CHEM 122L General Chemistry Laboratory Revision 3.


A Qualitative Analysis for Select Cations
• • • • • To learn about how to Develope of a Qualitative Analysis Scheme. To learn about Separation of Cations in an Aqueous Solution. To learn about Precipitation Equilibria. To learn about Complex Ion Formation. To learn about Flame Tests for Cations.

In this laboratory exercise we will separate and identify Cations dissolved in an Aqueous system. Since we will not quantify the amount of each Cation present, but instead merely discern its presence, such a scheme for separation and identification is referred to as a Qualitative Analysis. In our particular case, we will be testing for the presence of the following nine Cations: Ag+, Pb2+, Cu2+, Bi3+, Fe3+, Mn2+, Ni2+, Ba2+, Na+ Although this style of “wet chemical” analysis is no longer commonly used to determine the presence of these Cations, the development of this type of Qual scheme has many other applications in chemistry. Additionally, this exercise is useful as a study of Aqueous equilibria involving precipitates and complexes, each of which do have important applications in chemistry. Our general approach to separating these Cations is to Group them according to the types of precipitates they form: Chlorides (Cl-), Sulfides (S2-), Hydroxides (OH-), etc. We will proceed by selectively precipitating the Cations in each Group. Once a Group of Cations is precipitated, the Cations will be further separated using techniques specific to that Group. Once each Cation is separated from the others, a confirmatory test will be used to, as the name implies, confirm the Cation is actually present. These confirmatory tests are typically Cation specific and run the gamut from the formation of brightly colored complexes to producing distinctly colored flames in a Bunsen burner. Let’s consider an example. Suppose we are testing an Aqueous sample for the presence of Pb2+, Hg22+ and Ca2+ ions. (Somehow we know no other Cations are present.) We can start to develop a Qual scheme by testing separate samples of each Cation for precipitation with Chloride (Cl-). If we do this, we note Chloride precipitates form from Pb2+ and Hg22+ solutions. Thus the Chloride Group, or Group 1, Cations include these two ions. We further note that heating each of these precipitates causes the PbCl2 to re-dissolve. This is because PbCl2 is reasonably soluble in Water at high temperatures, but Hg2Cl2 is not.

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Thus, we have the beginnings of a Qual scheme for this Cation system; a method for separating the these Cations in a mixture of these Cations. To the mixture of Cations, add HCl to precipitate the Chloride salts, centrifuge and decant off the supernatant. This separates the Hg22+ and Pb2+ ions from the Ca2+. Now, add Water to the precipitate and heat. Again, centrifuge and

if you think about it. resulting in a dark grey precipitate of HgNH2Cl and Hg. And. all we see is a clear liquid. Separation of all the Cations is now complete. how would we ever know the Ca2+ was present in our system above. The Pb2+ precipitates as a golden yellow solid characteristic of PbCrO4. When the atom relaxes. this is represented as: . The resulting color is then observed directly. Maybe the only Cation present was Hg22+. Ba gives off green light. it would be nice to know that white Chloride precipitate is actually Hg2Cl2 and not some other Chloride salt. The presence of Ca2+ must be confirmed by a Flame Test. we now have a fully developed Qual scheme for this system of Cations. With these confirmatory tests in hand. In Flow chart form. The presence of Hg22+ is confirmed by adding Aqueous Ammonia. And. Confirmatory tests are very Cation specific. The presence of Pb2+ can be confirmed by adding a little Potassium Chromate (K2CrO4). How do we know Pb2+ is actually present. Li purple and Ca bright orange. Afterall. a photon whose wavelength is dependent on the orbital energy spacing is emitted. Many metal cations give off brightly colored light when a few drops are added to a burner flame.Page |3 decant off the supernatant. This is because the outer valence electrons are kicked into higher orbitals by the energy of the flame. The last piece needed to complete this Qual scheme is to add confirmatory tests. or if only other Cations are present. that clear liquid that we claim contains Pb2+ is also just a clear liquid. Typically a Flame Test is performed by dipping a small loop of Nicrome Wire into the test solution and placing the drop that hangs on the wire in a Bunsen burner flame. They give a “positive” result when the desired Cation is present and a “negative” result if not.

How do we know a precipitate will form? Is selective precipitation an effective method of separating Cations? How might we re-solubilize our various precipitates so as to run confirmatory tests.1M by adding HCl. 4) A ppt will form (Eq.Page |4 This is the type of scheme you will develop for our list of 9 Cations. both at 0. 3) For our Mercurous Chloride (Hg2Cl2) example. suppose we have a solution containing Cu2+ and Fe2+. 1) To determine if a precipitate will form we calculate the Reaction Quotient.? In order to predict whether or not a precipitate will form. 2) Hg22+(aq) + 2 Cl-(aq) (Eq. suppose our mixture is brought to [Cl-] = 0. If: Q > Ksp and if: Q < Ksp A ppt will not form (Eq. we have: Hg2Cl2(aq) where: Ksp = [Hg22+] [Cl-]2 = 1 x 10-18 (Eq. For Hg22+ precipitating as a Chloride (Cl-) salt. this is written as a Solubility Equilibrium and the Equilibrium Constant is referred to as a Solubility Product. 10-3 > 1 x 10-18 and a precipitate will form. Further suppose the Hg22+ Cation is at 0.10)2 = 10-3 So. 5) (Eq. Typically. based on the experimental conditions and compare the result with the Ksp. The relevant equilibria are: Ksp = 1 x 10-36 Ksp = 2 x 10-19 CuS(s) FeS(s) Cu2+(aq) + S2-(aq) Fe2+(aq) + S2-(aq) (Eq. We have: Q = [Hg22+] [Cl-]2 = (0.999% of the Cu2+ without also precipitating the Fe2+. Next.10) (0.1M. Ksp. Is it possible to bring the Sulfide (S2-) concentration high enough to precipitate 99.1M. Q. and one of unknown composition. we need to examine the equilibrium between the potential solid and its aqueous ions. to some of those pesky details. 6) . etc. Now. You will then use this scheme to test a solution of known composition. we desire to know if precipitation can be used to selectively precipitate one Cation and not another. For instance. for the Cations present.

For example. will remain.1) (10-30) = 10-31 Comparing this with the Ksp for FeS. selectively. we have a Sulfide Ion concentration of: Ksp = 1 x 10-36 = [Cu2+] [S2-] = (10-6) [S2-] or. using the Equilibrium Constant Expression. From the examples above. At this point. meaning 0.00001 x 0. For our system of 9 Cations. in an Ammonia (NH3) solution. Zinc Carbonate is an example of a precipitate that resolubilizes as the pH is lowered by adding Acid (H+) to the system: ZnCO3(aq) + 2 H+(aq) Zn2+(aq) + H2CO3(aq) (Eq. 8) (Eq. the complex ion is “formed” from the Cation (Ag+) and its ligands (NH3). 11) Another trick is to form complex ions of the Cation. Kf. and the Equilibrium Constant is a Formation Constant. precipitation using Sulfide Ion is an effective means of separating Cu2+ from Fe2+ in an aqueous system. 13) Ag+(aq) + 2 NH3(aq) The second of these reactions is referred to as a Formation Reaction. or 0.Page |5 First. we see: Q <<< Ksp (Eq. the Reaction Quotient. 12) (Eq. In other words.1M = 10-6M. no FeS will precipitate. Q. One method is to change the pH of the solution. 7) Thus. [S2-] = 10-30 M (Eq. A final concern is how to re-solubilize. salts that form co-precipitates.001%. These are: Group 1 Group 1 Cations precipitate as a Chloride. Ag+. 10) (Eq. for the FeS system under these conditions will equal: Q = [Fe2+] [S2-] = (0. we will selectively precipitate them in four Groups. 9) So. determine the Sulfide concentration needed to precipitate 99. forms an Ag(NH3)2+ complex: AgCl(s) Ag+(aq) + Cl-(aq) Ag(NH3)2+(aq) (Eq. we note Hg22+ (not a Cation in our system) is a Group 1 Cation: .999% of the Cu2+.

18) Other members of this Group precipitate as the Sulfide. another example not in our system. This is because the Basic environment causes the Hydrogen Sulfide equilibrium to shift toward the Right: H2S(aq) 2 H+(aq) + S2-(aq) (Eq. Thus. separate and confirm them. we will then examine methods for separating them and confirming their presence. we will proceed with the remaining Cations and categorize. we will proceed to the task of analyzing a mixture of these possible Cations of unknown composition.Page |6 Hg22+(aq) + 2 Cl-(aq) Group 2 Hg2Cl2(aq) (Eq.. Thus. a Qual Scheme for these Cations will be constructed. only very insoluble Sulfides will precipitate in this Group. Once this is determined. is a member of this Group: Cd2+(aq) + S2-(aq) CdS(s) (Eq. Cr3+ is an example: Cr3+(aq) + 3 OH-(aq) Cr(OH)3(s) (Eq. 2. Because Ammonia solutions are Basic (OH-): NH3(aq) + H2O NH4+(aq) + OH-(aq) (Eq.e. And. did not precipitate as a Group 2 Cation. 19) drastically increasing the Sulfide Ion (S2-) concentration. Having completed this task. Once this has been completed with the individual Cations.) to suddenly precipitate. 16) Group 3 These Cations precipitate in an Ammoniacal Solution. They will remain in solution even after performing the procedures to precipitate the Group 1. Group 4 These are Cations that do not precipitate. 14) Group 2 Cations do not precipitate as Chlorides but will precipitate upon treatment with Hydrogen Sulfide (H2S). 17) many of the Cations in this Group precipitate as Hydroxides. This causes Sulfides that are otherwise more soluble (i. . having done this. Hydrogen Sulfide dissociates as a weak acid: H2S(aq) 2 H+(aq) + S2-(aq) (Eq. Cd2+. we will initially treat all 9 of our Cations individually with the Group 1 precipitating reagent (HCl) to determine which are members of this Group. the equilibrium will shift left and the concentration of S2. and 3 Cations. 15) If the solution is already Acidic.will remain fairly low. In an aqueous environment.

the Sulfide Ion (S2-) is generated in an Acidic environment. when in Concentrated form: HCl. Week 2 1. Suppose it is raised to pH = 9. If the H2S concentration is maintained at 0. . Consult an appropriate source and determine the Concentration of each of the following species. H2SO4. A 10mL solution of 0. What is the [S2-] concentration under these conditions? Assume the H2S concentration is again 0. 2.) In the Group 3 precipitations. what is the [S2-] concentration? (Ka1 = 1 x 10-7 and Ka2 = 1 x 10-13 for H2S. giving a total volume of 30mL. You will need this Flow Chart in order to complete the second part of the laboratory exercise.7 x 10-5 for PbCl2 at 25oC. What are the concentrations of Cl. Prepare a Flow Chart indicating how you will separate and confirm the presence of each of the ten Cations in a mixture of these Cations. You will not be allowed to start the second part of the laboratory without this Flow Chart. the pH is raised by adding Ammonia. 4.1M.and Pb2+ after the mixing? Will a precipitate of PbCl2 form? (Ksp = 1.01M Pb2+ solution. and NH3.) In the Group 2 precipitations. 3.Page |7 Pre-Lab Questions Week 1 1.010M HCl is mixed with 20mL of a 0.1M and the pH = 1.

you will be starting with 9 different samples. Sodium (Na) will impart a bright yellow color to a flame. As you move through these procedural steps. Since almost all solutions have traces of Na+ present. Pb2+. The procedural steps below are written for this style of testing. 4. It is important that you realize some of the procedural steps may need to be modified because you will have only a single sample containing the various Cations and not. Ni2+ and Ba2+ salts are toxic. forming a precipitate of this Cation is difficult. Week 1 Confirmation for the Presence of Na+ Because Na+ salts are generally soluble. 2. many samples containing a single Cation. Wash your hands after their use. Once you identify each Group of Cations.Page |8 Procedure During Week 1 you will test the precipitation and confirmation reactions for each Cation individually. Mn2+. you must decide if the . each sample containing a single Cation. HNO3. During Week 2 you will follow your flow chart for the separation and identification of Cations in a mixture. Thioacetamide is toxic and produces toxic H2S gas. Bi3+. This is necessary because you need to show the test confirms the presence of the target Cation and is negative for other Cations. Thus. You will first identify the Cations in a given Group. and then move on to separating and confirming their presence. 5. it is important to run the confirmatory tests on all the Cations in that Group. Additionally. H2SO4 and HCl are acids and will burn your skin. Ag+ will stain your skin. you should begin to build a flow chart for how the Cations can be separated from a mixture. as is the case during Week 1’s analysis. You will do this for two mixtures. General Precautions 1. 3. Therefore we will confirm the presence of Na+ using a Flame Test. a mixture of known Cation composition and a mixture of unknown composition. Cu2+. CrO42. Na+ selective confirmatory reagents are also difficult to come toxic and will burn your skin.

Stir the solution and test its acidity with litmus. 1. This will be done on the basis of the intensity of the color. add 6 drops of 6M NH3. Continue to add HNO3 until the solution is acidic. discard the supernatant. Add 20 drops of 6M HNO3 to the decantate.2M NaCl. before contaminating reagents are added. Add 15 drops of Water to each of the solids and place the test tubes into a hot-water bath. Xn+(aq) + n Cl-(aq) 2. Centrifuge and discard the supernatant. Precipitation of Group 1 Cations 1.Page |9 yellow Flame color is due to the presence of Na+ in the original solution. a yellow precipitate. 7. Also. pour the supernatant into a clean test tube. 5. add another 2 drops of 6M HCl and repeat the centrifugation and completeness of precipitation steps. The Group 1 Cations will form a Chloride precipitate. AgCl(s) + 2 NH3(aq) Ag(NH3)2+(aq) + Cl-(aq) (Eq. run a flame test on distilled Water and 0. Confirmation for the Presence of Pb2+: Add 3 drops of 1M K2CrO4 to the supernatant containing Pb2+. If a precipitate did form. confirming the presence of Pb2+. 21) 3. PbCrO4. should form. and then centrifuge. Using a clean Nicrome Wire loop. 4. Centrifuge and decant each supernatant into a clean test tube. 22) . stir thoroughly. Confirmation for the Presence of Ag+: To the AgCl precipitate from Step 5 that did not dissolve in Hot Water. Wash each solid by adding 5 drops of Cold Water and stirring. Repeat this procedure two more times. stir the solution. If the supernatant is cloudy. Retain those solids that do not dissolve. Quickly Centrifuge the hot solution. Pb2+(aq) + CrO42-(aq) PbCrO4(s) (Eq. Add 4 drops 6M HCl. Test for completeness of precipitation by adding 1 drop 6M HCl. perform a Flame Test on each of the original Cation solutions. 20) If the Cation did not produce a precipitate. Continue this process until the supernatant remains clear. Stir using a stir rod for ~ 1 minute. or due to contamination imparted during the Qual Scheme. A white cloudiness confirms the presence of Ag+. XCln(s) (Eq. set it aside for the Precipitation of Group 2 Cations analysis. for comparison. Measure out 10 drops of each of the known Cation solutions. 6.

Precipitation of Group 2 Cations 1. In the fume hood. If more precipitate forms. heat each solution in a Hot Water bath for 10 minutes. X2Sn(s) + 2n H+(aq) 2 Xn+(aq) + n H2S(aq) (Eq.P a g e | 10 Ag(NH3)2+(aq) + 2 H+(aq) + Cl-(aq) AgCl(s) + 2 NH4+(aq) (Eq. Dissolution of the precipitate is the result of H+ combining with Sulfide (S2-) to reform H2S. centrifuge and discard the supernatant. adding 2 drops of Thioacetamide and allowing it to stand for 1 minute. Do this by adding 1 drop 0. Now. Do this for each Cation that produces an additional precipitate. gently heat over a low flame. In the fume hood. 27) 3. Test the supernatant for completeness of precipitation by.2M NH4NO3 solution and 9 drops Water to the second precipitate. 24) (Eq. Combine this additional precipitate with that initially formed for each appropriate Cation. 26) 2 Xn+(aq) + n S2-(aq) If the Cation did produce a precipitate. add 10 drops of 6M HNO3 to each precipitate and heat in a Hot Water bath until the precipitate dissolves. CH3CS(NH2) (aq) + 2 H2O H2S(aq) S2-(aq) + 2 H+(aq) X2Sn(s) H2S(aq) + NH4CH3CO2(aq) (Eq. Centrifuge the solution to remove any Sulfur that forms. again in the fume hood. 2. If the Cation did not produce a precipitate. Save the precipitate and keep track of which supernatant belongs to which precipitate because if precipitation is not complete. (A light-colored residue of Sulfur may remain. 23) At this point you should have confirmed the presence of the Pb2+ and Ag+ ions. mixing and transferring to the first precipitate. keep it for the Precipitation of Group 3 Cations analysis. 25) (Eq. . Centrifuge and decant the supernatant. in a fume hood. This should allow the Thioacetamide to decompose into Hydrogen Sulfide (H2S) and allow the Sulfide precipitates to form in an Acidic environment. add 10 drops of 1M Thioacetamide (CH3CS(NH2)) to each of the solutions from the Precipitation of Group 1 Cations that did not form a precipitate in Step 1 of that procedure. Centrifuge the solution and decant the supernatant into a clean test tube. Mix thoroughly. the additional precipitate collected from the supernatant will have to be combined with the initial precipitate. add a few more drops of Thioacetamide and heat it in a Hot Water bath for 5 minutes.) If the precipitate has not dissolved in 5 minutes.

Separation of Bi3+ and Confirmation for the Presence of Bi3+ and Cu2+: In a fume hood. The formation of a jet-black precipitate confirms the presence of Bi3+. In a fume hood. Add 2 drops 2M NH4NO3 to each of the solutions from the Precipitation of Group2 Cations that did not form a precipitate in Step 1 of that procedure. 29) This can be confirmed by centrifuging the gelatinous mixture and discarding the supernatant. 34) If a precipitate forms. . Xn+(aq) + n OH-(aq) X(OH)n(aq) (Eq. H2S(aq) S2-(aq) + 2 H+(aq) (Eq. causing the H2S equilibrium. A deep blue color confirms the presence of Cu2+. 33) This means Group 3 Cations that form slightly soluble Sulfides will now precipitate. Bi3+(aq) + 3 NH3(aq) + 3 H2O Bi(OH)3(s) + 3 NH4+(aq) (Eq.P a g e | 11 5. The Ammonia produces a Basic (OH-) solution. 28) A white gelatinous precipitate indicates Bi3+ is present.2M SnCl2 to the precipitate and stir. Stir. Add 6 drops of 6M NaOH and 4 drops of freshly prepared 0. NH3(aq) + H2O OH-(aq) + NH4+(aq) (Eq. 2 Xn+(aq) + n S2-(aq) X2Sn(s) (Eq. It will allow for the precipitation of Group 3 Cations as Hydroxides. 2 Bi(OH)3(aq) + 3 Sn(OH)42-(aq) 2 Bi(s) + 3 Sn(OH)62-(aq) (Eq. 32) It also consumes H+ ions. test for completeness of precipitation by Centrifuging the sample and. 30) At this point you should have confirmed the presence of the Cu2+ and Bi3+ ions. Precipitation of Group 3 Cations 1. 31) This does two things. to shift Right.ion. Wash the precipitate once with 10 drops of Hot Water. Discard the washings. in a fume hood. Cu2+(aq) + 4 NH3(aq) Cu(NH3)42+(aq) (Eq. adding an additional drop of 15M NH3. by Le Chatelier’s Principle. add dropwise 15M NH3 until each solution is basic to litmus and add 3 more drops. dramatically increasing the concentration of S2. add dropwise 15M NH3 until each solution is basic to litmus and add 2 more drops.

Re-precipitate the Cations of this Group as Hydroxides by adding 6M NaOH until the solution is strongly Basic. X2Sn(s) + 2n H+(aq) 2 Xn+(aq) + n H2S(aq) (Eq. Allow the solution to stand.and indicates the presence of Mn2+ originally. If the precipitate is pasty. 3. A pink or purple color is due to the formation of MnO4. Add 12 drops of Water and divide each solution into three parts.2M KSCN. To the second part. 2 Mn2+(aq) + 5 NaBiO3(s) + 14 H+(aq) 2 MnO4-(aq) + 5 Bi3+(aq) + 5 Na+(aq) + 7 H2O (Eq. Mn2+ and Ni2+: To the first part for each. 39) Ni(HDMG)2(s) + 4 NH3(aq) + 2 NH4+(aq) . Mix and add a few grains of Sodium Bismuthate (NaBiO3). 38) To the third part.P a g e | 12 2. Mix thoroughly and Centrifuge. In a fume hood. Fe3+(aq) + SCN-(aq) Fe(SCN)2+(aq) (Eq. If the Cation did not produce a precipitate. A brick red color indicates the presence of Fe3+ because Ferric Thiocyanate has formed (Fe(SCN)2+). Centrifuge and decant. 4. Stir and heat in the Hot Water bath for 3 minutes or until the precipitate dissolves. 37) 5. The Hydroxides dissolve because of combination with the Acid. 35) The Nitric Acid (HNO3) oxidizes the Hydrogen Sulfide (H2S) to keep the Sulfide precipitate from reforming. Warm in a Hot Water bath until the precipitate dissolves. add 2 drops 0. Centrifuge the solution to remove any Sulfur that forms. add a solution prepared from 4 drops 3M HNO3 and 4 drops Water. 36) Xn+(aq) + n H2O (Eq. Ni2+(aq) + 6 NH3(aq) Ni(NH3)62+(aq) + 2 H2DMG(aq) Ni(NH3)62+(aq) (Eq. Confirmation for the Presence of Fe3+. treat each precipitate with 3 drops 16M HNO3 and 9 drops 12M HCl. To each precipitate add 20 drops of Water and 10 drops of 6M H2SO4. Add about 4 drops of Dimethylglyoxime (DMG). keep it for the Analysis of Group 4 Cations. add 12 drops of Water. X(OH)n(aq) + n H+(aq) The Sulfides dissolve as before. The DMG complexes with Ni2+ to form a pink precipitate. add 6M NH3 until the solution is Basic to litmus.

A yellow precipitate indicates the presence of Ba2+.P a g e | 13 (Eq. add 8 drops of 6M Acetic Acid (CH3CO2H) and 1 drop of 1M K2CrO4. as is the case during Week 1’s analysis. 41) Confirmation for the Presence of Na+: This was done as a Flame Test on the original sample. At this point you should have confirmed the presence of the Ba2+ and Na+ ions. Re-do any tests that are not consistent with the “known” results. Obtain an “unknown” mixture of cations. Analysis of Group 4 Cations 1. Week 2 During this week’s lab you will follow your flow chart for the separation and identification of Cations in a mixture. 2. many samples containing a single Cation. It is important that you realize some of the procedural steps may need to be modified because you will have only a single sample containing the various Cations and not. a mixture of “known” Cation composition and a mixture of unknown composition. 1. Mn2+ and Ni2+ ions. Perform your analysis on this sample. Identify the cations in this mixture. Perform your analysis on this sample. Obtain a “known” mixture of cations. At this point you should have a complete Flow Chart for the separation and confirmation of the presence of any of our 9 Cations. You will do this for two mixtures. Confirm your results with your laboratory instructor. Confirmation for the Presence of Ba2+: To each of the remaining solutions. 40) At this point you should have confirmed the presence of the Fe2+. Ba2+(aq) + CrO42-(aq) 2. BaCrO4(s) (Eq. .

P a g e | 14 Data Analysis 1. Identify the cations in the “unknown” mixture. .

P a g e | 15 Post Lab Questions Complete all the questions in the “Titrator Precipitation” appendix. .

For Silver Chloride: Ksp = 1. Otherwise. These problems will revolve around the precipitation reactions used to classify the various cations into Groups. will a precipitate form? To answer this question.precipitation to separate the Group I cations from the others.1) (1 x 10-9) = 1 x 10-10 Since Q < Ksp.are mixed. If: Q > Ksp then a precipitate will form. no precipitate will form.P a g e | 16 Appendix . what level of Ag+ will remain in solution? Ag+(aq) + Cl-(aq) AgCl(s) AgCl(s) Ag+(aq) + Cl-(aq) This is the type of equilibrium problem we have leveraged in developing our Qual Scheme.1 M [Cl-] = 1 x 10-9 M we have: Q = [Ag+] [Cl-] = (0. will AgCl precipitate if Chloride ion is added? And. Basically. Recall. How do we enter this information into Titrator so as to obtain this same answer? Well. we want certain cations to precipitate in the presence of a given anion. if we have a solution that is 0.1M Ag+. and we want the other cations to remain in solution. these will form a Basis Set from which all the other Species that make-up the system can be formed. we need to calculate the reaction quotient Q for the system.Titrator Precipitation In this exercise we will model some of the equilibrium problems encountered during the execution of the Qual Analysis lab.82 x 10-10 So. if a precipitate does form. Let us start by asking if Ag+ and Cl. will a given pair of ions form a precipitate at the concentrations encountered during the implementation of the Qual Scheme? For instance. for a system that is prepared such that: [Ag+] = 0. we used Cl. such as Chloride Ion. For our system of three Species . We will start with the most basic question. first start by identifying the Components for the system. it will not. Specifically.

This will mimic the addition of 6M HCl to the system. Because we are adding Ag+ and Cl.000 x 10-1M [Cl-] = the system. it makes sense to include these as Components. Titrator does this rather easily in 2 iterations. The “Free” concentration of each species is: [Ag+] = 1. Titrator reports it as having a non-zero “concentration”.may change forms when precipitating as AgCl. Also.000 pCl = -9. Keep in mind. They can be entered as: Component Ag+ ClType Total Total Total Conc 0. we have reversed the normal solubility equilibrium.concentrations will remain unchanged and the AgCl “concentration” is zero. Specify the Titrant composition as: . the original Ag+ and I.P a g e | 17 (AgCl. Confirm the above results.74* ∆H ∆S +1 +1 Coefficients: Ag+ Cl*Equilibrium written as: Ag+ + ClAgCl logK = .000 x 10-9M [AgCl] = 0 M pAg = -1. let’s Titrate the system with Chloride Ion.pKsp = 9. (Note: As a solid precipitates. the “concentration” of a pure solid cannot actually change. Enter this system into Titrator.) Questions: 1. because Titrator requires that we write all equilibria as Formation reactions for the Species in question. Now. the system is solved. Ag+ and Cl-) we will require two Components. The AgCl itself will be formed from these basis components and so we will enter it as a Species: Species AgCl Dissolved/Ppt Precipitate logK 9. their Formal concentrations will not change.74 This Species is designated as a potential “Precipitate”. Finally.1 1 x 10-9 Guess Log Free M Charge +1 -1 Note we are using a “Total” constraint on the concentration as we have Formally added this amount of each. Although the Ag+ and Cl.000 pAgCl = ~ This is as expected for a case where no precipitate forms. This does not mean that it will precipitate. This is a formal scheme for indicating how much precipitate has formed. only that it has the potential to precipitate. Click on “Titrate”.

as before. Let us start simply with just the Hydrogen Sulfide equilibrium in Water. consider the precipitation reactions involved in separating the Group II and Group II cations. will Chloride precipitation provide an effective means of separating Ag+ and Pb2+ in solution? Next.P a g e | 18 Titrant Composition Primary: Concentration: Cl6M Set Experimental Volumes Initial Sol’n Vol: 5 mL Titrant Vol/Addition: 0. Has all the Ag+ effectively precipitated out of solution before the PbCl2 begins to precipitate? In other words.7 x 10-5. Determine the same values at the previous volume increment. What is the volume titrant needed to drop the Ag+ concentration to 0. the Group III cations could precipitate as either the Hydroxide or the Sulfide salts. Group II cations precipitate at low pH’s. whereas Group III cations require a high pH before they precipitate. In practical terms. 3.01M? (You will have to consult the tabulated results to determine this volume. Further. H2S is added to the mixture and the pH is increased by adding Ammonia. This involves the following two reactions: H2S(aq) Ka1 = 10-7 H+(aq) + HS-(aq) . Now add a second cation to the system. Pb2+. PbCl2(s) It’s solubility equilibrium is: Pb2+(aq) + 2 Cl-(aq) with a Ksp = 1.005 mL Number of Points: 100 Now click “Titrate” and display the AgCl concentration (Molarity) as the 2nd Species. could these precipitation reactions be used in a Qual Scheme for Ag+ and Pb2+? Explain. What volume titrant must be added in order to precipitate the PbCl2? Use the information provided by Titrator to determine QAgCl and QPbCl2 at this volume.) 2. Titrate the system with Cl.

Suppose the system contains the cations Cu2+ (Group II) and Mn2+ (Group III). (Note: We are ignoring the fact that the H2S in solution will also equilibrate with gaseous H2S. we need to couple in the autoionization of Water: H2O H+(aq) + OH-(aq) Kw = 10-14 We will take the H2S concentration as fixed at 0. as we noted was present by the rotten egg smell in the laboratory.1 55.1M as this component is continuously regenerated by the Thioacetamide that is also present. each at 0.1M concentration. Given the following Solubility Products: Solid CuS Cu(OH)2 MnS Mn(OH)2 Ksp 8 x 10-37 4.) A Titrator definition for this system is: Component H2S H2O H+ Species OHHSS2Type Free Free Total Dissolved/Ppt Dissolved Dissolved Dissolved Total M 0.P a g e | 19 H2S(aq) 2 H+(aq) + S2-(aq) K = Ka1 x Ka2 = 10-7 x 10-13 = 10-20 Additionally.5 0 logK -14 -7 Coefficients: H+ H2S H+ H2S -1 +1 -2 +1 Guess Log Free M 0 0 -7 ∆H Coefficients: Charge 0 0 +1 ∆S H+ H2O -1 +1 -20 Coefficients: Questions: 4.8 x 10-20 3 x 10-11 2 x 10-13 . Enter this system into Titrator and determine the concentrations of [S2-] and [OH-].

001 mL Number of Points: 100 What volume NH3 must be added before MnS precipitates out? Will the Hydroxide also precipitate at this point? Explain using a quantitative arguement. add a little Ammonia to the system: NH3(aq) + H2O NH4+(aq) + OH-(aq) Kb = 1.75 x 10-5 In order to add this to our Titrator definition. Will any of the solids precipitate? (You do not need to enter the Cu and Mn species into Titrator. Solve the system and then Titrate it with Ammonia: Titrant Composition Primary: Concentration: NH3 1M Set Experimental Volumes Initial Sol’n Vol: 5 mL Titrant Vol/Addition: 0. we need to re-write it as (why?): NH3(aq) + H+(aq) NH4+(aq) K = (1. Add this to the above system.concentration is required to precipitate the Mn2+. Start with a “Total” Ammonia concentration of 10-20.) . (Determine by hand calculation what S2. Simply use the results from Titrator for the H2S system and calculate the Q’s by hand.75 x 10-5) (10+14) = 1.75 x 10+9 Questions: 5.P a g e | 20 determine the reaction quotient Q for each possible precipitation reaction.) In order to raise the pH and increase [S2-]. Then check the tabulated Titrator results to see what volume NH3 is required to produce this concentration.

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