Introduction Cations that are mixed in an aqueous solution can be separated by selective precipitation.

It is done by adding reagents which contains the anions required to precipitate one or more cations in the mixture (Zumdahl, 2010). Selective precipitation is ensured when the Qsp value of the more soluble compound is almost equal to its Ksp. It also makes certain that the Ksp value of the less soluble compound is outdone (Silberberg, 2006). Ions in a mixture can be identified by qualitative analysis. The analysis requires the cations to be separated in five major groups: 1. Insoluble chlorides; 2. Acid-insoluble sulfides; 3. Base-insoluble sulfides and hydroxides; 4. Insoluble phosphates; and 5. Alkali metal and ammonium ions. Different schemes are devised to separate this ion groups such as flame test and precipitation reaction. There are several types of reactions that are used in qualitative analysis. Acid-base reactions is one of the most popular in the quantitative analysis. Acid, as defined by Bronsted and Lowry, is a proton donor while the base is an proton acceptor. When the ion product (Qsp) is greater than the solubility product principle (Ksp) precipitate is formed and this is called as precipitation reaction. This kind of reaction also is widely used in qualitative analysis. Addition to that, oxidation-reduction reactions and disproportionation (auto ionization) reactions are considered during a separation of ions. Formation of complex ions are also favored in qualitative analysis. Complex ions are formed when a central metal cation is bonded to form two up to six lone pairs of electrons on surrounding ligands. Ligands are the molecules that can donate one or more lone pairs of electrons. The objectives of this exercise were: The experiments were performed in the Room 105 Wing B of the Institute of Chemistry in the University of The Philippines Los Banos on February 22, 2012.

Materials Reagents Concentrated HNO3 6M HCl 6M NH3 Acetic acid K4fe(CN)6 1% dimethylgyoxime (DMG) 6M CH3COOH Solid Na2S2O3 Na2HPO4 6M NaOH 0.2M Na2S Apparatus Hot plate Stirring rod Dropper Centrifuge tubes centrifuge Iitmus paper watch glass evaporating dish hot water bath Pasteur pipe

Procedure For the determination of the presence of group d cations, a solution contining the cations was gathered by the group and label it as cd1. 6M NH3 was added to the solution until neutral then it was made slightly acidic by adding 2 drops of of 6M acetic acid. Also, 4 drops of K4Fe(CN)6 were added to the solution. Another drop of CD1 was obtained and again, 6M NH3 was added to it. 1% Dimethylglyoxime was added also in the solution. The results were then recorded. 6M NH3 was added to the remainder of cd1 until neutral and 2 drops of 6M CH3COOH was added to the solution also to make it slightly acidic. Then, 0.3 grams of Na2S2O3 was added. The solution was heated for 10 minutes in a hot water bath. The tube was then cooled and centrifuged. For the centrifugate of the remainder of CD1, 6M NH3 was added to the solution until basic. 8 drops of 0.1M Na2HPO4 was added to the tube and it was allowed to stand for few minutes. After standing, the tube was centrifuged. For the precipitate of the remainder of CD1, 50 drops of 6M NaOH was added then the solution was stirred and centrifuged. Then, the supernatant was complete decanted in a tube. 6M acetic acid was added to the centrifugate until it was slightly acidic then, 4 drops 0.1m of k4f3(cn)6 was also added. The precipitate was washed twice with distilled water. 6 drops of 6M HCl was then added and the solution was stirred and centrifuged. The supernatant was quickly decanted in a tube. The precipitate was discarded. 6 drops of the centrifugate was obtained and each three drops was put in separate tubes. 6M NH3 was added to each of the tubes until it was neutral. 2 drops of 6M acetic acid was added to one of the tubes to make the solution slightly acidic and then, five drops of 0.1M k4fe(cn)6 wad also added. While on the other tube, five drops of 0.2M Na2S was added. The reaction was observed and recorded. Data Results and Discussion For the determination of the group D cations, ammonia and oxalate from the previous analyses must be removed by heating the solution to dryness. The ammonium ions were present and the following reaction occur:

The oxalate present in the sample decomposed and it produced co2 gas. The chemical reaction was: It is important to remove the traces of ammonia and oxalate in the solution for it could interfere in the determination of the group d cations. Concentrated hno3 was added and was heated to dryness. The addition of nitric acid produced the oxides of the cations and stayed solid in the solution. The reactions were represented by the chemical equations:

6M HCl was added to dissolve the oxides. This was done to liberate the group d cations that were dissolved in an aqueous solution. (equation) The solution was now tested for the presence of Cu2+, Ni2+, Mg2+, Zn2+ and Cd2+. In CD1a, for the confirmation of the presence of cu2+, the test solution was made neutral by nh3 and slightly acidic by the addition of ch3cooh. Hexacyanoferrate was then added. The resulting precipitate and supernatant liquid was maroon in color. The purpose of adding ch3cooh was for the test solution to be made slightly acidic to prevent the formation of hydrogen cyanide. This poisonous gas was produced when the hexacyanoferrate was added in a strongly acidic solution. The addition of hexacyanoferrate in the solution formed a precipitate for it reacted to copper to form copper hexacyanoferrate which was maroon in color as its distinct appearance. The reaction was represented by: As shown in cd1b, nh3 and 1% dmg was added to the test solution. It produced a cherry red solution that confirmed the presence of ni2+ ions. The solution was made slightly basic in order the precipitate formed. The dmg must be deprotonated before it reacts with Ni2+ ion. The deprotonating of dmg with ammonia was shown in the equation: The deprotonated dmg reacted with the free ni2+ ions and produced nickel dimethylglyoxime complex, which was characterized by a cherry red precipitate. The Ni2+ ions form a highly colored precipitate with dimethylgloxime ions only. The reaction was as followed: In the remainder of Cd1, as shown in the table, nh3, ch3cooh and na2so3 were added in the solution and heat was applied. The reaction produced a black precipitate. The test solution was made slightly acidic by the addition of ch3cooh. The separation of group d cations was needed to confirm the presence of mg2+. This was done by precipitating the zn, cu, ni and cd as sulfides. The sulfide ions were provided by sodium thiosulfate. By the application of heat and the slightly acidic solution, sodium thiosulfate dissociated. The net ionic disproportionation reaction was shown: The free sulfide ions reacted with the cations. The chemical equations and the characteristic colors were shown below: The zn, cu, ni and cd sulfides were insoluble while the magnesium ions did not formed a sulfide, thus the magnesium ion remained in the solution and did not precipitate. The color of the precipitate of the zn and cd were masked by the blackness of the precipitate of ni and cu. For the further confirmation of the presence of mg2+ cations, as shown in the table (CD2), nh3 and na2hpo4 was added to the solution. The solution was made slightly basic with aqueous ammonia. The reaction involved was: The ammonium ions and hydrogen phosphate ions reacted with the magnesium ions in the solution. It was shown in the equation: The product formed, mg nh4po4, which was characterized by the white precipitate confirmed the presence of mg2+ in the test solution. The supernatant was blue because of the unreacted cu, zn, ni and cd cations.

In table 1.1, in the portion of pd1, naoh was added in the solution. The product formed was from the reaction of hydroxide ions with the zinc sulfide in the solution. This was done to liberate the zinc ions in the form of tetrahydroxozincate complex. The reaction was shown: In cd3, 12M HCl and k4fe(cn)6 was added. White precipitate was observed after the addition. The addition of acid liberates the zinc2+ from its hydroxide (tetrahydroxozincate complex in pd1). The reaction was shown below: For the confirmation of the presences of zinc2+ in the solution k4fe(cn|)6 was used. After the addition of k4fe(cn)6, zn2fe(cn)6 was formed and it was characterized as white precipitate. (equation) After the confirmation of zinc2+, in pd2, 6m hcl was added. Dissolution of some precipitate had taken place while some black precipitate remained. The addition of acid liberated mostly the cadmium ions from its sulfide while the nis and cus remained insoluble in their sulfides. The reaction of cadmium ions with the acid was represented in the equation: For the confirmation of cadmium ions in the solution, two ways was used. Nh3, ch3cooh and k4fe(cn)6 was added to the tube with three drops of cd4. A pink precipitate was observed. Nh3 and 0.2M Na2s were added to other tube with three drops of cd4. No precipitate was observed. The first way to confirm the presence of the cadmium ions, k3fe(cn)6 was used as an indicator. Cd2fe(cn)6 was the product of the reaction of cd2+ ions and k4fe(cn)6 and was characterized by white precipitate. (equation) However, the desired color of the precipitate was not obtained. Instead, it produced a pink precipitate. The result of the experiment was attributed in some errors. One possible explanation was that the cu2+ ions were not completely eliminated before the test for the presence of cd2+ ions. The presence of cu2+ produced pink precipitate that was manifested in the experiment. The second pattern to confirm the presence of cadmium ions in the solution was by adding nh3 and na2s. cds was the product of the reaction of cd2+ ions and na2s and was seen as yellow precipitate: (equation) Yet, the desired yellow precipitate was not seen. By the addition of na2s, no precipitate was formed. The errors in the experiment may be attributed in the absence or insufficiency of cadmium ions present in the solution. If the ions were really absent or insufficient, precipitation would not be observed. The zinc and cadmium ions formed both white precipitates when reacting with k4fe(cn)6. The precipitate can be determined if it is zinc or cadmium ions by means of sulfide precipitation. Zinc ions will not form any colored precipitate with sulfide ions while cadmium will react to sulfides forming CdS, which is a yellow precipitate. Acid was dropped on the the zinc ions and cadmiums ions in the test solution before adding k4fe(cn)6. This is done to favored the reaction that favors the formation of the confirmatory compounds of zinc and cadmium, cd2fe(cn)6 and zn2fe(cn)6. (equations)

The less favorable reaction by the addition of acid was the formation of the toxic gas, HCN. (equation) Conclusion For the confirmation of the presence of group d cations namely: , reagents that contains the anions needed to precipitate the cations were obtained. Results showed that the formation of maroon precipitate after adding k4fe(cn) to the test solution confirmed the presence of copper ions. Also, the presence of nickel ion was established upon addition of dimethylgyoxime and cherry red precipitate was formed. Addition of sodium hydrogen phosphate confirmed the presence of magnesium ions by forming a white precipitate while the addition of k4fe(cn)6 confirmed the presence of zinc ions by forming also, a white precipitate. For the verification of cadmium presence in the test solution, two ways of precipitation were observed. A portion of the test solution was subjected in k4fe9cn)6 and a pink precipitate was produced. In the other portion of the solution, na2s was added but no precipitate was formed. The results were invalid, thus errors in the experiment were considered. In the experiment on the quantitative analysis of group d cations, it can be established that the ph of the solution was crucial in seperating the cations. The solution must be acidic to liberate most of the ions that were in a compound and also to prevent the evolution of toxic gases. However, some solution must be basic in order to deprotonate some reagents thus permitting the occurrence of confirmatory reactions. Moreover, the different principles in separation of the cations were very important. The formation of a specific complex ion gave characteristic color thus increasing the possibility of accurate confirmation of ions. Oxidation-reduction reactions were also needed to reduced or oxidized some ions in order to react with other reagents. It was concluded that understanding the effect of the ph and principles of separation of ions were essential in quantitative analysis. For further study, it was recommended to use other reagents for the precipitation reactions. It was also recommended that the ph of the test solution should be monitored for the results not to be flawed.