Chemistry 112 Laboratory: Precipitation of Metal Sulfides Page 17

Precipitation Reactions

Y ou have already seen how precipitation reactions are used in qualitative

analysis. The separation of the ions of the silver group, and their identifi-
cation, depended on reactions of this type. In this experiment you will exam-
ine the precipitation reactions of the following seven metal cations:
Antimony (III), Sb3+ Bismuth (III), Bi3+
Cadmium (II), Cd2+ Manganese (II), Mn2+
Mercury (II), Hg2+ Tin (IV), Sn4+
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) Æ 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, Metal sulfide chemistry is compli-
you will be able to identify the metal cation in an unknown solution. cated. See R. J. Myers, Journal of
Chemical Education, Vol. 63, pp.
687-690, 1986.
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 col-
ors. This might be a feature you are acquainted with, since so many common Many elements are found in nature
minerals are metal sulfides. For example, there is Fool's Gold (iron pyrite, as their sulfides. In Chemistry
& Chemical Reactivity see pages 140-
FeS2), red cinnabar (HgS), black galena (PbS), and lemon-yellow orpiment
141 and the iron pyrite on page 19
(As2S3). (Figure 1.8b).
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 solu-
tion that contains a very small concentration of sulfide ion. Mercury(II)
sulfide is an example of a highly insoluble sulfide.
Hg2+(aq) + S2-(aq) Æ 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) Æ 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) Æ MnS(s) A sample of lead sulfide, PbS, and

In the course of this experiment you will find that there are indeed vast dif- a model of the compound. See
Figure 18.14 in Chemistry & Chemical
ferences in the solubility of the metal sulfides to be studied.
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 A Lewis acid is an acceptor of elec-
tron pairs, while a Lewis base is a
the oxide ion, O2- (a Lewis base) to give the carbonate ion. donor of electron pairs. The union of
a Lewis base and acid means that an
•• 2– electron pair can be shared between
O
••
••

•• •• 2– them, giving rise to a chemical bond.

••
O

••
See page 828 of Chemistry & Chemical
•• •• •• •• Reactivity.
O C O O C 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) Æ 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) Æ 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) Æ HS-(aq) + OH-(aq) Kb = 1 x 105

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while H2S is predominant in acidified solution. See Chapter 19 of Chemistry & Chemical
Reactivity for a discussion of the general
S2-(aq) + 2 H3O+(aq) → H2S(aq) + 2 H2O(l)
principles of precipitation reactions.
In either case, you are safe in assuming that an aqueous solution of S2- con-
tains 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) Æ NiS(s) + 2 H3O+(aq)

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

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 Ksp Values for Metal Sulfides.
and HgS are examples), so we need additional tests. One way to differenti- Ksp values for metal sulfides are difficult
ate precipitates is by exploring the conditions needed to dissolve the solid. to define. This is due to the fact that
sulfides undergo hydrolysis in water,
Consider nickel sulfide as an example.
thus causing the solubility to be greater
NiS(s) Æ Ni2+(aq) + S2-(aq) than predicted by the Ksp value. See
Nickel sulfide will dissolve if the equilibrium can be shifted to the right, away the discussion on page 766 of Chemistry
& Chemical Reactivity (A Closer Look).
from NiS(s) and toward the ions. To do this, we use Le Chatelier's Principle See also a set of corrected Ksp values
(text book, pages 674-679 in 5th edition or pages 770-776 in 4e): A change for metal sulfides on page A.25 on the
in any of the factors that determine an equilibrium will cause the system to 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) Æ [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) Æ 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) Æ 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) Æ S(s) + 2e-
we 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)
Æ 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) Æ 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)
Æ 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 Step 1. In a few cases a white
precipitate will form when distilled
about 5 drops of a known solution in a test tube and then add distilled water water is added initially to the known
so that the test tube is about half-filled. Add 3 drops of 6 M HCl and then 3 or unknown solution. For example,
drops of ammonium sulfide, (NH4)2S, to each test tube. HEAT. MIX WELL! because the known or unknown solu-
• If a sulfide precipitate forms, centrifuge and decant, discarding the liquid. tions already contain hydrochloric
acid, an insoluble oxychloride such
Wash the precipitate twice with a few drops of distilled water. Note the as SbOCl can form.
color and appearance of each precipitate, then set them aside for further
Sb3+(aq) + Cl-(aq) + 3 H2O(l)
testing in Step 2 below. Æ SbOCl(s) + 2 H3O+(aq)
• The ions Mn2+, Zn2+, and Sn2+ may form a precipitate here, but precipita- Adding more HCl should dissolve this
tion may not be complete. If little or no precipitate was formed, add a few more basic salt. However, if it is not dis-
drops of (NH4)2S and then a few drops of NaOH. Mix well If a precipitate solved after adding 3 drops of HCl,
still does not form, continue adding 2 M NaOH a few drops at a time, add a few more drops of acid until
the solid does dissolve. NOTE: When
mixing thoroughly after each addition, until the solution is basic and a doing your unknown, observing this
precipitate forms. behavior could be a clue as to the
Be sure to test the basicity of the solution in this step with red litmus. When presence of Sb3+ and/or Bi3+.
the solution is basic, the litmus paper will turn blue. Adding NaOH here neu-
tralizes the H3O+ in the solution, thereby converting an H2S into S2- ion.

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 redis-
solve the sulfide precipitates. Add at least 10 drops of (NH4)2S to each pre- The chemistry of Steps 3-5 is
cipitate. Stir well and note any changes. If the precipitate does not dissolve, go explained by point 2 on page 4.
to step 4. However, before doing so, make sure you have made a very valiant Notice that elemental sulfur can be
attempt to dissolve the precipitate! formed by the oxidation of S2- by
nitric acid. You may see evidence
of the sulfur as a yellow, orange, or
STEP 4. gray solid that floats on top of the
solution.
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 undis-
solved, 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 note-
book with tape or a staple. The observations you make on your unknown solu-
tions 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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