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

sample D contained both chloride and nitrate. The efficacy of those three methods were them compared with each other on the basis of accuracy. and gravimetric analysis. The remainder of this paper will offer details regarding the data analysis and conclusions that can be drawn regarding the soundness of the data. was 59.05% (N=2). For ionexchange. using gravimetric analysis. However.1|Likhtshteyn This experiment gave students the opportunity to learn about three experimental approaches that can be used to determine salt content in a sample. The various components of the liquid distribute themselves between the two phases by different chemical interactions. a stationary and a mobile phase. the negatively charged chloride/other anions from either the unknown or evidence sample were exchanged with the hydroxide ions associated with the resin. was 0.05 (N=3). this is not a problem for the unknown because only the chloride anion was . The analysis was completed by titrating the displaced OH. the instrumental technique high-pressure ion chromatography (HPIC). the resin used was IONAC ® Anion Exchange Resin. The results from HPIC yielded . For the water sample.eluted from the column. All types of chromatography involve the use of two phases. According to the HPIC data. traditional ion-exchange chromatography. Chromatography can be used for the separation. ions of like charge are separated by the ability of the analyte (resin) to displace an ion of like charge from the stationary phase. using ion-exchange. Another objective was to determine the % chloride. in a water sample by ion-exchange chromatography and HPIC to identify the source of water found as evidence at Henry’s crime scene. A flaw with this method is that chloride may not be the only anion exchanged by the column. in ionexchange chromatography. the average mg of chloride per mL water in sample D. was 59. the mobile phase was then applied to the column and collected. After the resin was added to the column as a slurry.008150mg/mL of nitrate in the water sample. identification and quantitative determination of chemical components in a mixture. The average chloride content in unknown #786.078 mg/mL. Specifically. The average chloride content in the unknown. In this experiment. A method used to determine chloride content in the unknown was Ion-Exchange chromatography. and maybe nitrate. The objective of this experiment was to determine the % chloride in an unknown sample using ionexchange chromatography and gravimetric analysis. using ion-exchange analysis.85% ± 0. expertise required. time required. cost of chemicals and equipment and cost of waste disposal. the sample was applied to the top of the resin bed.0798mg/mL of chloride and .

Despite confidence in the accuracy of the results. the exchange of OH. Additionally. Another method used to determine the %Cl. and be more accurate. the %Cl. The sample was titrated using 0. sources of error must be considered in discussion. and endpoint determination are always errors associated with titrations. due to the limited availability of crucibles and oven space. The incorrect packing of column.in the unknown was gravimetric analysis. which would have also yielded an incorrect %Cl.0500 M HCl solution using phenolphthalein as the indicator. Three titrations were done in order to obtain a standard deviation.99% yield and purity.is believed to be more accurate. including any solvent present..05 (N=3). The average chloride content determined is based on three precise trials using ion exchange. Specific to this experiment. Two crucibles were used for gravimetric analysis. The weight of the crucible was taken before and after in order to determine the weight of precipitate. The criteria for a successful analysis are that the separation process must leave little analyte in the original sample. and are as follows. minimize error. and remained colorless for 30 seconds. 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.85% ± 0. The average chloride content in the unknown was 59. Using this method. Another source of error could have been the titration of the eluate. this could have allowed some of the resin to pass through into the eluate which would have yielded incorrect %Cl-. such as incorrect installment of the kim wipes and poorly packed resin.ions could have been limited which would have affected the %Clas well. a standard . Moreover. Due to such limitations. Precision also lends confidence in the assessment of accuracy.2|Likhtshteyn present. if the eluate was at a higher flow rate. over or under titration. the results were accurate based on the range provided (45% to 70%).yield. Similarly. The insoluble compound produced is then dried and weighed as precipitate. the solution was titrated until the pink color disappeared. the compound analyzed (analyte) is separated as an insoluble compound from the other components of that sample. Due to the precision of data. the resin might not have been completely converted to the basic form. and the substance to be weighed must have a defined composition and be capable of being isolated in 99. only two chloride contents were determined. none of the determinations were discarded in calculating average. The small standard deviation proposes that the three trials were extremely similar in their %Cl. and therefore quite precise. due to a small standard deviation.

When comparing the time required. In order to maintain consistency and increase accuracy. Discussion concerning accuracy is not as complete for the gravimetric analysis because not enough trials were run. which supports the accuracy of the gravimetric method. With regards to expertise required for the . However. This may have yielded a lower value for sample #1.34%). the ion-exchange method was feasibly completed in one lab period. extensive conclusions cannot be drawn regarding precision. the same balance was used in weighing both the empty crucibles and the crucible with precipitate. The average was used because of the difference in the mass of unknown used in each crucible.3|Likhtshteyn deviation was not determined. despite the fact that a larger mass of unknown was precipitated in that crucible. sources of error must be discussed. the %Cl obtained is in the range of unknown samples (45% to 70%) provided in the report requirements. gravimetric analysis takes triple the amount of time to complete. which calls for a discussion of similarities and differences between the two methods. and then dried in the oven in order to obtain a constant weight. an average was taken.05% (N=2). 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. sample 1 (56. Due to lack of a standard deviation. Based on experiment procedure. whereas the gravimetric analysis required three lab sessions. compared to ion-exchange. The difference between the two % yields is . The empty crucibles needed to be rinsed. and a standard deviation was not determined.80. Whereas the gravimetric analysis allowed for two trials. Moreover. To further understand the gravimetric analysis. With regards to accuracy. and did not negatively affect the final average with regards to comparative accuracy with ion-exchange. the ion-exchange method was more accurate because it called for multiple trials to be run on the sample. which suggests an accurate determination.76%) and sample 2 (61. This would be considered a determinant error. Additionally. which caused the Ag+ to photo reduce to Ag0 and created a purplish coat. filtering the unknown must be done extremely carefully as to not lose any of the precipitate. Determinations were not discarded in calculating an average. therefore to obtain most correct results. This produced a standard deviation which allows extensive discussion of precision and accuracy. comparing the obtained average to that of the ion-exchange method is a good indication of accuracy. As mentioned above. the ion exchange and gravimetric methods yielded very similar results. The average of % Chloride in the unknown was 59. due to limited availability of crucibles and oven space. An error made after digestion was the accidental exposure of sample #1 to UV light. and are as follows.

00 50. 125mL volumetric pipet 25mL volumetric flask 100mL Total Ion-Exchange Chromatography More accurate One lab session Careful procedure $290.32 .68784g .34 Item Silver Nitrate Nitric Acid Beaker (250 mL) stir bar hot plate filter crucibles crucible holder filter flask.00 7. 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. Moreover.86 600.33 40.32 Comparable Table 3: Cost Analysis for Gravimetric Analysis Quantity 1 36. Clearly.36 34. the ion-exchange method calls for titration of the eluate which must be done carefully. cost analysis is represented in tables 2 and 3.13 428.25 27. Similarly.1N) Soluble chloride (unknown) column lonac resin 101 sodium hydroxide phenolpthalein erlenmeyer flask.11 80.99 0.02 1. ion-exchange requires more expertise than does the gravimetric analysis. yet challenging. Additionally. gravimetric analysis is the more expensive method. both methods use hazardous chemicals and therefore are comparable in waste disposal. and proper.87 4. ion-exchange requires more precise and careful procedure.22 17.24 0. A summary of these comparisons are represented in table 1 below.83 7.4|Likhtshteyn methods. drying and weighing of the crucibles with precipitate.06 5.34 Comparable Gravimetric Analysis Less Accurate Three lab sessions Trivial procedure $600. 500mL filter flask w/o side arm.00 17.5116g 1 25g 6g 1g 4 1 1 Cost ($) 126. With regards to cost of waste disposal.52 5. due to the cost of the hot plate.2 L 2 1 1 2 1 1 1 2 1 Cost ($) 5.00 3. the resin must be compressed in order to obtain the desired flow of the sample through the resin.00 16. 500mL vacuum collar 2-hole rubber stopper Total Quantity . insertion of the kim wipe for filtration. Ion-exchange requires careful handling of the resin.55 290.65mL . gravimetric analysis requires the trivial rinsing. On the other hand.32 12.

HPIC is a quick method with increased sensitivity and the ability to analyze for multiple ions simultaneously. The errors associated with ion-exchange are corrected in the HPIC data provided. or ammonium groups in the case of anion analysis. The chloride content in water for Evidence D was 0. The column is packed with beads that are derivatized with sulfonic acid. therefore more time was spent on analysis of unknowns. incorrect flow rate.5|Likhtshteyn In addition to using ion exchange for analysis of the unknown. Only one trial of the water analysis was run because the water evidence wasn’t evaluated for accuracy. an assumption made was that chloride was the only anion in the water sample. and titration errors are all applicable to the water sample. Different ions have differing affinities for the resin and the mobile phase which results in separation of the sample. Another method introduced in this experiment was HPIC which functions similarly to the ionexchange chromatography previously described. Separation of the sample takes place in the column if more than one anion is present in the sample. and is pumped through under pressure past the injector and into the column. The mobile phase is in a reservoir that is attached to the pump. The water sample was titrated with 0. but the unknown sample was. as with the unknown. Therefore.0100 M HCl using phenolphthalein indicator. this corrected for any base that may have been present in the water sample.078mg/mL. The water sample was applied to the column. Incorrect packing of the column. which was followed by the addition of purified water. The ion-exchange method for the evidence is comparable to that of the unknown explained earlier. the pH of the eluate was tested until it reached 6. carboxylic acid groups. 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 sources of error associated with the water sample are comparable to those previously discussed for the unknown. A blank titration was run prior to using the column. For the ion-exchange analysis of water. or any base present in the flask residue. This pertains to a flaw in the ion-exchange method for the water sample. it can only detect one anion at once. neither precision nor accuracy can be discussed without HPIC data. The sensor monitors the resistance between the two electrodes in the detector and produces a signal that is directly . All the samples in this experiment contained chloride and some also contained concentrations of nitrate. the method was also used to determine the average mg of chloride /mL water of Evidence sample D. The water sample is injected into a stream of the mobile phase and solvent is pumped through the column.

The presence of nitrate. comparable .008150 mg/mL of nitrate in the sample. it can be noted that ions elute differently depending on the charge and ionic radius. the chloride ion will elute first.000 (per unit) Hazardous Waste. This detection is temperature sensitive and therefore the column is contained in a temperature constant heater. a lot of errors associated $290. Table 4: Ion Exchange Chromatography vs HPIC Element of Comparison Accuracy Ion-Exchange Chromatography Less accurate and sensitive. a total of . Comparing this to the experimental data from ion-exchange analysis (. one anion HPIC More Accurate and sensitive. in addition to chloride. The HPIC data was provided to the class via blackboard. Moreover. HPIC data yielded .6|Likhtshteyn related to concentration. retention time is the time taken for a particular compound to travel from the column to the detector. nullifies the accuracy of the assumption made for water sample D for the ion-exchange method. After analyzing the HPIC data provided for sample D. it was determined that both chloride and nitrates are contained in the sample. multiple anions Time Required Expertise of method Cost of Chemicals & Equipment Waste Disposal One lab session (4 hours) Careful procedure. A small difference between the two methods suggests that there is a high level of accuracy in the obtained experimental results. followed by the nitrate ion.34 Hazardous Waste. A conductivity detector was used for the HPIC data in this experiment. The retention time is provided with each signal. proposes a difference of . A table summarizing the similarities and differences is presented below. The time depends on the differing affinities that ions have for the resin and the mobile phase. the mg/mL obtained in the experiment for evidence D is a sum of the nitrate and chloride mg/mL. which makes sense based on the characteristics of the respective anions and their affinities. Therefore. Due to the molecular size. In looking at the retention time of the standards provided for the nitrate and chloride sample. two peaks are present on the HPIC data.07985 mg/mL of chloride and . the relative order of the retention times increase as the concentrations for both chloride and nitrate are increased. comparable One lab session (1 hour) Use of instrument properly $17. and the respective samples were analyzed.088 mg/mL of chloride and nitrate together.078 mg/mL).01 mg/mL.

HPIC is able to detect multiple anions simultaneously which corrects a flaw with the ion-exchange. and demonstrate that ion-exchange is quite accurate in determining chloride analysis. whereas manual ion-exchange calls for about 3-4 hours. therefore more accuracy is expected of such an instrument. The effectiveness and accuracy can be attributed to the stark difference in cost between the two methods. both methods use hazardous wastes that must then be disposed of in according to hazardous waste guidelines. Clearly.91ppm of sodium chloride and 99. Moreover.000 (Alibaba). careful and meticulous work in the ion-exchange process will lead to accurate results as demonstrated with the obtained data.16ppm 766.18ppm 11. An HPIC machine can cost around $17. Table 5: Concentrations of sodium chloride and sodium nitrate ion in samples A-E Sample Ppm of sodium chloride A B C D E 111.27x+6591. it is clear that ion-exchange chromatography is the more superior choice for chloride analysis. and the use of an automatic pump to push the solvent through the column in HPIC.430 y=759.068 Sample B contains 766.5 y=385.97x-57.23ppm of sodium nitrate. the water found on Henry’s clothing was from sample B salt-water . However. which is similar to the experimentally determined concentrations of Henry’s shirt.63ppm 9. To further verify this conclusion the HPIC results were compared to the ion-exchange results. This makes HPIC a more accurate and sensitive method for chloride detection. The HPIC instrument requires about an hour for an analysis of such samples.8 Ppm of sodium nitrate 91. for the evidence.91ppm 261.31ppm 131. the water removes from his clothing was determined experimentally to contain 800ppm of sodium chloride and 100ppm of sodium nitrate.21ppm 99.72ppm 1601.7|Likhtshteyn A difference concerning accuracy between the two methods is the use of gravity for the flow of mobile phase in ion exchange. Therefore. the HPIC method is superior to that of ionexchange. The table below summarizes the concentrations of each anion in samples A-E. However. With regards to Henry’s death. After comparing the ion-exchange chromatography to the gravimetric analysis.23ppm 40. of the unknown sample. With regards to waste disposal. the HPIC instrument does indeed provide a more sensitive and more accurate method for analysis when dealing with multiple anions simultaneously.

. 2. N .alibaba.8|Likhtshteyn aquarium found in his home. . Print. Fall 2011 247-266. <http://www. Work Cited 1." Laboratory I: Introduction to Chemical Analysis Lab Manual. instead he was most likely murdered in his own home. " A l i b a b a . d . p . W e b . "Experiment 4.com/showroom/ion c h r o m a t o g r a p h y. n . 1 Nov 2011. Henry was not dragged out to the ocean adjacent to his property. h t m l > . " 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 .

48/0.72   2 ..7  407:--078945507 %49.   ":.::2..4.399 489                                         .

.8 .07.88 41 90 :3343  90 2094/ .3..//943 94 :83 43 0.30 147 .84 :80/ 94 /0907230 90 .0 2 41 .   $     ¾    °  3 .47/0 .

843 347 .8 .907 41 .3.30 2094/ 147 90 0.550/9490.3-0/8..88 41 :33438  %0701470  30907 570.47/0.90/ 9     :83 503459..8 85039 43 .:7.  -:9 90 :3343 8.0/   %0 .9 41 90 :3343 05.0 8..//943415:710/.907147./03.03 3/.907 0. 41 90 . %0..943 .80 5708039 3 90 1.250 .0 .8 708/:0  %0 .-0 94 9.83 9 0./03.250   %0 43 0.:880/94:9!/.:7. .907 .4:23 .4770.3..9 2.0 8 .907 8.250  47 .8 9 90 :3343  3 430 97.0....425.3 997.88 .4:23  98 .:80 90 .8 7:3 5747 94 :83 90 .947  ..90/ 147 .../03.707    -.907 8.8  90701470 2470 920 .8 90890/ :39 9 70./03..8 7:3 -0.3 -..3 -..81440/-90.907 8.30/ 0.250 ..90/ 147 .250 .2  .:.7.90790541900:.0 -003 5708039 3 90 .80 9.90 .8 997.8 2.4390393.9.

7-4./0.943.. 1.9 ./0/  34907 2094/ 3974/:.9 .47/0 .5 570. .3.9147.0 390.90 479043 0./  .947 .947..4770.9 .9.9 8 /70.9.47/0 .343 .0397.94341908.4770.304:8  %0 24-0 5.. 8970.3/ 394 90 .-9 94 .2508 3 98 05072039 . 6:.9078.55.30.-0949480570.90 .88  1107039 438 .3/997..70.4:239035.3/ 90 24-0 5..3438 3 84:943 %0803847 2439478 90 70889.3/ 84.9 43.30 .9078. 9.89. 83. 2094/ 9 3..24:39 41 0.8841.3/ .3/85:250/974::3/0757088:705.90/390!/.7-0/  %0 .4:23  ! 8 .70807.907 8.30/ .479. 1:3..98.0  %0 84:7.884.70 /07.:880/14790:3343  3.90/990.8083..3.7041.:80/ -90.884./090.3430 .34190.3/ 574/:.343 ./8 9.943077478..4:8/8.7 9490 43 0.70.250 %00:039174290.9434190 8.3..039 8 5:250/ 974: 90 .250.113908 147 90 7083 . 6:.947. 3 90 43 0...0/ 3 98 05072039 .90/943 0.4:8 /08.8 90 43 .0/ 9 -0.90/ 394 .3/ 8420 ..8808974:.4:23 3..38 94 .80 .9 430 .343 - 708543/3 94 .-09490 .39108 90 .0 /11073 .3 43 /090.343857080393908..742.085..43.89 90 30.30/ .70.0/94905:25 .947 .250 $05.2509.3/ 90 .2 41 90 24-0 5.9 41 90 84:943 .88:259432.9438 82.99.0397.250  %8 5079. ./ 74:58  47 .574.80 41 .2   90 8.974/08 3 90 /090.30.425.439.80 .2243:2 74:58 3 90 .9438..0 -09003 90 94 00.8 ! .30 2094/ 147 90 .250 9 ..0 147 2:950 438 82:9.250 8 30.4770.7. 708:98 3 805..90/ 9 8:143.943841397.907 .907 8.3....7.08 41 07747 ..84 . .80/ 80389.70.4:23 8 5.343 3 90 .08 ..4:23 1 24709.250 %0077478.3.4:23  %0 .30 3 .9 .95.439.43/:.43.7. .907 8.3/.

/0/ 90.3.9078.8.79.47/0.302094/ %0701470 902.9:7080389..80  3 443 .947 .88:25943 2. 2..80/ .43.30/3.//943 94 .0 8.90789.30/3908.70.439. . 41 90 .90/94.9.7/  .908.0/  1907 .439.43/:.9.90  3 .4:238.70 .47/0.9438147-49.3/.902507..3/ 43.03147.2508 070 .3/ 90 70850.8 574.7.890. %0 570803.9 90 70903943920419089.7/8574.3/397./0/14790397.0174290.8 :80/ 147 90 ! /..0397.80.9.250   9 .9 438 ./:8  :0 9490 240.:..3438 .9.-4.0 47/07 41 90 7090394392083..47/0  3:108 90 .80/ 43 90 .3-03490/9.9.9..907  %0 ! /.4254:3/9497..8 /0907230/ 9.5.70..4:239490/090.08 80380 -.9..390.9 438 0:90 /1107039 /0503/3 43 90 .90 43  4704.0 147 90 7083 .9:70.0397.07  90 70.3.70903943920 890 9209..3/397.0 41 397.:7.3/ 907 .3/9070147090.9.90./0/ 94 90 .703.2509450.8 41 90 70850.3/.70.9 /090. 7.7 80  90 .2501479043 0.0 .113908 9.88 .0.7057080394390!/.3/ 90 24-0 5.9 -49 ..4389.113908   .83./0/ 147 8.:..943 %070903943920 8574..3 90 ! /.943 8 902507. 574.90. -./0 147 . 3 98 05072039  %8 /090.47/0 43  0:90 1789  1440/ - 90 397.250 9.43.47/08.   $     ¾    °  70.947 %0920/0503/8 43 90 /11073 .7.

8:24190397.08.3/.90./03.47/02.24-9.30/39005072039 1470.

9.0/0/ 2.2 !/.

3/   2.241 .47/0 .

 949. 41  2.90 3 90 8.250  .2 41 397.

30 .3/ 397. /.2 41 .47/0 .88  2.90 940907  425.73 98 94 90 05072039..3.9. 1742 43 0.

0 41  2.2  57454808 . /110703.

30742.30742...947..8 6:52039 .  0.3438 %20#06:70/ 507980412094/ 4894102.3//110703.343 ! 470.. 708:98   9...-0 30.:7.2   82. 3 90 4-9.947.. 30.425.739082.-0  .-0 8:22.7/4:8..-043..30/ 05072039.4941077478.0  2:950.8! 0203941425.0/:70 .890 .-808843 4:78  .884.0 -09003 90 94 2094/8 8:0898 9.8908548.08857080390/-04  %.5 088.90.3/80389.0 41 .890 .90/   .:7.-808843 4:7  &80413897:2039574507   507:39  .5.7.425.90.7/4:8.:7.. 43 ..701:574..3/80389.7843 ..0 430.7908. /110703..7.9 9070 8 .:7.

88 4190:3343 8.493 .90.3..904338.3 4:7 147 .304:8 970.90  %0 9.3.7/894 037 8 /0..30  40..90 3 /0907233 .425.3.439.89089.9438410.8 /0907230/ 05072039.7 9.304:8.9 .07 !8.30 8 6:90 .:7.47/3 94 .88 %41:7907.:84390!708:98070.:7.30 .9  90 .0397.7  90 ! 2094/ 8 8:50747 94 9.3/90:8041.98./0907230/ .07198..890/8548.8147.30.  1907.7/110703.7/4:8..30 .:7.:7.90  552  552  552  552        $.47/0/090.3/80389..343882:9.79490 05072039.742..07 90!3897:2039/4083/00/574.947.02094/147..997-:90/949089.3/.. 94 ..489-09003 9094 2094/8 3 ! 2. 8.3.943841037 8879  %0701470 90.74:3/   -.:7..3.088  0.90/ 41 8:..739043 0.88 41 8:.8803/0.3...30 708:98  147 90 0.0733.8/0243897.7/4:8 .90 9.250. 8 050.742..4.0.08 1742 8 .08!.34338..3/84/:2397.2508  $.907 . -49 2094/8:80 .82..4:233! %82.43.943  4704.425..3 .30//..43.2508.70/949043 0.489 .:942.493.890 :/0308  0.4770.-.  90701470 2470 .-0900390942094/8890:80417.30..0.2508  070...817428.-043..30 574. .-0 -04 8:22.   $     ¾    °  /110703.039974:90 .07  .3/  552 41 84/:2 397.-4:9 4:78 %00110.0  ./03.701: .803430.439.92:950..3/ 209.47/0 .5:25945:89084.90 .47/0 .250 !524184/:2....594907.30 .-094/090...:4:8 47 3 90 43 0.882..5 8 90 2470 8:50747 .90/9904-9..92:89903 -0/85480/41 3 .38 55241 84/:2.:7.947.3/ 55241 84/:2397.2470.9..9.3 3897:2039  9 70.30  %0 ! 3897:2039 706:708 .9.907 7024.47/0.0.0 147 .247080389.9 43 0.9 43 0.90708:98./ 94 .1.708 90 .7/894.3:.88 40..3/ /0243897.0397..43.9147901441 24-05.0 3. 43 0.3/2470 .9 41 43 0..3.0397....902094/147.43.990 43 0.47/0.47/0        552  552  552  552        !524184/:2397..3  552 41 84/:2 .392:950.3-0 .03088.90714:3/43037 8 .:7../0..-4:9 .2508   %.47/0..250  9 8 .2097.343882:9.94384184/:2.

5    .0399485745079  3890.88. 9 4  7 .   $     ¾    °  . 3: 1 .   5  3 /   0 -     4 ..0.. .9439402./.7:214:3/38420 037.8248902:7/070/3843420      4790/   5072039 .3:.3.0/4:994904.6:..3.8349/7. 9 : 7 0 7 8      ..    !739      4 3   7 4 2. .      9 9 5  ./0.9473974/:.-.-47. .

.

. .    .   .. . 4 2.

8  4  7 4 4 2.

9 4  7 .  4 3 .  7 4 2. 5   9 2      .

Sign up to vote on this title
UsefulNot useful