Chemistry 112 Laboratory: Precipitation of Metal Sulfides

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Precipitation Reactions

ou have already seen how precipitation reactions are used in qualitative analysis. The separation of the ions of the silver group, and their identification, depended on reactions of this type. In this experiment you will examine the precipitation reactions of the following seven metal cations: Antimony (III), Sb3+ Cadmium (II), Cd2+ Mercury (II), Hg2+ Zinc, Zn2+ Specifically, you will study the conditions under which each of these ions forms an insoluble metal sulfide, 2 Sb3+(aq) + 3 S2-(aq) Sb2S3(s) and the conditions necessary to redissolve each of the precipitates. Based on these reactions, and the characteristic colors of the metal sulfide precipitates, you will be able to identify the metal cation in an unknown solution.
Metal sulfide chemistry is complicated. See R. J. Myers, Journal of Chemical Education, Vol. 63, pp. 687-690, 1986.

Bismuth (III), Bi3+ Manganese (II), Mn2+ Tin (IV), Sn4+

METAL SULFIDE CHEMISTRY

Perhaps the most noticeable feature of metal sulfides is their color. In contrast with the white chlorides of the silver group ions, the metal sulfides cannot only be white but may also be black, yellow, orange, brown, or many other colors. This might be a feature you are acquainted with, since so many common minerals are metal sulfides. For example, there is Fool's Gold (iron pyrite, FeS2), red cinnabar (HgS), black galena (PbS), and lemon-yellow orpiment (As2S3). Another feature of metal sulfides is that, while most are NOT soluble in water, the degree of insolubility varies widely. We can classify them roughly as follows: Highly insoluble: Sulfides of this type precipitate from a highly acidic solution that contains a very small concentration of sulfide ion. Mercury(II) sulfide is an example of a highly insoluble sulfide. Hg2+(aq) + S2-(aq) HgS(s) Moderately insoluble: These sulfides are precipitated from a neutral or weakly acidic solution where the concentration of sulfide is larger. Zinc sulfide can be considered in this category. Zn2+(aq) + S2-(aq) ZnS(s) Somewhat soluble: Sulfides in this category require a much larger concentration of S2- ion in solution before precipitation can occur. Manganese(II) sulfide is an example of the more soluble metal sulfides. Mn2+(aq) + S2-(aq) MnS(s) In the course of this experiment you will find that there are indeed vast differences in the solubility of the metal sulfides to be studied.

Many elements are found in nature as their sulfides. In Chemistry & Chemical Reactivity see pages 140141 and the iron pyrite on page 19 (Figure 1.8b).

A sample of lead sulfide, PbS, and a model of the compound. See Figure 18.14 in Chemistry & Chemical Reactivity, page 882.

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Another feature of sulfides is that some can behave as acids while others are basic. In this course we have already discussed these terms as applied to metal and nonmetal oxides. For example, CO2 is an acidic oxide in that it gives weakly acidic solutions when dissolved in water. H2O(l) + CO2(g) H2CO3(aq) H2CO3(aq) + H2O(l) H3O+(aq) + HCO3-(aq) Note that this reaction is in essence the reaction of CO2 (a Lewis acid) with the oxide ion, O2- (a Lewis base) to give the carbonate ion.
2 O C O O O
A Lewis acid is an acceptor of electron pairs, while a Lewis base is a donor of electron pairs. The union of a Lewis base and acid means that an electron pair can be shared between them, giving rise to a chemical bond. See page 828 of Chemistry & Chemical Reactivity.

O C

2 O

In general, non-metals form acidic oxides. In contrast, the metal oxide CaO (calcium oxide) is a basic oxide because it gives a basic solution when placed in water. CaO(s) + H2O(l) Ca(OH)2 Ca2+(aq) + 2 OH-(aq) In general, metals form basic oxides. Just as there is an oxide/H2O system of reactions, there is a sulfide/H2S system. For example, an acidic sulfide may dissolve in a solution containing the basic sulfide ion as follows: As2S5(s) + 3 S2-(aq) 2 AsS43-(aq) In general, the metalloids, the elements along the metal/nonmetal border in the periodic table, form acidic sulfides. As this includes only Ge, As, Sb, and Te, there are relatively few that you will have to worry about in the laboratory. The vast majority of the sulfides we work with are metal sulfides and so do not dissolve in solutions containing excess sulfide ion.

GENERAL PRINCIPLES
One of the purposes of this laboratory is to illustrate some of the general principles of chemical equilibrium, a subject discussed in class and described in Chapters 16-19 of your text book. Although we cannot discuss this topic in detail here, a few principles that apply directly to this experiment are outlined below.

A. Sulfide Ion and Hydrogen Sulfide

The sulfide ion, S2-, that you need to precipitate the metal sulfides in this experiment is supplied by the water-soluble salt ammonium sulfide, (NH4)2S. In aqueous solution it dissociates completely to give S2- ion. (NH4)2S(aq) 2 NH4+(aq) + S2-(aq) The S2- concentration in neutral or acidic solution is actually extremely small, however, because the ion readily combines with a source of protons to form the HS- ion or H2S, hydrogen sulfide. In water a major product is HS-, S2-(aq) + H2O(l) HS-(aq) + OH-(aq) Kb = 1 x 105

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while H2S is predominant in acidified solution. S2-(aq) + 2 H3O+(aq) H2S(aq) + 2 H2O(l) In either case, you are safe in assuming that an aqueous solution of S2- contains a reasonable concentration of H2S. Thus, when you are asked to write a balanced equation for the reaction of a metal ion with sulfide in a neutral or acidic solution, it is best to use H2S, as in the following equation. Ni2+(aq) + H2S(aq) + 2 H2O(l) NiS(s) + 2 H3O+(aq)

See Chapter 19 of Chemistry & Chemical Reactivity for a discussion of the general principles of precipitation reactions.

B. Solubility
Solubility and insolubility are crude descriptions of a dynamic equilibrium of the type (the double arrows, , are meant to convey this feature) NiS(s) Ni2+(aq) + S2-(aq) As described in Chapters 17 and 19 of your text book, this equilibrium can be described by the mathematical expression Ksp = [Ni2+][S2-] where the equilibrium constant for the reaction, Ksp (where the subscript sp stands for solubility product"), has a value of 3.0 x 10-21. Values of Ksp for the metal sulfides to be studied in this experiment are given in a table below. Notice that all of these compounds have very small values of Ksp, and so all are quite insoluble. For sulfides of the same formula, the smaller the value of Ksp, the lower the solubility of the compound. Thus, CdS is less soluble than ZnS because Ksp for CdS (3.6 x 10-29) is less than (is a smaller number than) the Ksp for ZnS (1.1 x 10-21). Metal Sulfide Sb2S3 Bi2S3 CdS MnS HgS SnS2 ZnS Ksp 1.6 x 10-93 1.6 x 10-72 3.6 x 10-29 5.1 x 10-15 3.0 x 10-53 1.0 x 10-70 1.1 x 10-21
The structure of ZnS. The Zn2+ ions in the unit cell are arranged as a face centered cubic lattice, and the S2- ions occupy tetrahedral holes within the lattice. There is a net of 4 Zn2+ ions and 4 S2- ions within the unit cell. See Chapter 13 of Chemistry & Chemical Reactivity. (See the Models folder on the General Chemistry Interactive CD-ROM. )

C. Dissolving Precipitates and Le Chatelier's Principle

One can often identify a metal ion by the color of its sulfide precipitate and by the conditions under which it precipitates. However, often several ions precipitate under the same conditions and have nearly the same color (Bi2S3 and HgS are examples), so we need additional tests. One way to differentiate precipitates is by exploring the conditions needed to dissolve the solid. Consider nickel sulfide as an example. NiS(s) Ni2+(aq) + S2-(aq) Nickel sulfide will dissolve if the equilibrium can be shifted to the right, away from NiS(s) and toward the ions. To do this, we use Le Chatelier's Principle (text book, pages 674-679 in 5th edition or pages 770-776 in 4e): A change in any of the factors that determine an equilibrium will cause the system to

Ksp Values for Metal Sulfides. Ksp values for metal sulfides are difficult to define. This is due to the fact that sulfides undergo hydrolysis in water, thus causing the solubility to be greater than predicted by the Ksp value. See the discussion on page 766 of Chemistry & Chemical Reactivity (A Closer Look). See also a set of corrected Ksp values for metal sulfides on page A.25 on the textbook.

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change in such a manner that the effect of the disturbance is minimized or counteracted. In this case if we could remove Ni2+ or S2- from solution in some way, more solid NiS will dissolve in an attempt to maintain the concentrations of these ions constant, and the solid would dissolve. The following methods represent several ways to accomplish this: 1. The cation can be removed from solution by forming a complex ion as you did when you dissolved AgCl in NH3 in a previous experiment. AgCl(s) + 2 NH3(aq) [Ag(NH3)2]+(aq) + Cl-(aq) The added ammonia "sweeps" Ag+ out of the solution in the form of its complex ion, and the AgCl precipitate dissolves. In this experiment, a somewhat similar reaction occurs when excess S2- ion is added to certain precipitates. For example, the sulfide SnS2 dissolves because it forms a complex sulfide with excess S2- ion. SnS2(s) + S2-(aq) SnS32-(aq) 2. The anion can be removed from solution. Here the S2- ion can be removed by adding excess acid because the very stable weak acid H2S is formed. MnS(s) + 2 H3O+(aq) Mn2+(aq) + H2S(aq) + 2 H2O(l) Yet another way to accomplish this is to destroy the sulfide ion by turning it into elemental sulfur. Because this is an oxidation reaction S2-(aq) S(s) + 2ewe need a add a powerful oxidizing agent, and 6 M HNO3 does this very well in this experiment. 3 S2-(aq) + 2 NO3-(aq) + 8 H3O+(aq) 3 S(s) + 2 NO(g) + 12 H2O(l) Notice that HNO3 can be used to dissolve insoluble metal sulfides not only by removing S2- by oxidation but also by forming H2S. S2-(aq) + 2 H3O+(aq) H2S(aq) + 2 H2O(l) Nitric acid is a double-barreled reagent! 3. If all else fails to dissolve a metal sulfide, our panic button is aqua regia, a mixture of HNO3 and HCl. As described above, HNO3 can remove S2- by oxidizing it to elemental sulfur. In addition, the Cl- ion can form a very stable complex ion with some metal cations. For example, mercury(II) sulfide is quite insoluble in HNO3 and HCl when each is used separately. However, a mixture of the acids dissolves HgS readily and completely. The net reaction is 3 HgS(s) + 2 NO3-(aq) + 8 H3O+(aq) + 12 Cl-(aq) 3 HgCl42-(aq) + 2 NO(g) + 12 H2O(l) + 3 S(s)

EXPERIMENTAL PROCEDURE
The Known Solutions
In the first stage of the experiment you will investigate the chemistry of the sulfides of the following seven metal ions: Sb3+ Bi3+ Cd2+ Mn2+ Hg2+ Sn4+ Zn2+

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Follow the steps given below, and pay particular attention to the marginal notes that are given for each step. Your observations can be entered in the attached table (which can then be taped or stapled into your lab book).

STEP 1.
Clean and dry 7 test tubes, one for each of the 7 ions to be studied. Place about 5 drops of a known solution in a test tube and then add distilled water so that the test tube is about half-filled. Add 3 drops of 6 M HCl and then 3 drops of ammonium sulfide, (NH4)2S, to each test tube. HEAT. MIX WELL! If a sulfide precipitate forms, centrifuge and decant, discarding the liquid. Wash the precipitate twice with a few drops of distilled water. Note the color and appearance of each precipitate, then set them aside for further testing in Step 2 below. The ions Mn2+, Zn2+, and Sn2+ may form a precipitate here, but precipitation may not be complete. If little or no precipitate was formed, add a few more drops of (NH4)2S and then a few drops of NaOH. Mix well If a precipitate still does not form, continue adding 2 M NaOH a few drops at a time, mixing thoroughly after each addition, until the solution is basic and a precipitate forms. Be sure to test the basicity of the solution in this step with red litmus. When the solution is basic, the litmus paper will turn blue. Adding NaOH here neutralizes the H3O+ in the solution, thereby converting an H2S into S2- ion.
Step 1. In a few cases a white precipitate will form when distilled water is added initially to the known or unknown solution. For example, because the known or unknown solutions already contain hydrochloric acid, an insoluble oxychloride such as SbOCl can form. Sb3+(aq) + Cl-(aq) + 3 H2O(l) SbOCl(s) + 2 H3O+(aq) Adding more HCl should dissolve this basic salt. However, if it is not dissolved after adding 3 drops of HCl, add a few more drops of acid until the solid does dissolve. NOTE: When doing your unknown, observing this behavior could be a clue as to the presence of Sb3+ and/or Bi3+.

STEP 2.
Once all of the metal sulfides have been precipitated, centrifuge and decant, discarding the liquid as above. Wash each precipitate twice with distilled water. Again note the color and appearance of each precipitate, and set each aside for further testing according to step 3 below.

STEP 3.
In the remaining steps, you will investigate the conditions needed to redissolve the sulfide precipitates. Add at least 10 drops of (NH4)2S to each precipitate. Stir well and note any changes. If the precipitate does not dissolve, go to step 4. However, before doing so, make sure you have made a very valiant attempt to dissolve the precipitate!
The chemistry of Steps 3-5 is explained by point 2 on page 4. Notice that elemental sulfur can be formed by the oxidation of S2- by nitric acid. You may see evidence of the sulfur as a yellow, orange, or gray solid that floats on top of the solution.

STEP 4.
Take any precipitate that was not dissolved in Step 3, centrifuge the test tube, decant the solution, and then wash twice with distilled water to remove any (NH4)2S. Add a few drops of 6 M HNO3 to each precipitate, then mix well and heat in a boiling water bath. Note any changes. If a precipitate is still undissolved, go to Step 5.

STEP 5.
If a precipitate still remains after Step 4, severe action is called for! Add about 5 drops of concentrated HCl to the solid + nitric acid mixture from Step 4. Heat in a boiling water bath and stir vigorously.
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THE UNKNOWN SOLUTIONS

When you have completed your observations, outline a logical approach for identifying the ion present in a solution that is known to contain ONE and only one of the seven ions you have just investigated. Show your scheme to your instructor and obtain three unknown solutions. As you investigate the three unknown solutions, be sure to write down completely the observations you make. If you do not report the correct ion, you and your instructor can then analyze your work and can probably discover where you made your mistake. Report your results to your instructor before leaving the laboratory. Be sure to match your result with the unknown number given to you by your instructor.

WRITING UP THE NOTEBOOK

The observations made on the known solutions may be written on the report sheet available in the lab, and this sheet can then be attached to your notebook with tape or a staple. The observations you make on your unknown solutions should be written in your notebook. Be sure to note that if you do not report observations on your unknown, you will not receive credit for the experiment, even if the results were correct. In addition to your observations, you should answer the following questions: 1. Write balanced equations for each of the following reactions: a) Cd2+(aq) + H2S(aq) b) Bi3+(aq) + H2S(aq)

2. The three observations below give clues to the identity of one ion in an unknown solution. Identify the ion. a) An unknown solution precipitates a white solid when distilled water is added. The solid disappears when excess HCl is added. b) This unknown immediately precipitates a very dark colored precipitate (black or deep black-brown) when H2S is added. c) The dark precipitate above dissolves, with some effort, when it is heated with 6 M HNO3.

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Test

Tin(IV)

Antimony(V)

Manganese(II)

Zinc

Add water

Add 6 M HCl

Add (NH4)2S

Add 2 M NaOH

Excess (NH4)2S

Add 6 M HNO3

Add conc. HCl

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Test

Bismuth

Cadmium

Mercury(II)

Add water

Add 6 M HCl

Add (NH4)2S

Add 2 M NaOH

Excess (NH4)2S

Add 6 M HNO3

Add conc. HCl

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