CH 317 Experiment 1: Qualitative Chemical Analysis

Objective: This experiment represents a problem in qualitative analysis. You will be issued a
liquid sample of approximately 0.1 M concentration. Each sample contains two or more metal
salts, each from a different ion group. Your assignment is to identify the species present by
your observations and by the use of the selective precipitation procedure provided.

Introduction

One of the important aspects of chemistry is analysis: qualitative analysis is concerned with the
identity of the species present in a sample whereas quantitative analysis deals with the amount,
or percentage, of a species present in the sample. In this unit we address techniques of qualitative
analysis, whereas methods for quantitative analysis are discussed in subsequent units in this
course.

All questions of analysis involve a consideration of the properties of matter. Recall from your
previous knowledge of chemistry that properties are characteristic of different sample of matter.
Thus knowledge of a melting point, a color, the way a substance reacts with another reagent, e.g.,
HCl, is often sufficient to identify the substance. In this unit we consider methods of qualitative
analysis based on chemical properties and physical properties, or a combination of the two.

Chemical Properties/Physical Properties

A chemical property refers to the way a substance is changed into another substance, i.e., its
reactivity with another substance, or the way it reacts. Sometimes the reactivity is very obvious,
for example, metallic sodium is almost never observed in its pure state in a conventional
laboratory because this metal reacts rapidly with oxygen to form white sodium oxide, or with
water vapor to form white sodium hydroxide. Thus, it is highly probable that a piece of sodium
will always be covered with a white crusty-looking coating. This chemical property of sodium,
its rapid reaction with oxygen or water vapor, can be clearly seen if a piece of sodium is cut in
the air with a sharp knife. The sample appears lustrous where the knife cuts into it, but the shiny
surface rapidly becomes coated with a film that dulls the surface. In time the surface acquires a
crusty-white coating as more oxygen and water vapor diffuse through the film of the original
reaction product.

Physical properties of a substance are those that do not involve a change in the chemical identity
of the substance. Common physical properties include the temperature at which a substance
melts (melting point) or boils (boiling point), its color, and density.

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This rather detailed description of the chemical property of sodium illustrates the difficulty of
separating chemical properties from physical properties. For example, we know that a chemical
reaction has occurred when sodium is exposed to air because the appearance of the sodium has
changed. The characteristic metallic luster of sodium is a physical property, but the process
which causes the surface to change is a chemical property. Factors that contribute to the
appearance of a sample, e.g., color, surface, quality, statements of crystallinity, are invariably
classified as physical properties. Thus, the fact that a chemical reaction has occurred when
sodium is exposed to air is deduced from the change in physical properties.

The Strategy of Qualitative Analysis

The basis for identification of substances lies in their chemical and physical properties. The
simplest properties used for identification are those that can be directly observed by the
experimenter. Thus the color of a substance and the results of its reaction with various reagents
are commonly used for identification purposes. If we limit ourselves to reagents that produce
observable effects, we must then form colored substances (in solution or as a precipitate), form
gaseous products that can be visually seen to leave the solution or to produce a characteristic
odor, or cause a previously insoluble substance to dissolve.

A single common example will suffice to illustrate these points. A solution can be identified as
containing Cl- ions by treating it with a solution of AgNO3, with which it produces a white
precipitate of si1ver chloride (AgCl). In this case the sample, which was suspected to contain Cl-,
was caused to react with a reagent that produced a visual effect (a white precipitate). The
supposition that AgCl and not some other unknown, insoluble substance was formed can be
verified by considering the properties of AgCl; this substance is insoluble in aqueous HNO3.
Thus if we isolate the white solid and treat it with aqueous HNO3 and it fails to dissolve, we can
conclude that the original solution contained Cl-. Experimentation has demonstrated that no two
species -- Cl- and something else -- would both give an insoluble white product with AgNO3 that
is insoluble in HNO3. There are, in fact, other ions that give a white precipitate with AgNO3, but
they are soluble in HNO3, A knowledge of the chemistry and properties of silver compounds
therefore gives us definitive proof that the unknown solution contains Cl-.

A second possible strategy would be to dissolve the mixture in water and to find reagents that are
specific for (react with) only one cation or anion. If such a reagent existed and reaction yielded a
precipitate, we could filter the reaction mixture and then test the filtrate with another reagent.
Thus, from a series of precipitations and separations, we could obtain the necessary information
to decide the presence or absence of each ion. Unfortunately, such an ideal set of reagents does
not exist for the collection of ions we have chosen to use as examples for our study. With only a
few exceptions, a reagent that gives a characteristic reaction with one ion gives a characteristic
reaction with other ions in the group as well, or else its characteristic reaction with one ion is

2
 interfered with by other ions. That is, a given ion must be generally free of the presence of other
(interfering) ions before it may be identified.

TABLE 1. COMMON IONIC SPECIES OF THE ELEMENTS

Cations

Silver Group/Group Copper-Arsenic Aluminum-Nickel Barium-Magnesium

I Group/ Group II Group/Group III Group/Group IV

Ag+ Cu2+ Al3+ Ba2+

Pb2+ Pb2+ Cr3+ Ca2+

Hg2+ Bi3+ Fe3+ Mg2+

Hg22+ Cd2+ Mn2+ Na+

As3+ Co2+ K+

Sn2+ Ni2+ NH4+

Sn4+ Zn2+

A classical method of separation involves the use of only 3 reagents -- HCl, H2S and NH4OH --
all as aqueous solutions. Most of the common cations can be separated into one of four possible
groups. For example, consider the common cations listed in table 1. These cations are
representative of all cations.

The cations in table 1 can be separated into four groups by the addition of specific group reagents.
The unknown is dissolved in water so that we are working with an aqueous solution. The addition
of the group reagent causes the cations of that group to precipitate; the remaining ions remain in
solution, so a separation has occurred. The outline of the group precipitation scheme is shown in
Figure 1 in the form of a flow diagram. You should study this flow diagram carefully because it
presents the essence of the whole plan of group separation of the cations.

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Cation Groups

The Silver Group/Group I. Dilute hydrochloric acid is the group reagent (precipitant) for the
first group that is separated: this group is called the silver group. Separation of the cations of the
silver group from all the other cations depends on the fact that the chlorides of silver (AgCl),
lead (PbCl2), and mercury (I) (Hg2Cl2) are insoluble in dilute HCl, whereas the chlorides of all
the other metals are soluble.

The Copper-Arsenic Group/Group II. The group reagent for the second group is H2S.
Separation of the cations of the copper-arsenic group depends on the fact that their sulfides are
insoluble in dilute HCl, where as the remaining sulfides are soluble.

The Aluminum-Nickel Group/Group III. The group reagent for the third group is a mixture
of NH4OH and (NH4)2S, which precipitates a mixture of hydroxides and sulfides that are
insoluble in alkaline solution.

The Barium-Magnesium Group/Group IV. The ions of the fourth group form soluble
chlorides, sulfides, and hydroxides and remain in solution after all the ions of the first three
groups have

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Figure 1. The group separation scheme.
been precipitated. There is no group reagent for the barium-magnesium group.

The identification of the ions present in each group involves a detailed consideration of the
chemistry of the ions in the group. These details can be obtained from any good qua1itative
analysis book.

GENERAL DISCUSSION OF THE PROCEDURE FOR ANALYSIS OF THE GROUP I

CATIONS: Pb2+, Ag+

Since the properties of the cations in Group I differ considerably, it is easy to find a procedure
for separating and identifying them. In the standard procedure, PbCl2 is separated from the other
two insoluble chlorides by adding water to the solid precipitate and heating the mixture to about
l00 C. At that temperature PbCl2 dissolves in appreciable quantities. The hot liquid is separated
from the solid and a solution of K2CrO4 is added, precipitating yellow PbCrO4 if lead is present
(precipitation of traces of Ag2CrO4 is prevented by making the solution slightly acidic with
HC2H3O2).

The remaining AgCl-Hg2Cl2, precipitate is then treated with 6 M NH3. Any AgCl dissolves by
formation of Ag(NH3)2+ ion. If Hg2Cl2, is present, it reacts with ammonia to form a precipitate of
Hg and HgNH2Cl, which is black. The solution which may contain Ag(NH3)2+ is acidified,
destroying the complex ion and liberating Ag+. Precipitation of white, curdy AgCl by reaction of
silver ion with chloride ion in the solution confirms the presence of silver.

If Hg2Cl2 is present in large excess, there is a complication. The mercury liberated by reaction of
the chloride with ammonia may reduce Ag+ to the metal before the Ag(NH3)2+ complex ion can
be removed from the system.

2 Hg(l) + 2 Ag+(aq) Hg22+(aq) + 2 Ag(s)

Under such conditions the black precipitate of Hg, HgNH2Cl and Ag can be dissolved in aqua
regia (a mixture of HNO3 and HCl), producing HgCl2. which is soluble, and AgCl2- ion. The
silver chloride complex ion is convened to AgCl on dilution, and then dissolved in NH3;
reprecipitation of AgCl on acidification establishes the presence of silver.

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GENERAL DISCUSSION OF THE PROCEDURE FOR ANALYSIS OF THE GROUP II
CATIONS: Cu2+, Bi3+, and maybe Pb2+

The general solution of the Group II cations is typically highly acidic; salts of bismuth, tin, and
antimony precipitate unless the solution is roughly 1 M in H+ ion. The solution is treated with
H2O2, which oxidizes any Sn(II) present to Sn(IV), since the latter forms a more easily
centrifuged sulfide precipitate.

The pH of the solution is adjusted to 0.5, and H2S, as furnished by the decomposition of
thioacetamide, is introduced. The cations of Group II precipitate as sulfides, while those of
Group III, which form more soluble sulfides, remain in solution at this relatively high H+ ion
concentration.

Following separation of the Group II sulfides, they are treated with 1 M NaOH. This dissolves
the sulfides of tin(IV) and antimony(III), SnS2 and Sb2S3. The sulfides of the other Group II ions
are left essentially unaffected.

Of the remaining sulfides, CuS, Bi2S3, PbS, and CdS are dissolved in 6 M nitric acid. Mercuric
sulfide, HgS, is insoluble in nitric acid. It is dissolved in aqua regia. The presence of Hg2+ in the
resulting solution is established by reaction with Cu(s) and by addition of SnCl2, which
forms Hg2Cl2 and some mercury metal.

Ammonia is added to the solution containing Cu2+, Bi3+, Cd2+, and Pb2+. Copper(II) and
cadmium(II) stay in solution as complex ions. Bismuth(III) and lead(II) precipitate as the
hydroxides. Copper is identified by the blue color of its complex ion in the NH3 solution and by
precipitation of red-brown Cu2Fe(CN)6. Following reduction of copper(II) to the metal in part of
the NH3 solution, the presence of cadmium(II) is established by precipitation of yellow CdS.

Any Bi(OH)3 present in the ammonia precipitate is dissolved in HCl and tested for by
formation of BiOCl on addition of water and formation of black bismuth metal on reduction
with SnCl2 under basic conditions. Lead(II) is identified by dissolving the remaining lead
precipitate in acetate solution and precipitating white PbSO4 with sulfuric acid.

The NaOH solution containing tin and antimony complex ions is treated with HCl, which
reprecipitates the sulfides. These are then dissolved in hot HCl; half the solution is reduced with
Al wire, forming Sn2+ and black Sb metal. The presence of tin is shown by reaction with HgCl2.
Any antimony present in the other half of the solution is precipitated as peach-colored Sb2OS2 by
addition of thiosulfate, a reaction with which tin(IV) does not interfere.

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GENERAL DISCUSSION OF THE PROCEDURE FOR ANALYSIS OF THE GROUP III
CATIONS: Fe2+ and Fe3+, Co2+, Ni2+, Cr3+

The common property of the Group III cations is that they will precipitate from solution in the
presence of sulfide ion at a pH of about 9. The aluminum and chromium ions form hydroxides
under these conditions, and the rest of the cations form sulfides. The precipitation is carried out
using thioacetamide in an NH3-NH4+ buffer.

Following separation of the precipitate, it is treated with HCl; in principle, all the solids should
dissolve, since they will not form under acidic conditions. However, NiS and, particu1arly, CoS
very quickly change their crystalline structures after precipitation and become almost insoluble
in acid. Hence they can be separated from the other species. The cobalt and nickel sulfides are
dissolved in aqua regia and are identified by their reactions with specific reagents.

The hydrochloric acid solution of the other cations is made strongly basic with NaOH. Addition
of hypochlorite ion, ClO-, causes oxidation of Cr(III) to yellow CrO42-, and of Mn(II) to MnO2.
After removal of excess hypochlorite, the solid phase contains Fe(OH)3, MnO2 and some
Ni(OH)2,; in the solution we have Al(OH)4-, CrO42-, and Zn(OH)42- ions. Treatment of the solid
with H2SO4 produces Fe3+ and Ni3+, but fails to dissolve the MnO2. The manganese dioxide can
be separated, dissolved, and the presence of manganese established by reaction with sodium
bismuthate to form purple permanganate ion.

The iron and nickel ions are tested for with thiocyanate and ferrocyanide (for Fe3+) and
dimethylglyoxime (for Ni3+). The basic solution which may contain Al(III), Cr(VI), and Zn(II) is
made acidic; addition of NH3 in excess causes Al(OH)3 to precipitate and leaves CrO42- and
Zn(NH3)42- in solution. The Al(OH)3 is dissolved and in the presence of aluminon forms a red
lake on being made basic with NH3. Chromate ion is precipitated as yellow BaCrO4: this is
dissolved in HNO3 and treated with H2O2, producing blue CrO3. Zinc(II) is identified by a
characteristic reaction with a solution of potassium ferrocyanide.

GENERAL DISCUSSION OF THE PROCEDURE FOR ANALYSIS OF THE GROUP IV

CATIONS: Ba2+, Ca2+

The ions remaining in solution after the separation of the Group III cations are those of the
alkaline earths, the alkali metals, and ammonium. These ions pass through the analysis scheme
unaffected by chloride ion or by sulfide ion in acidic and in basic media.

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Because substances containing sodium, potassium and ammonium ions are used in the general
separation scheme, tests for the presence of Na+, K+ and NH4+ are carried out on an original
sample of solution, one that has not been treated with any reagents. The characteristic flame test
is used to detect sodium; the evolution of NH3 from a sample made basic with NaOH is used for
identification of ammonium ion. Potassium ion is also identified by a flame test made on the
original sample.
Precipitation of sodium or potassium salts from the solution containing the Group IV cations is
not practical.

Barium and calcium are separated from the alkali metal ions and, to some extent, from
magnesium by precipitation of their carbonates under the slightly basic conditions prevailing in
an ammonia-ammonium chloride buffer. The precipitate is dissolved in acetic acid, and,
successively, barium(II) is separated as the chromate, calcium(II) as the oxalate, and
magnesium(II) as an ammonium phosphate salt. Magnesium and potassium are also tested for in
the solution remaining from the carbonate precipitation.

Experimental Procedure

** Note: Make sure to record all observations throughout the experiment

** Note: Start a boiling water bath to be used throughout the experiment

** Note: Beware of using the correct chemical; many chemicals are easily mistaken for each
other

Ex K2CrO4 and K2C2O4, or 6M HCl and 1M HCl

You may assume that the 10mL unknown solution contains about 10 mg of a nitrate salt of
each cations. This is a sufficient amount for good qualitative tests.

NOTE: Prior to beginning, save 3 mL of your sample for Group IV analysis!

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Group I Cations

Step 1. Using a graduated cylinder, transfer 5 mL of your unknown sample into a test tube. Add
0.5 mL of 6 M HCl to the sample, a white solid should precipitate. Stir well using your glass stir
rod and centrifuge the solution. Decant the liquid and Save it for group II analysis. To ensure
precipitate was complete add 3 drops 6 M HCl to the liquid, decant again if more solid
precipitates. Continue until no solid precipitation occurs. To the solid add 1mL DI H2O,
centrifuge and decant. Repeat once more. Discard the wash and keep the solid.

Step 2. To the solid from step 1, which contains the chlorides of group I cations, add about 4
mL of DI H2O. Heat in the boiling water bath for at least 3 minutes, stirring constantly. Quickly,
centrifuge and decant the liquid which may contain Pb2+ into another test tube. Save the solid.

Step 3. Confirm the presence of lead. To the liquid form step 2, add 2 drops 6 M acetic acid and
3-4 drops of 1M K2CrO4. The formation of a yellow precipitate of PbCrO4 confirms the presence
of lead. Centrifuging out the solid may help in identification since the liquid phase is also
orange. After testing the solution can be discarded.

Step 4. If lead is present, take the solid from step 2 and add 6 mL of DI H2O. Heat in the boiling
water bath for 3 minutes. Centrifuge the liquid and repeat step 3 until no positive test for lead
occurs, or until the no solid remains. If no solid remains, then all the solid was lead, move onto
group II. If no positive test for lead occurs, but there is still solid present move onto step 5 with
the remaining solid.

Step 5. If lead is not present, add 6 M NH3 to the solid from step 2, until the solid is dissolved,
about 1-2 mL, and stir well, all the solid should dissolve. A black or dark grey precipitate
establishes the presence of the mercury (I) ion. Centrifuge and the decant the liquid into a test
tube.

Step 6. Confirm the presence of silver. To the liquid from step 5, add 3 mL 6M HNO3. Check
with pH paper to see that the solution is acidic. A white precipitate of AgCl confirms the
presence of silver.

Step 7. Alternative silver test. If the step 5 test for silver was inconclusive and mercury was
present, add 1mL 12 M HCl and 0.5mL 6 M HNO3 to the precipitate from step 4. Heat in a
boiling water bath for 4 minutes. Pour the liquid into a 30 mL beaker and boil gently for 1
minute. Add 3 mL of DI H2O. If AgCl is present a white solid should precipitate. Centrifuge and
decant off the liquid, discarding it. Confirm AgCl by dissolving the precipitate in 0.5mL 6 M NH3
and reforming with 1mL HNO3.

Each step in the qualitative analysis procedure is performed for a definite reason. You should go
9
over the steps until you known them well and why they are needed. Given experimental
observations made on a sample that is taken through the Group I procedure, you should be able
to determine whether a given cation in the group is present, absent, or still in doubt.

Figure 2. Flow chart for the analysis of the Group I cations.

1
0
 Group II

CAUTION: Reaction of thioacetamide with acidic media releases H2S, a highly toxic gas.
This portion of the experiment must be run in a fume hood!

Start group II with the solution saved in step 1 of the group I analysis

Step 1. To the saved solution from step 1, group I, add 0.5mL 3% HOOH. Pout into a 30mL
beaker and carefully boil down the solution to half its original volume.
Step 2. Swirl the liquid around in the beaker to dissolve any salts that may have formed, then
pour the solution into a test tube. Add 1-2drops 6 M HCl. Using pH paper test to see that the
solution is acidic. If it is not add more 6 M HCl until it becomes acidic. Once the proper pH has
been established add 1 mL of 1M thioacetamide and stir.

Heat the test tube in a boiling water bath for a least 5 minutes. The group II ions will precipitate
out of solution. The precipitates will usually be initially light, gradually turning black. Continue
to heat the test tube for 2 minutes after the precipitate blackens. Cool the test tubes under the
water tap and let stand until the test tube is cool enough to touch. Centrifuge out the precipitate,
and decant the solution into a test tube. The solution should be saved for analysis of the group
III cations. To the solid add 1 mL of 1M NH4Cl and 1 mL DI H2O. Centrifuge and decant,
discard the liquid.

Step 3. To the precipitate from step 2 add 1 mL of DI H2O and 1 mL 1 M NaOH. Heat in the
boiling water bath for 2 minutes. Centrifuge and decant, discard the liquid. Wash the
precipitate once with 2 mL of water and 1 mL of NaOH and once with 3 mL of water. Stir,
centrifuge, and decant, discarding the liquid each time.

Step 4. To the solid from step 3, add 1mL of DI H2O and 1 ml of 6 M HNO3. Heat in the
boiling water bath. Most of the reaction will occur within 1 minute, as some of the sulfides
dissolve and sulfur is formed. There may be a substantial amount of dark residue, which is
mainly free sulfur. Continue heating until no further reaction appears to occur, at least 2
minutes after the initial changes. Centrifuge and decant the solution into a test tube. Discard the
solid.

Step 5. To the solution from step 4, add 6 M NH3 until the solution is basic. Then add 0.5 mL
more and stir. If copper is present the solution will turn blue. A white precipitate in the solution
is indicative of bismuth (or possibly lead). Centrifuge and decant the solution, which may
contain Cu(NH3)42+, into a test tube, save the liquid for step 9. Wash the precipitate with 1 mL
of DI H2O and 0.5 mL 6M NH3. Stir, centrifuge, and decant.

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Step 6. If a precipitate was not present in step 5, move onto step 9. To the precipitate from
step 5, add 0.5 mL of 6 M HCl and 0.5 mL of DI H2O. Stir to dissolve any Bi(OH)2 that is
present. A white insoluble residue may contain lead. Centrifuge and decant the solution into
a test tube, save for step 7. To the solid add 1 ml of DI H2O and 0.5 mL of 6 M HCl.
Centrifuge and discard the wash, save the solid for step 8.

Step 7. Confirm the presence of bismuth. Add 2-3 drops of the decantate from step 6 to 300
mL of water in a beaker. A white cloudiness due to precipitation of BiOCl appears if the
sample contains bismuth. To the rest of the decantate, add 6 M NaOH until it is basic; a
white precipitate is Bi(OH)3. To the mixture add 2 drops of 0.1M SnCl2 and stir; if bismuth is
present, it will be reduced to a black metallic bismuth.

Step 8. Confirm the presence of lead. To the white precipitate from step 6 add 1 mL of 0.5 M
NaC2H3O2, sodium acetate. Heat gently if necessary to dissolve any lead-containing salts.
Add 1 mL DI H2O and 1 mL 6M H2SO4. A white precipitate of PbSO4 established the
presence of lead.

Step 9. Confirmation of the presence of copper. To further confirm the presence of Cu(II),
add 6 M acetic acid to half of the blue solution from step 5 until the color fades and the
solution becomes acidic. Then add 1-2 drops of 0.2 M K4Fe(CN)6 which will produce a red-
brown, or purplish, precipitate of Cu2Fe(CN)6 n the presence of copper.

11
Figure 3. Flow chart for the analysis of the Group II cations.

12
Group III

Start group III with the solution saved in step 2 of the group II analysis

Step 1. Pour the solution into a 30 mL beaker and boil until the volume is reduced to
approximately 2 mL. Remove from heat and add 1mL of 1 M NH4Cl and swirl the solution to
dissolve any crystallized salts. Add 6 M NH3 drop by drop until the solution becomes basic (as
indicated by pH paper). Add another 0.5 mL of NH3. Then add 1mL 1 M thioacetamide and stir
well. Pour the solution into a test tube and place in a boiling water bath for five minutes. Stir the
mixture occasionally as the precipitation proceeds.

Centrifuge out the precipitate and decant the liquid into a test tube. Add a few drops of 1
M thioacetamide to the liquid and put the test tube into the boiling water bath for a few minutes
to check for complete precipitation of the group III cations. Save the solution for analysis of the
group IV cations. To the precipitate, wash twice with 1mL 1 M NH4Cl and 2 mL of water and a
few drops of 6 M NH3, stirring well between washes. Discard the wash liquid.

Step 2. To the precipitate from step 1, add 1mL 6 M HCl. Mix and pour the slurry into a 30 mL
beaker. Boil the liquid for about 1 minute. Add 1 mL water, stir, and pour the slurry into a test
tube. Centrifuge and decant the liquid into a test tube, label and save for step 6. Wash the solid
twice with 1mL 6 M HCl and 1mL water, stirring and centrifuging between washes. Discard the
wash liquid.

Step 3. To the precipitate from step 2, add 1mL 6 M HCl and 1mL HNO3. Mix and put the test
tube in a boiling water bath for 1 minute. The precipitate should dissolve. Pour the solution into a
30 mL beaker and boil for 1 minute; add 2 mL of water and pour back into a test tube.

Step 4. Confirm the presence of cobalt. Pour one third the solution from step 3 into a test tube
and slowly add 1 mL of a saturated solution of NH4SCN in ethyl alcohol. If Co2+ is present, a
blue solution of Co(SCN)42- forms, either way the solution can be discarded. To the rest of the
solution add 6 M NaOH drop by drop until a precipitate remains after stirring, if no precipitate
forms, move onto step 6. Then add 0.5 mL of 6 M acetic acid to dissolve the precipitate. Pour
half the solution into a new test tube. To one of the solutions add 0.4g solid KNO2. Add 1mL
water and stir. A yellow precipitate of K3Co(NO2)6, which may form over a period of ten
minutes also confirms and presence of cobalt.

Step 5. Confirmation of the presence of nickel. To the over half of the solution from step 4, add
0.5 mL of dimethyglyoxime. A rose colored precipitate proves the presence of nickel.

Step 6. To the liquid from step 2, add 6 M NaOH until the solution is basic, then add 0.5 mL
more. Pour the solution into a 30 mL beaker and boil for 2 minutes. Remove from heat and add
1mL 1 M NaClO. Swirl the beaker for 30 seconds. Boil the liquid for 1 minute. Add 0.5 mL 6 M
NH3 and boil for another minute. Transfer the solution to a test tube and centrifuge the out the

13
solid. Save the liquid for step 10. Wash the solid twice with 2 mL of water and 0.5 mL 6 M
NaOH; centrifuge each time, discarding the wash.

Step 7. To the precipitate from step 6, which may contatin Fe(OH)3 and Ni(OH)2, add 1mL
water and 1mL 6 M H2SO4, if there is no precipitate move onto step 10. Stir and heat the tube for
a few minutes in the water bath; centrifuge out any undissolved solid. Decant the liquid into a
test tube and save for future steps. Discard the solid.

Step 8. Confirm the presence of iron. To one third of the liquid from step 7, add 2 mL water and
1-2 drops of 1 M KSCN. Formation of a deep red solution of FeSCN2+ is a definitive test for
iron. To another third of the liquid add 1-2 drops K4Fe(CN)6. A dark blue solution or precipitate
of KFe[Fe(CN)6] offers also indicates the presence of iron.

Step 9. Alternative confirmation of the presence of nickel. To one third the liquid from step 7 ,
add 6 M NH3, drop by drop until the solution is basic; add 4-5 more drops of 6 M NH3.
Centrifuge out any brown Fe(OH)3 solid and decant the solution into a new test tube. Add 0.5
mL dimethylglyoxime to the liquid. The formation of a rose colored solution proves the presence
of nickel.

Step 10. To the liquid from step 6, add 6 M acetic acid slowly until the solution is acidic.
Transfer the solution to a 30 mL beaker and boil it down to a volume of about 3 mL. Pour the
solution into a test tube. Add 6 M NH3, drop by drop until basic, then add 0.5 mL more. Stir the
mixture for 1 minute, centrifuge out any solid. If the solution is yellow, chromium is probably
present.

Step 11. Pour the solution into a 30 mL beaker, bring the solution to a boil, remove from the
source of heat, and add 0.5 mL 1 M BaCl2. In the presence of chromium, you obtain a very fine
yellow precipitate of BaSO4. Pour the slurry into a test tube and put in a boiling water bath for a
few minutes. Then centrifuge out the solid and decant the solution into a test tube. Discard the
liquid. Wash the precipitate with 2 mL water, centrifuge and discard the wash. If there is no
precipitate move onto group IV.

Step 12. Confirmation of the presence of chromium. To the precipitate from step 11, add 0.5 mL
6 M HNO3 and stir to dissolve the BaCrO4. Add 1mL water, stir the solution, then cool it under
the water tap. Add 2 drops of 3% HOOH. A blue solution which fades quickly confirms the
presence of chromium.

14
Figure 4. Flow chart for the analysis of the Group III cations.

15
Group IV

Start group IV with the solution saved in step 1 of the group III analysis

Step 1. Pour the solution into a 30 mL beaker and boil it down to a volume of 2 mL, if you have
less than 2 mL you can skip this step. Transfer the liquid to a test tube and centrifuge out any
solid matter, which may be discarded. Put the liquid back into the beaker and add 1mL 6 M HCl
and boil the solution to dryness. Transfer the beaker to a hood and heat the dry solid to drive off
all the ammonium salts that were added in previous steps. Stop heating when the visible smoke
from these salts is no longer being evolved. Let the beaker cool, and then add 0.5 mL 6M HCl
and 2 mL water. Warm the solution gently to dissolve the remaining salts. Pour the solution into
a test tube; discard any insoluble material by centrifuging and decanting.

Step 2. To your solution add 6 M NH3 until the solution becomes basic by pH paper; add 0.5 mL
more. Then add 1mL 1 M (NH4)2CO3 and stir. Put the test tube in a hot, but not boiling, water
bath, and without any heating, leave the tube in the bath for two minutes, stirring occasionally.
Centrifuge and decant the liquid. Wash the precipitate, which may contain BaCO3, CaCO3 with 2
mL water. Centrifuge out the precipitate, and discard the wash.

Step 3. Confirm the presence of barium. Add 0.5 mL 6 M acetic acid to the precipitate from step
2 and stir to dissolve the solid. Add 1mL water and 2 drops 6 M NH3 and mix. Then add 0.5 mL
1 M K2CrO4. A yellow precipitate indicates the presence of barium. Stir for a minute and
centrifuge out the solid.

Step 4. Confirm the presence of barium. Dissolve the solid from step 3 in 0.5mL 6 M HCl. Add
1mL water and 0.5 mL 6 M H2SO4 and stir the solution for 30 seconds. A white precipitate of
BaSO4 establishes the presence of barium

Step 5. To the liquid from step 3, add 6 M NH3 until the solution becomes basic by pH paper. At
this point the solution becomes yellow. Add 0.5 mL 1 M K2C2O4, stir and let the solution stand
for 1 minute. A white precipitate of CaC2O4 H2O is confirmation for the presence of calcium.

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Figure 5. Flow chart for the analysis of the Group IV cations.

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