Identifying a Simple Salt

The basic testing procedure for identifying a salt is as follows.

Appearance of compound
The compound will most likely be in solid form. Note the color and shape of the crystals. Ionic
compounds formed from the representative elements tend to be white or colorless, while ions of
transition elements tend to be colored. The following is a table of the colors of metal ions in solution
with NO3-.
Ion Color
Co2+ rose
Co3+ violet
Cr3+ violet
Cu2+ blue
Fe2+ pale green, pale violet
Fe3+ yellow-brown
Mn2+ pale pink
Ni2+ blue-green
Heating effect
Heating a compound can cause a liquid to condense on the inside of the test tube. This is probably water,
indicating that the compound is a hydrate. If a gas is given off, note the color and odor of the gas. The
nitrate, carbonate, and sulfite ions may decompose, as illustrated by the reactions:
2 Pb(NO3)2(s) + heat → 2 PbO(s) + O2(g) + 4 NO2(g, brown)
CaCO3(s) + heat → CaO(s) + CO2(g, colorless, odorless)
CaSO3(s) + heat → CaO(s) + SO2(g, colorless, pungent)
Some bromides and iodides decompose to give Br2(g, orange-brown) and I2(g, purple).
Flame test
Solutions of ions, when mixed with concentrated HCl and heated on a nickel/chromium wire in a flame,
cause the flame to change to a color characteristic of the atom. Visible colors occur with the following
ions:
Sodium Bright yellow (intense, peristent)
Potassium Pale violet (slight, fleeting)
Calcium Brick red (medium, fleeting)
Strontium Crimson (medium)
Barium Light green (slight)
Lead Pale bluish (slight, fleeting)
Copper Green or blue (medium, persistent)

Solubility in water
Place one small spatula of the compound in 1 mL of water. If the compound is soluble this amount will
dissolve after considerable stirring. If the compound is moderately soluble, some of this amount will
dissolve. If the compound is insoluble, even a very small amount will not dissolve.
General solubility rules:
All nitrates are soluble.
Practically all sodium, potassium, and ammonium salts are soluble.
All chlorides, bromides, and iodides are soluble except those of silver, mercury(I), and lead(II).
All sulfates are soluble except those of strontium, barium, and lead(II), which are insoluble, and those
of calcium and silver which are moderately soluble.
All carbonates, sulfites, and phosphates are insoluble except those of sodium, potassium, and
ammonium.
All sulfides are insoluble except those of the alkali metals, the alkaline earth metals, and ammonium.
All hydroxides are insoluble except those of the alkali metals. The hydroxides of calcium, strontium, and
barium are moderately soluble. Ammonium hydroxide does not exist; ammonium hydroxide is a
misnomer for aqueous ammonia, NH3(aq).
Reaction with nitric acid
Add nitric acid to the compound and observe any reaction that occurs. If the compound dissolved in
water, it should dissolve in nitric acid. If it did not dissolve in water, but appears to be dissolving in nitric
acid, it is undergoing a chemical reaction. In general, compounds that contain anions that are the
conjugate bases of weak acids will react (unless the compounds are very insoluble). For example:
CaCO3(s) + 2 H+(aq) → Ca2+(aq) + H2O(l) + CO2(g, colorless, odorless)
NiS(s) + 2 H+(aq) → Ni2+(aq) + H2S(g, colorless, rotten egg smell)
Ca3(PO4)2(s) + 6 H+(aq) → 3 Ca2+(aq) + 2 H3PO4(aq)
The remaining tests must be perfomed on a solution of the compound.
If the compound is insoluble in water, dissolve it in nitric acid. Otherwise, dissolve in water.
Reaction with sodium hydroxide
Add NaOH dropwise to the solution, stir or shake the solution, and observe any reaction (if the
compound was dissolved in nitric acid, the first several drops will neutralize the acid so be sure to check
the pH with litmus paper). Look for a precipitate (refer to the solubility rules for hydroxides). If a
precipitate forms, continue adding NaOH. Some metal hydroxides are amphoteric and will form a
complex ion and redissolve. See Figures 1, 2, and 3 for an example of this reaction. The following ions
are amphoteric:
Species Acidic Solution Slightly Basic Solution Basic Solution
Al3+ Al3+(aq) Al(OH)3(s) Al(OH)4-(aq)
Cr3+ Cr3+(aq) Cr(OH)3(s) Cr(OH)4-(aq)
Pb2+ Pb2+(aq) Pb(OH)2(s) Pb(OH)42-(aq)
Zn2+ Zn2+(aq) Zn(OH)2(s) Zn(OH)42-(aq)
Sn4+ Sn4+(aq) Sn(OH)4(s) Sn(OH)62-(aq)
Reaction with ammonia
Add NH3 dropwise to the solution, stir or shake the solution, and observe any reaction. If a metal
hydroxide precipitate forms, continue adding ammonia. Some metal hydroxides fom a complex ion and
redissolve. See Figures 4, 5, and 6 for an example of this reaction. The following ions form ammonia
complexes:
Acid Solution Basic Solution Solution with Excess NH3 Color of Complex
Ni2+(aq) Ni(OH)2(s) Ni(NH3)62+(aq) violet
Cu2+(aq) Cu(OH)2(s) Cu(NH3)42+(aq) blue
 Zn2+(aq) Zn(OH)2(s) Zn(NH3)62+(aq) colorless
Ag+(aq) Ag2O(s) Ag(NH3)2+(aq) colorless
Cd2+(aq) Cd(OH)2(s) Cd(NH3)42+(aq) colorless
Reaction with hydrochloric acid
Add HCl dropwise until solution tests acidic to litmus paper and observe any reaction. A precipitate will
form with any cation that forms an insoluble chloride (refer to the solubility rules). For example:
Pb2+ + 2Cl- → PbCl2(s)
Reaction with sulfuric acid
Add H2SO4 dropwise until solution is acidic and observe any reaction. A precipitate will form with any
cation that forms an insoluble sulfate (refer to the solubility rules). For example:
Ba2+ + SO42- → BaSO4(s)
Reaction with silver nitrate
Add HNO3 dropwise until solution is acidic (unless of course it was dissolved in nitric acid), then add a
few drops of AgNO3 and observe any reaction. A precipitate will form with certain cations that form
insoluble silver compounds, but because of the acidic environment, some insoluble silver salts (e.g. salts
containing CO32-, S2-, and PO43- ions) are "destroyed." Cl-, Br-, and I- form insoluble compounds, while
SO42- forms a moderately insoluble compound.
Ag+ + Cl- → AgCl(s)
Reaction with barium nitrate
Add HNO3 dropwise until solution is acidic, boil the solution for two minutes, then test with litmus
paper. Continue adding and boiling until solution remains acidic after boiling. Cool the solution and add
a few drops of Ba(NO3)2 and observe any reaction. A precipitate will form with anions that form an
insoluble barium compound (except the ones destroyed by acid as in the above test).
Specific Tests
Sometimes the above tests can not definitively confirm the presence of a specific ion. In these cases, it
is necessary to do specific tests for a particular ion.
Example Unknown Salts
Sample 1 had the following characteristics:
Visual test: white crystalline powder
Heat test: brown gas given off
Flame test: no color identified
Solubility in water: soluble
Nitric acid: soluble
Hydroxide: formed an insoluble white precipitate, then dissolved with excess NaOH
Ammonia: formed an insoluble white precipitate which did not redissolve in excess NH3
Hydrochloric acid: formed an insoluble white precipitate
Analysis of observations:
The brown gas given off during the heat test indicates presence of the NO3- ion, since the NO3- ion
reacts to form brown NO2 gas as shown below:
2 Pb(NO3)2(s) + heat → 2 PbO(s) + O2(g) + 4 NO2(g)
The white precipitate which formed and then redissolved with the addition of sodium hydroxide
indicates the presence of an amphoteric cation. The possibilities are Al, Cr, Pb, Zn, and Sn. The reaction
occurs as follows:
Cr3+(aq) + 3 OH-(aq) → Cr(OH)3(s)
Cr(OH)3(s) + OH-(aq) → Cr(OH)4-(aq)
Since the cation does not form an ammonia complex, it eliminates Zn from the list of possible cations
established above.
There are only three cations which form precipitates with hydrochloric acid, Pb2+, Ag+, and Hg22+. Of
these three, only Pb2+ is amphoteric. The reaction with chloride occurs as follows:
Pb2+ + 2 Cl- → PbCl2(s)
Conclusion: Sample 1 is Pb(NO3)2

Sample 2 had the following characteristics:

Visual test: white crystalline powder
Heat test: no reaction
Flame test: green color observed
Specific barium test (precipitation with CrO42-): formed an insoluble yellow precipitate
Solubility in water: insoluble
Nitric acid: produced odorless, colorless gas
Analysis of observations:
The green color observed during the flame test indicates the presence of barium. Although the
remaining tests could be done to confirm the presence of barium, none is specific for just the Ba2+ ion.
Therefore, the specific barium test is used.
The yellow precipitate produced by the barium test confirms the presence of barium. The reaction
occurs as follows:
Ba2+(aq) + CrO42-(aq) → BaCrO4(s)
The odorless, colorless gas produced by the addition of nitric acid is CO2.
This indicates the presence of the CO32- ion.
Conclusion: Sample 2 is BaCO3
Sample 3 had the following characteristics:
Visual test: yellow/brown solid
Heat test: no reaction
Flame test: no reaction
Solubility in water: soluble
Nitric acid: soluble
Sodium hydroxide: formed an insoluble white precipitate which did not redissolve in excess NaOH
Ammonia: formed an insoluble white precipitate which did not redissolve in excess NH3
Hydrochloric acid: no reaction
Specific iron(III) test (formation of a thiocyanate complex): solution turned blood red
Silver nitrate: formed an insoluble white precipitate
Specific chloride, bromide, iodide test: precipitate dissolved with addition of 6 M ammonia
Analysis of observations:
The color of the solid is characteristic of the Fe3+ ion.
Since the compound forms an insoluble precipitate with hydroxide, it eliminates the alkali metals,
calcium, strontium, and barium. Since the cation is not amphoteric, it also eliminates aluminum,
chromium, lead, zinc, and tin.
The cation does not form an ammonia complex, which eliminates nickel, copper(II), silver, and cadmium.
Since there is no reaction with Cl-, Hg22+ is also eliminated. Of the ions which have not been eliminated
(Fe3+, Mn2+, Bi2+), Fe3+ is the most likely. A specific ion test is needed to confirm the presence of Fe3+.
The red solution produced by the iron(III) test confirms the presence of iron(III). The reaction occurs as
follows:
Fe3+(aq) + SCN-(aq) → Fe(SCN)2+(aq)

The precipitate formed by the addition of silver nitrate indicates the presence of either chloride,
bromide, or iodide. Although the colors are different (AgCl white, AgBr cream, AgI yellow), they are
difficult to distinguish, and a specific ion test is needed to determine which one is present.
The specific ion test indicated that the anion present is Cl-. The reaction occurs as follows:
Ag+(aq) + Cl-(aq) → AgCl(s)
AgCl(s) + 2 NH3(aq) → Ag(NH3)2+(aq) + Cl-(aq)
Conclusion: Sample 3 is FeCl3
Specific Tests
Cation Identification Tests
Generally Soluble Cations
Ammonium Ions:
Take a small amount of the material to be tested and place it in a 50-mL beaker. Add 6 M NaOH and
smell cautiously. The odor of ammonia indicates the presence of ammonium ions. If you do not smell
ammonia, warm the beaker and again smell the emitted vapors. The liberated ammonia will also change
the color of a moistened strip of red litmus paper held at the entrance of the test tube.
NH4+(aq) + OH-(aq) → NH3(g) + H2O
This test is very reliable. It should be performed whenever the generally soluble cations, NH4+, Na+,
and K+, are suspected.
Sodium Ions:
The most common method of identification of Na+ is the flame test. Sodium imparts a brilliant, long
lasting, yellow flame that masks colors from other ions. The test may be performed on a small sample
of the unknown treated with concentrated HCl or a few drops of solution unknown treated with
concentrated HCl. The flame should be bright and it should last as long as that of 0.1 M NaCl. Sodium is
a common impurity and traces will be found in almost any unknown. You must learn to distinguish
between an unknown that has sodium ion as the cation and an unknown that has sodium ion as an
impurity.
Potassium Ions:
The most common method of identification of K+ is the flame test. The test may be performed on a
small sample of the unknown treated with concentrated HCl or a few drops of solution unknown treated
with concentrated HCl. The violet flame is not intense but it is clearly visible in the absence of sodium
ions. Cobalt glass filters yellow light from sodium impurities and allows the violet flame to be seen. Do
not confuse the glowing wire for the potassium flame.
Cations That Form Insoluble Chlorides
Silver Ions:
Although Ag+, Pb2+, and Hg22+ all form insoluble white chlorides, Ag+ is the only one of these cations
that forms an ammonia complex. Therefore, AgCl dissolves readily in aqueous NH3. When the resulting
solution is acidified with HNO3, AgCl reprecipitates.
AgCl(s) + 2NH3(aq) → Ag(NH3)2+(aq) + Cl-(aq)
Ag(NH3)2+(aq) + Cl-(aq) + 2H3O+ → AgCl(s) + 2NH4+ + 2H2O
Add 3 M HCl dropwise to the solution being tested. If a white precipitate is formed, centrifuge and
remove the supernatant liquid. Add 6 M NH3 solution to the precipitate. If the precipitate dissolves, add
6 M HNO3. Formation of a white precipitate indicates Ag+.

Lead Ions:
Although PbCl2 is insoluble at room temperature, its solubility is increased dramatically at higher
temperatures; it dissolves readily in boiling water. Pb2+ also forms an insoluble white sulfate, which
dissolves in a solution containing acetate ion due to the formation of the weak electrolyte,
Pb(CH3COO)2. The addition of chromate ion to this lead acetate solution yields a precipitate of yellow
lead chromate.
Pb2+(aq) + SO42-(aq) → PbSO4(s)
PbSO4(s) + 2CH3COO-(aq) → Pb(CH3COO)2(aq) + SO42-(aq)
Pb(CH3COO)2(aq) + CrO42-(aq) → PbCrO4(s) + 2CH3COO-(aq)
To the solution to be tested add 3 M HCl dropwise. (A large excess of HCl must be avoided because of
the formation of the soluble chloro complex, PbCl42-.) Centrifuge and remove the supernatant from the
white precipitate (PbCl2). Add hot water to the precipitate and stir. If the precipitate dissolves, Pb2+ is
indicated. Add 3 M H2SO4 to the hot solution. Centrifuge and remove the supernatant liquid from the
white precipitate (PbSO4). To the precipitate add 3 M NH4(CH3COO) and stir. If the white precipitate
was PbSO4, it will dissolve. To confirm, add a few drops of 0.5 M K2CrO4 to the resulting solution. A
yellow precipitate of PbCrO4 indicates the presence of Pb2+.
Mercury(I) Ions:
When Hg2Cl2 is treated with aqueous NH3 a reaction occurs in which free mercury and
amidochloromercury(II) are formed.
Hg2Cl2(s) + NH3(aq) → Hg(l) + HgNH2Cl(s) + HCl(aq)
The HgNH2Cl is a white solid, while the Hg in a finely divided state appears black. The resultant mixture
is gray to black.
Add 3 M HCl to the solution to be tested for Hg22+. If a white precipitate forms, centrifuge and remove
the supernatant liquid. To the precipitate, add 6 M NH3 and stir. The appearance of a gray to black
precipitate is positive for Hg22+.
Cations That Form Insoluble Sulfates
Identification tests for Pb2+ and Ag+ (Ag2SO4 is moderately soluble) are described above (Cations that
form Insoluble Chlorides). Ba2+, Sr2+, and Ca2+ form moderately soluble sulfates.
The alkaline earth ions Mg2+, Ca2+, Sr2+, and Ba2+ are one of the best examples of a periodic
relationship among the elements of a family. Solubilities of their compounds are graduated nicely and
the separations (qualitatively) can be accomplished readily. Flame tests are very important.
Barium Ions:
Barium ions can be identified by precipitation of its insoluble yellow BaCrO4 salt. If Ca2+ or Sr2+ are
present they will also precipitate in the presence of high concentrations of CrO42-. However, the
chromates of Ca2+ and Sr2+ are moderately soluble; their precipitation can be prevented by addition
of acetic acid. This weak acid provides sufficient hydronium ions to lower the CrO42- concentratiion
enough to keep CaCrO4 and SrCrO4 in solution but to allow the BaCrO4 to precipitate.
2CrO42-(aq) + 2H+(aq) → Cr2O72-(aq) + H2O
The flame test on the solid chromate is important for confirmation.
To about 1 mL of solution add 10 drops of 6 M CH3COOH. Then add a few drops of 0.5 M K2CrO4 solution.
The appearance of a yellow precipitate indicates the presence of Ba2+. To confirm, dissolve the
precipitate in concentrated HCl and flame test.
Strontium Ions:
Strontium can be identified, in the absence of calcium, by precipitating its sulfate. To the solution add
0.1 M H2SO4 dropwise. The formation of a finely-divided, crystalline, white precipitate indicates the
presence of Sr2+. (Ba2+ must be absent, of course.) To confirm, dissolve the precipitate in concentrated
HCl and flame test.
Calcium Ions:
If Ba2+ and Sr2+ are absent, Ca2+ may be precipitated as the oxalate from neutral or alkaline solutions.
Test the acidity of the solution with litmus paper. If it is acidic, add 3 M NH3 until basic. Then add 0.2 M
(NH4)2C2O4 solution. The formation of a white precipitate indicates the presence of Ca2+. Confirm by
adding a few drops of concentrated HCl and flame testing.
Cations That Form Ammonia Complexes
Cadmium Ions:
Cadmium forms a yellow precipitate with sulfide ion either from a neutral solution containing free Cd2+
or from an ammoniacal solution of Cd(NH3)42+. Since most sulfides are insoluble, and many of them
are black, the presence of other metal ions may make it difficult to detect the yellow color of CdS.
Therefore, separations must be as complete as possible before testing for Cd2+.
Cd2+(aq) + S2-(aq) → CdS(s)
Cd(NH3)42+(aq) + S2-(aq) → CdS(s) + 4NH3
To a solution of Cd2+ or to a solution thought to contain Cd(NH3)42+ add 0.1 M Na2S solution dropwise.
The formation of a yellow precipitate confirms the presence of Cd2+.
Copper(II) Ions:
The very distinct deep blue color of the copper ammonia complex can be used to identify Cu2+. This
identification can be carried out in the presence of other cations which form either colorless ammonia
complexes or white precipitates. Thus, Zn2+, Cd2+, Al3+, among others, will not interfere.
In relatively dilute solutions the color of the ammonia complex may not be intense enough to give an
unqualified identification, and some other test for confirmation must be used. Cu2+ forms a very
insoluble reddish-brown hexacyanoferrate(II).
2Cu2+(aq) + Fe(CN)64-(aq) → Cu2Fe(CN)6(s)
Other cations that react with this reagent to form highly colored precipitates must be absent (Co2+ and
Fe3+ for example). Acidify the test solution with acetic acid. Then add a few drops of 0.1 M potassium
hexacyanoferrate(II) solution (K4Fe(CN)6). A red-brown precipitate confirms the presence of Cu2+.
Nickel(II) Ions:
Nickel(II) is one of the easiest cations to identify. Ni2+ forms a red precipitate with dimethylglyoxime in
a buffered acid solution. Palladium(II) is the only other cation which forms a precipitate with this reagent.
However, a few other cations can interfere. Cobalt(II) preferentially forms a dark brown solution with
dimethylglyoxime, and excess reagent must be used in its presence.
Acidify the solution to be tested with 6 M CH3COOH. Then add about one mL of 0.2 M NaOOCCH3
solution. Add dimethylglyoxime solution dropwise. A bright red precipitate is positive for Ni2+.
Zinc Ions:
Zinc forms one of the few insoluble white sulfides. It is precipitated from a solution of the ammonia
complex. Small traces of cations that form dark colored sulfides will obviously interfere.
Add an excess of 3 M NH3 to the test solution, so that any zinc present is in the form of Zn(NH3)42+.
Then add a few drops of 0.1 M Na2S solution. A white precipitate indicates the presence of Zn2+.
Cations That Form Amphoteric Hydroxides
Aluminum Ions:
Aluminum is generally identified by making use of the amphoteric property of its hydroxide and the red
color of the "lake" AlOH3 forms with the reagent, aluminon. Aluminon is a dye (an organic molecule,
usually fairly large, that absorbs visible light). As the Al(OH)3 precipitates the dye is adsorbed on the
Al(OH)3 particles. The adsorption of the dye is called "laking." Aluminum is a fairly common impurity
and care must be taken that trace quantities are not reported. Since most laboratory manipulations are
carried out in glass containers, silica gel, which physically resembles aluminum hydroxide, is also a
common impurity.
Adjust the pH of about 1 mL of the test solution (with 3 M NaOH and 3 M HNO3) to precipitate the
hydroxide. Centrifuge the mixture. Remove the mother liquor with a capillary pipet and wash the
precipitate with distilled water. Centrifuge the mixture. Remove the mother liquor with a capillary pipet
and wash the precipitate with distilled water. Centrifuge the mixture and remove the mother liquor with
a capillary pipet. These repeated washings remove other ions from the precipitate. Dissolve the
precipitate in 3 M HNO3. If any precipitate does not dissolve in the nitric acid, remove the supernatant
to a clean test tube and discard the residue. Add two drops of aluminon reagent (avoid any excess). Add
3 M NH3(aq) until the solution is basic. Centrifuge. A red, gelatinous precipitate (sometimes called a red
lake) indicates Al3+.
Any precipitate that remains after the addition of the nitric acid is probably silica gel, SiO2•xH2O. Silica
gel is present in many solutions; it is leached from glass containers. Any silica gel present must be
removed before the addition of the aluminon and the ammonia because silica gel will also give a red
lake.
Do not confuse traces of red-brown ferric hydroxide for the red lake. Other precipitates will also form
colors with the reagent. The supernatant liquid will be an intense blue-purple color if too much reagent
has been added. This color has nothing to do with the presence of aluminum. The color of the reagent
is sensitive to changes in pH, (the reagent is an acid-base indicator).
Chromium(III) Ions:
Chromium can be taken through a series of colored tests which leaves no doubt as to its identity.
Chromium(III) forms a steel green hydroxide which dissolves in excess strong base to give a deeply green
colored solution of the hydroxy complex. Treating this complex with 3% hydrogen peroxide gives the
yellow solution of the chromate ion, which upon acidification with dilute nitric acid gives the orange
color of dichromate. Treatment of the cold solution of dichromate with 3% hydrogen peroxide gives the
intense blue color of a peroxide of chromium. (The actual composition of this peroxide is not known,
but it is believed to have the empirical formula CrO5.) This peroxide readily decomposes to the pale
violet color of the original hydrated chromium(III) ion. In low concentrations of dichromate the blue
color is fleeting, and attention must be focused on the test tube during the addition of the hydrogen
peroxide to avoid missing the color change.
Cr(OH)4- (green) --(H2O2)--(OH-)→ CrO42- (yellow)
CrO42- --(H+)→ Cr2O72- (orange)
Cr2O72- --(H2O2)--(HNO3)→ CrO5 (blue)→ Cr(H2O)63+ (violet)
The following color changes are all indicative of Cr3+. Add an excess of 6 M NaOH to about one mL of
test solution. To this green solution add 10 drops of 3% H2O2. Heat the test tube in the water bath until
the excess H2O2 is destroyed as indicated by the cessation of bubbles. Acidify the yellow solution with
3 M HNO3. Cool the resulting orange solution in an ice bath. To the cooled solution add a drop or two
of 3% H2O2 and observe the immediate fleeting blue color.
Tin(IV) Ions:
Sn4+ is most conveniently identified by reduction of Sn4+ to Sn2+ with iron. The Sn2+ solution is treated
with HgCl2 solution, whereupon Sn2+ is oxidized to Sn4+ and, simultaneously, HgCl2 is reduced to
Hg2Cl2 (a silky, white precipitate). The Hg2Cl2 is further reduced by Sn2+ to Hg, which appears black.
Sn4+(aq) + Fe(s) → Sn2+(aq) + Fe2+(aq)
Sn2+(aq) + 2HgCl2(aq) → Sn4+(aq) + Hg2Cl2(s) + 2Cl-(aq)
Sn2+(aq) + Hg2Cl2(s) → Sn4+(aq) + 2Hg(l) + 2Cl-(aq)

Add some concentrated HCl to the solution to be tested for Sn4+. Place an iron brad (or small iron wire)
in this solution and heat in a water bath for 5 minutes. Take the clear solution (filter if necessary) and
add HgCl2 solution dropwise. The appearance of a silky, white precipitate, which then turns black,
confirms the presence of tin.
Other Cations
Manganese(II) Ions:
Manganese is easily identified by oxidation of Mn2+ to purple MnO4- using sodium bismuthate
(NaBiO3). Heat must be avoided to prevent the decomposition of permanganate ion to brown, insoluble
manganese dioxide. Chloride ion must be absent, because it reduces permanganate ion to either
manganese dioxide or manganese(II) depending upon the conditions.
Acidify the test solution with 3 M HNO3. Add solid NaBiO3 and stir. Centrifuge. If the supernatant has
the characteristic purple color of MnO4-, Mn2+ was present.
2Mn2+ + 14H+ + 5NaBiO3 → 5Bi3+ + 5Na+ + 7H2O + 2MnO4
Bismuth(III) Ions:
Bismuth(III) forms a highly insoluble hydroxide which upon treatment with the hydroxy complex of tin(II)
is immediately converted to free bismuth, a black precipitate.
3Sn(OH)42-(aq) + 2Bi(OH)3(s) → 2Bi(s) + 3Sn(OH)62-(aq)
Precipitate Bi3+ from the test solution with 3 M NaOH and centrifuge the precipitate. Then, to a solution
of tin(II) chloride add with stirring 6 M sodium hydroxide until the precipitate of tin(II) hydroxide which
first forms just redissolves. This solution is then added dropwise to the precipitate of bismuth(III)
hydroxide. The rapid formation of a black color confirms bismuth.
Iron(III) Ions:
The Fe3+ ion is readily identified in a dilute nitric acid solution through the blood red color of its
thiocyanate complex. A large excess of reagent should be avoided.
Fe3+(aq) + SCN-(aq) → Fe(SCN)2+(aq)
Acidify the solution with 3 M HNO3. Then add a few drops of 0.1 M NH4SCN solution. The solution turns
red if Fe3+ is present.
Anion Identification Tests
Carbonate Ions:
The most characteristic reaction of carbonate is the formation of carbon dioxide upon treatment with
acid:
CO32-(aq) + 2H+(aq) → CO2(g) + H2O(l)
The colorless, odorless carbon dioxide can be identified by bubbling it through a saturated solution of
barium hydroxide, with which it forms a white precipitate of barium carbonate.
CO2(g) + Ba2+(aq) + 2OH-(aq) → BaCO3(s) + H2O(l)
Assemble a gas-liberation apparatus from a small test tube and a section of bent tubing. Dissolve or
suspend a portion of your compound in a small amount of water and place it in the small test tube. Add
about 0.5 mL of 6 M HCl and quickly fit the tube into the small test tube, allowing the gas liberated to
bubble into a 6" test tube of saturated Ba(OH)2 solution. The formation of a white precipitate in the
large test tube (if the gas liberated is odorless) is a positive test for carbonate. It is imperative to test
the gas-liberation apparatus by adding HCl to Na2CO3.
Sulfide Ions:
When treated with nonoxidizing acids (HCl, CH3COOH) sulfides react to liberate H2S gas (rotten-egg
odor). If the sulfide is very insoluble liberation of the gas may require concentrated acids (indeed some
sulfides, HgS, CuS, are so insoluble that dissolution requires special treatment). The gas is generally
identified by its odor and its precipitation of colored sulfides of various metal ions. Sulfides or hydrogen
sulfide also are oxidized to elemental sulfur and sulfate by oxidizing agents such as permanganate, nitric
acid, sulfuric acid, Fe(III), etc.
3H2S(aq) + 2H+(aq) + 2NO3-(aq) → 2NO(g) + 4H2O + 3S(s)
Acidify a sample with 6 M hydrochloric acid and warm. Cautiously smell the gas evolved and also test
the gas with a piece of filter paper moistened with lead acetate solution. A foul smelling gas which turns
lead acetate paper black constitutes a positive sulfide test.
Sulfate Ions:
Sulfate is conveniently identified by precipitation of BaSO4. Other insoluble barium salts contain anions
of weak acids (CO32-, SO32-and PO43-). Precipitation of these anions is prevented by acidifying the
solution.
Acidify the test solution with 6 M HCl, and add a few drops of 0.2 M BaCl2 solution. A white precipitate
indicates the presence of SO42-.
Nitrate Ions:
The most notable feature of the chemistry of the nitrate ion is its oxidizing ability as illustrated by the
following reactions:
3Fe2+(aq) + 4H+(aq) + NO3-(aq) → NO(g) + 2H2O + 3Fe3+(aq)
In the last reaction the nitrogen oxide reacts with excess Fe2+ to give the brown complex ion Fe(NO)2+.
It is the formation of this brown complex that is used to identify NO3- (called the brown ring test).
Acidify about 2 mL of the test solution with 3 M H2SO4 and then dissolve one-half spatula full of solid
FeSO4.7H2O in the acidified solution. Cool the solution and then carefully introduce about 0.5 mL of
concentrated H2SO4 by allowing it to flow down the side of the tilted test tube. Allow the solution to
sit undisturbed so that the sulfuric acid forms a definite layer. The formation of a brown color at the
interface of the layer constitutes a positive test for nitrate.
Phosphate Ions:
The precipitation usually used to identify phosphate is the formation of yellow ammonium
molybdophosphate from ammonium molybdate in acidic solution.
12MoO42- + 3NH4+ + PO43- + 24H+ → (NH4)3[P(Mo12O40)] + 12H2O
Acidify the sample with concentrated nitric acid and add several drops in excess. Then treat the solution
with ammonium molybdate reagent and warm. The formation of a yellow crystalline precipitate
confirms the presence of phosphate.
Chloride, Bromide, and Iodide Ions:
All three of these anions form insoluble silver salts. Although the precipitates are of different colors
(AgCl white, AgBr cream, AgI yellow) the colors are difficult to distinguish, and confirmatory tests are
necessary.
Silver chloride, the most soluble of the three, dissolves readily in 6 M NH3 solution because of formation
of the ammonia complex. Furthermore, when the solution of the ammonia complex is acidified, AgCl
reprecipitates. Neither AgBr nor AgI will dissolve readily in 6 M NH3, a much higher concentration of
NH3 being required to form the complex.
Cl-(aq) + Ag+(aq) → AgCl(s)
AgCl(s) + 2NH3(aq) → Ag(NH3)2+(aq) + Cl-(aq)
Ag(NH3)2+(aq) + Cl-(aq) + 2H+(aq) → AgCl(s) + 2NH4+(aq)
Bromide and iodide are usually identified by oxidation to the free elements with chlorine. The elements
thus formed are extracted into carbon tetrachloride and identified by their color.
2Br-(aq) + Cl2(g) → Br2(g) + 2Cl-(aq)
2I- (aq) + Cl2(g) → I2(s) + 2Cl-(aq)
Chloride:
Acidify the test solution with 3 M HNO3. Then add several drops of 0.1 M AgNO3. If a white precipitate
forms, centrifuge and remove the supernatant. To the precipitate add 6 M NH3 with stirring. If the
precipitate dissolves, add 6 M HNO3 to the solution. A white precipitate will form if the original test
solution contained Cl-.
Bromide and Iodide:
Acidify the sample with several drops of 6 M HCl and add 4-5 drops of carbon tetrachloride. Then add
about 0.5 mL of chlorine water and shake. Appearance of an orange-brown carbon tetrachloride layer
indicates the presence of bromide. Formation of a purple layer indicates iodide.