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QUALITATIVE ANALYSIS OF GROUP D (Hydroxides and Oxalates Soluble in Ammonia but Insoluble in Sodium Hydroxide)

I.

Introduction
Precipitation reactions happen throughout our lives even without noticing it and they are considerably important in different fields. The preparation of sodium bicarbonate is made through precipitation reactions. The deterioration of the tooth enamel which can lead to tooth decay, the production of barium sulphate to diagnose digestive tract disorders are also governed by precipitation reactions (Chang, 2010). According to Chang (2010), the solubility product constant or Ksp is the product of the molar concentrations of the constituent ions, each raised to the power of its stoichiometric coefficient in the equilibrium equation. Ksp follows the general equation n+ x m- y Ksp = [A ] [B ] The solubility quotient or ion product Q determines if precipitate would form and is of the equation n+ x m- y Q = [A ] o [B ] o According to Atkins & Beran (1992), just as the reaction quotient was used to determine the shift of the equilibrium, the comparison of the Q and Ksp determines if a precipitate will form. If Q>Ksp, there are excess ions which makes the solution supersaturated and precipitation will occur. If Q=Ksp, the solution would be saturated and in equilibrium thus no precipitation will occur. If Q<Ksp, the solution has very few ions making it unsaturated and no precipitation will occur. An application of the solubility product constant would be the qualitative analysis which involves simply identifying the presence or absence of cations and anions in a given solution (Brown & Lemay, 1985).

After the separation of the first four groups of cations, the Group D cations, will be precipitated and be separately identified. This group of cations include Cu2+, Mg2+, Ni2+, Zn2+, and Cd2+. II. Materials A. Reagents CC1 (Cations of Groups D-E from Group C Analysis) Concentrated HNO3

6M HCl 6M NH3 0.1M K4Fe (CN) 6 1% dimethylglyoxime (DMG) 6M CH3COOH Solid Na2S2O3 0.1M Na2HPO4 6M NaOH 0.2M Na2S Distilled water B. Apparatus and Equipment Centrifuge Tubes Test Tubes Centrifuge Hot plate Water bath Ice Stirring Rod Watch Glass Red and Blue Litmus Paper Pasteur pipets III. Procedure Ten drops of CC1 from the analysis of the Group C cations have been obtained and was heated to dryness over low heat. It was cooled then 6 drops of concentrated HNO3 was added then it was heated to dryness again. After cooling, 5 drops of 6M HCl was added to dissolve the residue formed. The solution was transferred quantitatively to a centrifuge tube using distilled water and was labelled as CD1.

One drop of CD1 was used to test the presence of the Cu2+ ion. The pH of the solution was determined using litmus paper. 6M NH3 was added until the solution became neutral. Two drops of 6M acetic acid was added to make the solution slightly acidic. Three to four drops of 0.1M K4Fe (CN) 6 was added to confirm the presence of the Cu2+ ion. The presence of the Cu2+ ion was confirmed upon formation of cupric hexacyanoferrate (II) which is a maroon precipitate. One drop of CD1 was used to test the presence of theNi2+ ion. The pH of the solution was determined using litmus paper. 6M NH3 was added until the solution became basic. 10-15 drops of the confirmatory reagent 1% dimethylglyoxime was added. Upon addition of DMG, the formation of a cherry red-nickel dimethylglyoxime was observed which confirms the identity of Ni2+ ion. The remainder portion of CD1 was used to test the remaining Group D ions including Mg2+, Zn2+, and Cd2+. 6M NH3 was added to make the solution neutral then 2 drops of 6M CH3COOH was added to make it slightly acidic. A crystal (about 0.2-0.3 g) of solid Na2S2O3 was added afterwards. The solution was heated it a boiling water bath for 10 minutes and was cooled afterwards in an ice-

water bath. It was then centrifuged and decanted. The precipitate was labelled as PD1 and the centrifugate was labelled as CD2. CD2 was used to determine the presence of the Mg2+ ion. 6M NH3 was added to make it basic and six to eight drops of 0.1M Na2HPO4 was added. It was left to stand for several minutes and centrifugation followed shortly. The presence of a white precipitate of magnesium ammonium phosphate confirms the presence of the Mg2+ ion upon addition of sodium hydrogen phosphate. 50 drops of 6M NaOH was added to PD1 using a Pasteur pipet. It was stirred, centrifuged, and decanted afterwards. The centrifugate was labelled as CD3 and the precipitate was labelled as PD2. CD3 was used to determine the presence of the Zn2+ ion in the solution. 6M acetic acid was added to the solution until it became slightly acidic. Four drops of the confirmatory agent 0.1 M K4Fe(CN)6 was added under the fumehood. The presence of a white precipitate of Zn2Fe(CN)6 upon addition of potassium hexacyanoferrate (II) confirms the presence of the Zn2+ ion. PD2 was washed twice with 10 drops of distilled water. Six drops of 6M HCl was added to the solution and was stirred and centrifuged. Upon decantation, the centrifugate was labelled as CD4 and the precipitate was labelled as PD4 but was discarded. CD4 was used to test the presence of the Cd2+ ion. Two centrifuge tubes each containing three drops of CD4 was used. In the first centrifuge tube, 6M NH3 was added until the solution became neutral. Two drops of 6M acetic acid was added to make the solution slightly acidic. Five drops of the confirmatory reagent potassium hexacyanoferrate (II) was added and led to the formation of a white precipitate of Cd2Fe(CN)6 which confirms the presence of the Cd2+ ion. In the second centrifuge tube, 6M NH3 was added to make the solution neutral. Five drops of the confirmatory reagent 0.2M Na2S was added to further confirm the presence of the Cd2+ ion. The presence of the Cd2+ ion can be confirmed upon formation of a yellow precipitate of CdS. IV. V. Data/Observations Discussion

Precipitation reactions happen throughout our lives even without noticing it and they are considerably important in different fields. The preparation of sodium bicarbonate is made through precipitation reactions. The deterioration of the tooth enamel which can lead to tooth decay, the production of barium sulphate to diagnose digestive tract disorders are also governed by precipitation reactions (Chang, 2010). According to Chang (2010), the solubility product constant or Ksp is the product of the molar concentrations of the constituent ions, each raised to the power of its stoichiometric coefficient in the equilibrium equation. Ksp follows the general equation n+ x m- y Ksp = [A ] [B ] The solubility quotient or ion product Q determines if precipitate would form and is of the equation n+ x m- y Q = [A ] o [B ] o

According to Atkins & Beran (1992), just as the reaction quotient was used to determine the shift of the equilibrium, the comparison of the Q and Ksp determines if a precipitate will form. If Q>Ksp, there are excess ions which makes the solution supersaturated and precipitation will occur. If Q=Ksp, the solution would be saturated and in equilibrium thus no precipitation will occur. If Q<Ksp, the solution has very few ions making it unsaturated and no precipitation will occur. An application of the solubility product constant would be the qualitative analysis which involves simply identifying the presence or absence of cations and anions in a given solution (Brown & Lemay, 1985).

There are 20 common cations that can be readily analysed in an aqueous solution using qualitative analysis. These cations are separated into 5 groups; from Group A to Group E (Chang, 2010). Group A cations include the ions Ag+, Hg22+, and Pb2+. Upon addition of HCl in a solution containing the common cations, these three will be selectively precipitated out as insoluble chlorides. Group B cations include the ions Bi3+, Fe3+, Cr3+ and Mn2+. These cations will be selectively precipitated out as hydroxides insoluble in ammonium hydroxide upon addition of NH3. Group C cations include Ba2+, Ca2+, Co2+, and Sr2+ ions. They will readily precipitate out as oxalates insoluble in ammonium hydroxide upon addition of ammonium oxalate. Group D cations include Cu2+, Mg2+, Ni2+, Zn2+, and Cd2+ ions. These cations will precipitate out as hydroxides and oxides soluble in ammonia but insoluble in sodium hydroxide upon addition of HNO3 and HCl. The remaining ions Na+, K+, and NH4+ are known as the soluble cations which are either determined using flame test or litmus paper test. (Brown & Lemay, 1985). The experiment focused on the determination of the ions which form hydroxides and oxides which are soluble in ammonia but insoluble in sodium hydroxide also known as the Group D cations. The addition of ammonium oxalate in the determination of the Group C cations led to the formation of ammonia complexes. Applying heat and addition of HNO3 simultaneously decomposes NH3 and C2O42- to CO2 and N2O. The Group D cations will be in the oxide form by then. HCl was used to dissolve the Group D oxides (including the Group E cations). Ni2+ can be readily confirmed by making drops of the solution basic and upon addition of 1% dimethylglyoxime, a cherry red precipitate of Ni(DMG)2 will form. Nickel is the only cation that can form a colored precipitate upon addition of DMG. The reactions upon determination of Ni2+ are as follows: Ni(H2O)62+(aq) + 6NH3 (aq) (double headed arrow) Ni(NH3)62+ (aq) + 6H2O (l) Ni (NH3)62+ (aq) + 2DMG (double headed arrow) Ni(DMG)2 (s) + 6NH3 (aq) Cu2+ can be readily confirmed by making drops of the solution neutral then acidic to prevent the formation of the toxic gas HCN. Upon addition of potassium hexacyanoferrate (II), the formation of Cu2Fe(CN)6 which is a maroon precipitate and confirms the presence of the Cu2+ ion. Even with the presence of other ions such as Zn2+ and Cd2+ that will precipitate with Fe(CN)6, the presence of the Cu2+ ion can still be confirmed because the formation of the maroon precipitate will mask the other colors. The absence of Cu2+ may lead to an observation of a white, yellow or pale green precipitate. The reaction upon determination of Cu2+ would be:

2Cu(NH3)42+ (aq) + 4H3O+ (aq) + Fe(CN)64- (aq) (double headed arrow) Cu2Fe(CN)6 (s) + 4NH4+ (aq) + 4H2O (l) The remainder of the solution was made neutral then slightly acidic by using acetic acid. Solid thiosulfate salt is added to generate sulfide ions by the disproportionation reaction: S2O32- (aq) + 3H2O (aq) (double headed arrow) S2- (aq) + SO42- (aq) + 2H3O+ (aq) The presence of the Mg2+ ions can be confirmed upon addition of Na2HPO4 to produce MgNH4PO4 which is a white precipitate. The blue supernatant can be explained due to the presence of unreacted Cd2+, Zn2+, and Cu2+ which forms complex ion formation with NH3. The reactions upon determination of Mg2+ are as follows: H3O+ (aq) + NH3 (aq) (double headed arrow) NH4+ (aq) + H2O (l) Mg2+ (aq) + NH4+ (aq) +HPO42- (aq) + OH- (aq) (double headed arrow) MgNH4PO4 (s) + H2O (l) Sodium hydroxide separates Zn2+ ions through complex ion formation: ZnS (s) + 4OH- (aq) (double headed arrow) Zn(OH)4- (aq) + S2- (aq) K4Fe(CN)6 reacts with Zn2+ to form a white Zn2Fe(CN)6 precipitate: 2Zn2+ (aq) + Fe(CN)6 4- (aq) (double headed arrow) Zn2Fe(CN)6 (s) The remaining precipitate was dissolved in an acidic medium, HCl to liberate mostly cadmium ions. The formation of black precipitates NiS and CuS are neglected and were discarded: CdS (aq) + 2H3O+ (aq) (double headed arrow) Cd2+ (aq) + H2S (g) + 2H2O (l) There are two ways to confirm the presence of Cd2+ ions. Addition of sodium sulfide forms a yellow precipitate CdS or a white precipitate will form upon addition of potassium hexacyanoferrate (II): Cd2+ (aq) + S2- (aq) (double headed arrow) CdS (s) Cd2+ (aq) + Fe(CN)64- (aq) (double headed arrow) Cd2Fe(CN)6 (s) There are several factors that can affect the separation of ions namely pH, oxidizing agents, Lewis bases and formation constants of complex ions. In the experiment, however, the effect of pH is dominantly favored. Since the solubility equilibrium involves OH- ions, the addition of hydroxide ions to the solution will decrease the solubility if the hydroxide-forming ion. Upon addition of an acid, the generation of H3o+ ions decreases the number of OH- ions which means a shift of the equilibrium to the right increasing the solubility of the hydroxide-forming ion (Atkins & Beran, 1992). VI. Conclusion The Group D cations readily precipitate out as hydroxides and oxides soluble in ammonia but insoluble in sodium hydroxide upon addition of HNO3 and HCl. The addition of basic solutions decreases the solubility of the hydroxide forms of the Group D cations while the addition of acidic solutions increases the solubility of the hydroxide forms of the Group D cations. Literature Cited/Bibliography

VII.

Chang, R. 2010. CHEMISTRY 10th Edition. New York, NY: McGraw-Hill Companies. p.735, 754. Atkins, P.W. & Beran, J.A. 1992. GENERAL CHEMISTRY 2nd Edition. USA: Scientific American Books p. 600, 605-609. Brown, T.L. & Lemay, Jr. H.E. 1985. CHEMISTRY: THE CENTRAL SCIENCE 3rd Edition. USA: Prentice Hall, Inc. p. 532-533.