation process must leave little analyte in the original sample, and the substance to be weighed must have a defined composition and be capable of being isolated in 99.99% yield and purity. Specific to this experiment, the chloride anion was precipitated as silver chloride by the addition of solubilized silver nitrate to a sample of the impure chloride unknown in solution. The weight of the crucible was taken before and after in order to determine the weight of precipitate. Two crucibles were used for gravimetric analysis; due to the limited availability of crucibles and oven space, only two chloride contents were determined. Due to such limitations, a standard

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deviation was not determined. The average of % Chloride in the unknown was 59.05% (N=2), sample 1 (56.76%) and sample 2 (61.34%). Determinations were not discarded in calculating an average. The average was used because of the difference in the mass of unknown used in each crucible; therefore to obtain most correct results, an average was taken. Due to lack of a standard deviation, extensive conclusions cannot be drawn regarding precision. However, the %Cl obtained is in the range of unknown samples (45% to 70%) provided in the report requirements, which suggests an accurate determination. Additionally, comparing the obtained average to that of the ion-exchange method is a good indication of accuracy. The difference between the two % yields is .80, which supports the accuracy of the gravimetric method. To further understand the gravimetric analysis, sources of error must be discussed, and are as follows. The empty crucibles needed to be rinsed, and then dried in the oven in order to obtain a constant weight. In order to maintain consistency and increase accuracy, the same balance was used in weighing both the empty crucibles and the crucible with precipitate. Moreover, filtering the unknown must be done extremely carefully as to not lose any of the precipitate. An error such as accidently spilling some of the precipitate while moving it in and out of the desiccator could have decreased the final yield of AgCl. An error made after digestion was the accidental exposure of sample #1 to UV light, which caused the Ag+ to photo reduce to Ag0 and created a purplish coat. This may have yielded a lower value for sample #1, despite the fact that a larger mass of unknown was precipitated in that crucible. This would be considered a determinant error, and did not negatively affect the final average with regards to comparative accuracy with ion-exchange. As mentioned above, the ion exchange and gravimetric methods yielded very similar results, which calls for a discussion of similarities and differences between the two methods. With regards to accuracy, the ion-exchange method was more accurate because it called for multiple trials to be run on the sample. This produced a standard deviation which allows extensive discussion of precision and accuracy. Whereas the gravimetric analysis allowed for two trials, due to limited availability of crucibles and oven space. Discussion concerning accuracy is not as complete for the gravimetric analysis because not enough trials were run, and a standard deviation was not determined. When comparing the time required, the ion-exchange method was feasibly completed in one lab period, whereas the gravimetric analysis required three lab sessions. Based on experiment procedure, gravimetric analysis takes triple the amount of time to complete, compared to ion-exchange. With regards to expertise required for the

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methods, ion-exchange requires more expertise than does the gravimetric analysis. Ion-exchange requires careful handling of the resin, and proper, yet challenging, insertion of the kim wipe for filtration. Moreover, the resin must be compressed in order to obtain the desired flow of the sample through the resin. Additionally, the ion-exchange method calls for titration of the eluate which must be done carefully. On the other hand, gravimetric analysis requires the trivial rinsing, drying and weighing of the crucibles with precipitate. Clearly, ion-exchange requires more precise and careful procedure. With regards to cost of waste disposal, both methods use hazardous chemicals and therefore are comparable in waste disposal. A summary of these comparisons are represented in table 1 below. Similarly, cost analysis is represented in tables 2 and 3; due to the cost of the hot plate, gravimetric analysis is the more expensive method.
Table 1: Ion Exchange Chromatography vs Gravimetric Analysis for the Unknown Element of Comparison Accuracy Time Required Expertise of method Cost of Chemicals & Equipment Waste Disposal
Table 2: Cost analysis for Ion Exchange Item buret hydrochloric acid (0.1N) Soluble chloride (unknown) column lonac resin 101 sodium hydroxide phenolpthalein erlenmeyer flask, 125mL volumetric pipet 25mL volumetric flask 100mL Total

Ion-Exchange Chromatography More accurate One lab session Careful procedure $290.34 Comparable

Gravimetric Analysis Less Accurate Three lab sessions Trivial procedure $600.32 Comparable

Table 3: Cost Analysis for Gravimetric Analysis Quantity 1 36.65mL .5116g 1 25g 6g 1g 4 1 1 Cost ($) 126.00 7.24 0.11 80.00 3.87 4.99 0.22 17.00 16.36 34.55 290.34 Item Silver Nitrate Nitric Acid Beaker (250 mL) stir bar hot plate filter crucibles crucible holder filter flask, 500mL filter flask w/o side arm, 500mL vacuum collar 2-hole rubber stopper Total Quantity .68784g .2 L 2 1 1 2 1 1 1 2 1 Cost ($) 5.83 7.06 5.52 5.13 428.33 40.00 50.00 17.25 27.32 12.02 1.86 600.32

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In addition to using ion exchange for analysis of the unknown, the method was also used to determine the average mg of chloride /mL water of Evidence sample D. The ion-exchange method for the evidence is comparable to that of the unknown explained earlier. A blank titration was run prior to using the column, this corrected for any base that may have been present in the water sample, or any base present in the flask residue. The water sample was applied to the column, which was followed by the addition of purified water; the pH of the eluate was tested until it reached 6. The water sample was titrated with 0.0100 M HCl using phenolphthalein indicator, as with the unknown. Only one trial of the water analysis was run because the water evidence wasnt evaluated for accuracy, but the unknown sample was, therefore more time was spent on analysis of unknowns. Therefore, neither precision nor accuracy can be discussed without HPIC data. The chloride content in water for Evidence D was 0.078mg/mL. All the samples in this experiment contained chloride and some also contained concentrations of nitrate. For the ion-exchange analysis of water, an assumption made was that chloride was the only anion in the water sample. This pertains to a flaw in the ion-exchange method for the water sample; it can only detect one anion at once. The sources of error associated with the water sample are comparable to those previously discussed for the unknown. Incorrect packing of the column, incorrect flow rate, and titration errors are all applicable to the water sample. The errors associated with ion-exchange are corrected in the HPIC data provided. Another method introduced in this experiment was HPIC which functions similarly to the ionexchange chromatography previously described. The water sample is injected into a stream of the mobile phase and solvent is pumped through the column. HPIC is a quick method with increased sensitivity and the ability to analyze for multiple ions simultaneously. The mobile phase is in a reservoir that is attached to the pump, and is pumped through under pressure past the injector and into the column. The column is packed with beads that are derivatized with sulfonic acid, carboxylic acid groups, or ammonium groups in the case of anion analysis. Different ions have differing affinities for the resin and the mobile phase which results in separation of the sample. Separation of the sample takes place in the column if more than one anion is present in the sample. The eluent from the column then passes through a detector which quantifies the amount of each anion by responding to a change in conductivity of the solution caused by the concentration and charge of cations and anions in solution. The sensor monitors the resistance between the two electrodes in the detector and produces a signal that is directly

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related to concentration. The retention time is provided with each signal; retention time is the time taken for a particular compound to travel from the column to the detector. The time depends on the differing affinities that ions have for the resin and the mobile phase. In looking at the retention time of the standards provided for the nitrate and chloride sample, it can be noted that ions elute differently depending on the charge and ionic radius. Due to the molecular size, the chloride ion will elute first, followed by the nitrate ion. Moreover, the relative order of the retention times increase as the concentrations for both chloride and nitrate are increased, which makes sense based on the characteristics of the respective anions and their affinities. A conductivity detector was used for the HPIC data in this experiment. This detection is temperature sensitive and therefore the column is contained in a temperature constant heater. The HPIC data was provided to the class via blackboard, and the respective samples were analyzed. After analyzing the HPIC data provided for sample D, it was determined that both chloride and nitrates are contained in the sample; two peaks are present on the HPIC data. The presence of nitrate, in addition to chloride, nullifies the accuracy of the assumption made for water sample D for the ion-exchange method. Therefore, the mg/mL obtained in the experiment for evidence D is a sum of the nitrate and chloride mg/mL. HPIC data yielded .07985 mg/mL of chloride and .008150 mg/mL of nitrate in the sample, a total of .088 mg/mL of chloride and nitrate together. Comparing this to the experimental data from ion-exchange analysis (.078 mg/mL), proposes a difference of .01 mg/mL. A small difference between the two methods suggests that there is a high level of accuracy in the obtained experimental results. A table summarizing the similarities and differences is presented below.
Table 4: Ion Exchange Chromatography vs HPIC Element of Comparison Accuracy Ion-Exchange Chromatography Less accurate and sensitive, one anion HPIC More Accurate and sensitive, multiple anions Time Required Expertise of method Cost of Chemicals & Equipment Waste Disposal One lab session (4 hours) Careful procedure, a lot of errors associated $290.34 Hazardous Waste, comparable One lab session (1 hour) Use of instrument properly $17,000 (per unit) Hazardous Waste, comparable

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A difference concerning accuracy between the two methods is the use of gravity for the flow of mobile phase in ion exchange, and the use of an automatic pump to push the solvent through the column in HPIC. This makes HPIC a more accurate and sensitive method for chloride detection. Moreover, HPIC is able to detect multiple anions simultaneously which corrects a flaw with the ion-exchange. The HPIC instrument requires about an hour for an analysis of such samples, whereas manual ion-exchange calls for about 3-4 hours. The effectiveness and accuracy can be attributed to the stark difference in cost between the two methods. An HPIC machine can cost around $17,000 (Alibaba), therefore more accuracy is expected of such an instrument. With regards to waste disposal, both methods use hazardous wastes that must then be disposed of in according to hazardous waste guidelines. Clearly, the HPIC method is superior to that of ionexchange. However, careful and meticulous work in the ion-exchange process will lead to accurate results as demonstrated with the obtained data. After comparing the ion-exchange chromatography to the gravimetric analysis, of the unknown sample, it is clear that ion-exchange chromatography is the more superior choice for chloride analysis. To further verify this conclusion the HPIC results were compared to the ion-exchange results, for the evidence, and demonstrate that ion-exchange is quite accurate in determining chloride analysis. However, the HPIC instrument does indeed provide a more sensitive and more accurate method for analysis when dealing with multiple anions simultaneously. With regards to Henrys death, the water removes from his clothing was determined experimentally to contain 800ppm of sodium chloride and 100ppm of sodium nitrate. The table below summarizes the concentrations of each anion in samples A-E.
Table 5: Concentrations of sodium chloride and sodium nitrate ion in samples A-E Sample Ppm of sodium chloride A B C D E 111.16ppm 766.91ppm 261.31ppm 131.63ppm 9.430 y=759.27x+6591.8 Ppm of sodium nitrate 91.21ppm 99.23ppm 40.18ppm 11.72ppm 1601.5 y=385.97x-57.068

Sample B contains 766.91ppm of sodium chloride and 99.23ppm of sodium nitrate, which is similar to the experimentally determined concentrations of Henrys shirt. Therefore, the water found on Henrys clothing was from sample B salt-water

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aquarium found in his home. Henry was not dragged out to the ocean adjacent to his property, instead he was most likely murdered in his own home.

Work Cited 1. "Experiment 4." Laboratory I: Introduction to Chemical Analysis Lab Manual. Fall 2011 247-266. Print. 2. " I o n C h r o m a t o g r a p h y M a n u f a c t u r e r s . " A l i b a b a . N . p . , n . d . W e b . 1 Nov 2011. <http://www.alibaba.com/showroom/ion c h r o m a t o g r a p h y. h t m l > .