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How Can Eleven Colorless Solutions

be Chemically Identified?
Developed by Department of Chemistry, Brown University

In this experiment, the following eleven colorless solutions will be supplied and labeled only with numbers.
The numbered solutions will be identified by mixing samples of the solutions with each other, analyzing pH,
and conducting flame tests. No other chemicals need to be used.

1.0 M sodium thiosulfate (Na2S2O3) 1.0 M ammonium chloride (NH4Cl)

1.0 M hydrochloric acid (HCl) 0.1 M zinc chloride (ZnCl2)
1.0 M sodium carbonate (Na2CO3) 0.1 M silver nitrate (AgNO3)
0.1 M sodium oxalate (Na2C2O4) 0.1 M aluminum nitrate (Al(NO3)3)
0.1 M barium nitrate (Ba(NO3)2) 3% hydrogen peroxide (H2O2)
0.1 M manganese (II) nitrate (Mn(NO3)2)

To prepare for this experiment, draw on the following information to develop a systematic and logical flow
chart that will be used to identify the solutions. The most efficient way to start the analysis is by using a
single unknown solution. When some unknowns have been identified, they can be used as reagents to
identify others. A similar problem using a different set of unknowns is shown at the end of the
Introduction. Once all solutions have been tentatively identified, you are required to perform addional tests
for verifying the solutions.

Flame Tests
When a drop of some of the unknown solutions is placed on a wire loop and vaporized in a flame, the flame
becomes brightly colored. The intense heat of the flame releases free (not bonded) atoms from molecules.
The electrons of these free atoms are raised to high-energy states by the hot flame. When the electron
returns to the ground state, light with a discrete frequency (color) characteristic of the element is emitted.
Among the ions used in this lab, there are only two strong light emitters.

Metal Flame color

Sodium yellow/orange
Barium green

The sodium flame is so intense that only traces of sodium (e.g., from finger prints on the wire) give
somewhat yellow flames. Therefore it is important to inspect the flame from the wire before adding each
chemical. Remember how yellow the flame is just from the wire. When there is sodium present in the
sample the change in intensity of the orange flame color will be significant.

PH Tests
pH Paper Color Interpretation Solution
(See label on vial)
strong acid HCl
weak acid Al(NO3)3
weak base Na2CO3

While Al(NO3)3 and Na2CO3 solutions do not obviously contain excess H (H3O in water) or OH-, they do
+ +

react with water to change the pH:

3+ 3+
Al (aq) + 6 H2O(l) → [Al(H2O)6] (aq) (complex ion formation) (Eq. 1)
3+ 2+ +
[Al(H2O)6] (aq) + H2O(l) [Al(OH)(H2O)5] (aq) + H3O (aq) (Eq. 2)
2- - -
CO3 (aq) + H2O(l) HCO3 (aq) + OH (aq) (Eq. 3)

All the other unknown solutions are nearly neutral in pH and produce only ambiguous results with pH

Precipitation Reactions
When two of the solutions are mixed, a compound may form from the cation in one solution and the anion
in the other (double displacement reaction). If the compound is present at a concentration higher than its
solubility, it will precipitate. For example, the Ba from Ba(NO3)2 and the SO42- from Na2SO4 react to form

insoluble BaSO4.

Ba(NO3)2(aq) + Na2SO4(aq) → BaSO4(s) + 2 NaNO3(aq) (Eq. 4)

Most of the anions and cations in the list form insoluble compounds with at least some of the other ions.
+ + -
Those that form only soluble salts are Na , NH4 , and NO3 .

Since some precipitates form slowly, a general rule is to wait for about 2 to 5 minutes before discarding the
test mixture. Some precipitates take even longer to form and are noted in the accompanying table. Since the
dissolution and precipitation of salts is an equilibrium reaction, the concentrations of the ions will affect the
equilibrium position. Adding one more drop of a solution can produce a precipitate where there was none
A few precipitates formed from Ag ions will darken and finally turn black after several minutes due to the
formation of free metallic silver. Examples are Ag2CO3 and Ag2S2O3. This blackening, which requires
light, is essentially the same process that occurs in photographic film. Also note that the OH- ion
precipitates silver oxide.
+ -
2 Ag (aq) + 2 OH (aq) Ag2O(s) + H2O(l) (Eq. 5)

The precipitate is dark brown or black when formed, and may become blacker after a few minutes. This
reaction might be expected when Na2CO3 is added to AgNO3, since the basic Na2CO3 solution contains
OH- ions. However, white Ag2CO3 is obtained instead of Ag2O because [OH-] in the Na2CO3 solution is too
low to produce Ag2O in the presence of CO3 . After awhile this white Ag2CO3 precipitate may turn slightly

Gas-Producing Reactions
Reaction Odor Bubbles
+ -
NH4 (aq) + OH (aq) → NH3(g) + H2O(l) (Eq. 6) ammonia no
2- +
8 S2O3 (aq) + 16 H (aq) → S8(s) + 8 SO2(g) + 8 H2O(l) (Eq. 7) SO2 no
2- +
CO3 (aq) + 2 H (aq) → CO2(g) + H2O(l) (Eq. 8) none yes

Oxidation-Reduction Reactions
Reaction Observation
2+ -
Mn (aq) + H2O2(aq) + 2 OH (aq) → MnO2(s) + 2 H2O(l) (Eq. 9) dark brown ppt
+ -
2 Ag (aq) + H2O2(aq) + 2 OH (aq) → 2 AgO(s) + 2 H2O(l) (Eq. 10) black ppt

These precipitates (above) catalyze the breakdown of additional H2O2, producing O2 bubbles that may or
may not be visible.
The reaction of S2O3 in acid, discussed in the preceding section, is also an oxidation-reduction reaction.

Complex Ion Formation

Reaction Observation
2- 3- -
AgCl(s) + 2 S2O3 (aq) → Ag(S2O3)2 (aq) + Cl (aq) (Eq. 11) ppt. dissolves

Solubility of ionic compounds in water at 20 OC

Chloride ion Nitrate ion Carbonate Oxalate ion Thiosulfate

Cl- NO3-- ion CO32-- C2O42- ion S2O32-
Sodium NaCl Soluble NaNO3 Na2CO3 Na2C2O4 Na2S2O3
ion Na Soluble Soluble Soluble Soluble

Ammoniu NH4Cl NH4NO3 (NH4)2CO3 (NH4)2C2O4 (NH4)2S2O3

m ion Soluble Soluble Soluble* Soluble Soluble
Silver ion AgCl AgNO3 Ag2CO3 Ag2C2O4 Ag2S2O3
Ag Insoluble Soluble Insoluble Insoluble Insoluble**

Barium BaCl2 Ba(NO3)2 BaCO3 BaC2O4 BaS2O3

ion Ba2 Soluble Soluble Insoluble Insoluble Slightly
Manganes MnCl2 Mn(NO3)2 MnCO3 MnC2O4 MnS2O3
e ion Mn2 Soluble Soluble Insoluble**** Insoluble***** Soluble

Zinc ion ZnCl2 Zn(NO3)2 ZnCO3 ZnC2O4 ZnS2O3

Zn2 Soluble Soluble Insoluble Insoluble*** Soluble

Aluminum AlCl3 Al(NO3)3 Al2(CO3)3 Al2(C2O4)3 Al2(S2O3)3

ion Al3 Soluble Soluble Insoluble***# Soluble# Insoluble***

* (NH4)2CO3 is unstable, and releases NH3 gas.

** An equal number of drops of Ag and S2O32- solutions give a white precipitate that vanishes rapidly. In that case,
2- +
add one drop of S2O3 to 10 drops of Ag . This should produce a yellow precipitate that turns brown and then black in
one to two minutes.
*** Precipitate takes several minutes to form, and often the solution becomes only slightly turbid.
**** Precipitate slowly turns tan as it oxidizes in air to dark brown MnO2.
***** Precipitation may not be observed.
# These tests are sometimes inconclusive. Al3 can be identified more clearly by another test.


This problem is given as an example to show a logical approach to identify unknown solutions. These are
not the solutions that will be used in the actual experiment. Because the solutions are not the same, there
are a few more reactions involved.
2- +
SO3 (aq) + 2 H (aq) → SO2(g) + H2O(l)
- -
I is oxidized to dark brown I2 in acid solution by H2O2 or IO3
- 2- 2-
In acid solution, I2 is reduced to I by SO3 or S2O3 (thiosulfate)
Solutions of NaOH, H2SO4, Na2CO3, HCl, BaCl2, H2O, Zn(NO3) 2, NaI, NaIO3, Na2SO3 and Zn(NO3)2 can

be distinguished by the following tests:

1. pH tests. Two basic solutions (NaOH and Na2CO3) and two acidic solutions (H2SO4 and HCl) and seven
nearly neutral solutions (BaCl2, H2O, H2O2, Zn(NO3) 2, NaI, NaIO3 and Na2SO3).
2. Flame test. Find BaCl2 from the green flame and the group of five sodium compounds from the bright
yellow flame.
3. Mix a drop of BaCl2 with drops of each of the acidic solutions. A precipitate of BaSO4 identifies H2SO4;
the other acid must be HCl.
4. Mix a drop of BaCl2 with drops of each of the basic solutions. A precipitate of BaCO3 identifies Na2CO3;
the other base must be NaOH.
5. Mix a drop of NaOH with a drop of each of the remaining neutral solutions. A precipitate of Zn(OH) 2
picks out Zn(NO3) 2.
6. Mix a drop of Zn(NO3) 2.with a drop of each of the rest of the remaining neutral solutions and
precipitates of Zn(IO3) 2 and ZnSO3 form.
7. One of the neutral solutions (H2O, H2O2, NaI) that did not react with Zn(NO3) 2 is identified as NaI
because it gives a positive Na flame test.
8. Mix a drop of NaI with a drop of acid and add a drop of each of the two solutions that reacted with
Zn(NO3) 2. NaIO3 gives a brown solution of I2. Since two out of the three sodium containing solutions have
now been identified by precipitation-reactions, the remaining solution with no reaction must be Na2SO3.
9. Mix a drop of NaI with a drop of acid, and add a drop of the solutions left over from step 7— H2O or
H2O2. H2O2 produces a brown solution of I2 (which can be turned clear by adding a drop of Na2SO3). The
other solution must be water, since it is the only solution left at this point that has not been identified. A
sample flow chart illustrating this identification process is available in the procedure section below.


Safety Precautions
The compounds in this experiment are not toxic, but promptly wash off any spills. Although it
is harmless, silver nitrate will stain skin for a few days. The Bunsen burner flame can burn
skin or start a fire if exposed to flammable materials. As always, wear goggles.

Special Equipment 1.0 M sodium thiosulfate
General Equipment Transfer pipets (Na2S2O3)
(13×100 mm) test tubes Nichrome wire 1.0 M hydrochloric acid (HCl)
Test tube rack pH paper 1.0 M sodium carbonate (Na2CO3)
Watch glasses Bunsen burner 0.1 M sodium oxalate (Na2C2O4)
Striker 0.1 M barium nitrate (Ba(NO3)2)
0.1 M manganese (II) nitrate
1.0 M ammonium chloride
0.1 M zinc chloride (ZnCl2)
0.1 M silver nitrate (AgNO3)
0.1 M aluminum nitrate
3% hydrogen peroxide (H2O2)

Flow Chart for Sample Problem
Compounds in bold indicate when they are identified.

1. Use a plastic transfer pipet twice to obtain about 2 mL of each unknown solution in test tubes
labeled 1–11(the solution height in the tube should be about 1 inch). Store the tubes in a test tube rack,
with a transfer pipet in each.
2. Using the flow chart prepared in the pre-laboratory questions, carry out the necessary procedures to
identify all eleven solutions. Write down each test that is performed and the accompanying
experimental observations in the laboratory notebook. Any modifications to the planned procedure
should be recorded. The results of negative tests, in which nothing appears to happen, must also be
recorded. Below is a list of suggestions to ensure reliable results.
a. You should begin with a pH test, followed by a flame test and then other relevant reactions (Hint:
You may set up a flow chart in which H2O2 never undergoes a chemical reaction. It is then identified
simply by being the only one left after all other solutions have been identified ).
b. To test an unknown in the flame test, use the supplied needle-nose pliers to twist a small loop in the
end of the nichrome wire. Avoid touching the loop, as your hands are contaminated with sodium.
Clean the nichrome wire loop before testing each sample by heating the loop red-hot until it no
longer colors the flame. (Hint: The orange flame color might never dissapear completely. Make sure
you remember the coloring of the flame from the pure wire so you can compare it to the flame color
after adding sample) Allow the loop to cool so that it no longer glows, and use a transfer pipet to add
a drop of the solution to the wire. Heat the loop in the Bunsen flame and note the color. The sodium
flame is very intense and persistent. After a positive sodium flame test, cut the old loop off. Make a
new loop farther down the wire before testing the next solution. To save time and material, make

sure to do this only after a positive sodium flame, not after each test.
If you are unsure about the sodium content of a solution, make a note of this in your lab notebook
and move on to the next test. Most likely you will be able to figure out the missing solution later on.
However, you need to have a positive identification of BaCl2 (Green flame)
c. To make a pH measurement, use the pipet to moisten a strip of pH test paper with a single drop of
the solution being tested. With conscientious labeling of the spots, two or three tests can be made on
a single strip of pH paper. Do not label the pH paper directly, but lay the pH paper on a paper towel
and label the towel. Then compare the color of the paper to the color key given on the pH-paper vial.
Compare the pH of all eleven solutions by laying the pH strips side by side.
d. The majority of the tests should be carried out on a watch glass. First rinse the watch glass under tap
water, and then rinse it with a little distilled water. Dry it with a paper towel before proceeding with
the reactions. There should be no visible precipitate present on the watch glass before beginning a
new test. Add equal volumes of the solutions to the center of the glass and mix by gently swirling. A
couple of drops of each solution will suffice for most tests. A microspatula or a glass stirring rod can
also be used for mixing. As each locker is stocked with several watch glasses, a few mixtures may be
set aside for further observation after a period of time.
e. For the reactions involving gases, begin cautiously by waving vapors towards the nose. Odors may
not be noticeable unless the mixture is removed from the hood. Moist pH paper held over the
solution containing NH3 gives a basic indication (pH >> 7). The whitish precipitate of sulfur (S8) is a
diagnostic of the reaction of thiosulfate with acid, as is the choking stench of the sulfur dioxide
f. Avoiding contamination is very important. Be sure to wash the microspatula or glass stirring rod
with destilled water between mixtures. The watch glass should be cleaned between tests.
g. Please keep in mind that you can use Na2CO3 to provide OH- for reactions carried out under basic
conditions, such as Reactions 9 and 10 on page 2.
3. When all the solutions have been tentatively identified, perform one additional reaction for each
solution to double check the identity. An inconsistent verification test may indicate that the original
identification was incorrect and should be repeated. The verification test is to run additional
reactions for 10 of 11 solutions (10 reactions should be different from each other). You can use all
11 solutions for each of your tests. This reaction SHOULD be DIFFERENT than the one used in
the FINAL step of identifying that solution proposed in your flow chart. Absence of a reaction or no
reaction is NOT a suitable verification method. Your verification reactions should be chosen to give
a positive result such as precipitate or a color change (excluding PH or flame tests). Therefore you
need to come up with a total of 10 reactions. Although a verification reaction involves at least two
unknowns, count it as verifying only one of the ions and use another test to verify the second.
Sometimes the original identification can be verified by identifying the counterion. For instance, if
previously, NH4Cl was identified by ammonia smell, the identification can be verified by a reaction
that finds Cl-(e.g. silver nitrate).
4. Wash all watch glasses and test tubes thoroughly. Return the nichrome wire and pH-test vials to the
supplies table in the back of the room.


Collect all used solutions in a waste beaker in your hood. After completing the
experiment, dispose all used and unused solutions in the waste container in the hood in
the back of the room, next to the supplies bench. Transfer pipets go into the black “medical waste”
containers on the supplies table in the back of the room. Paper towels and pH strips go in the regular
wastebasket. DO NOT dispose of these in the red sharps containers next to the waste baskets ! Doing so
puts at risk the health of the lab managers who will have to remove inappropriatly disposed waste from the
sharps containers.