Chem 1B Dr.
White Saddleback College
Experiment 20/21: Separation and Identification of Group IV & Group V Cations
(Ba2+, Ca2+, Mg2+, Na+, K+, and NH4+)
Objectives
• To understand the chemical reactions involved in
the separation and identification of the Group IV (Ba
2+
2+ 2+ + +
and Ca ) & Group V cations, (Mg , Na , K , and
+
NH4 ).
• To successfully identify the Group IV & Group V
cation(s) present in an unknown solution.
• To complete a flow diagram summarizing the
behavior of your unknown.
Introduction
The cations left after separation of the Group III
2+ 2+
cations are those of the alkaline earth (Ba , Ca ,
2+ + +
and Mg ), alkali metals (Na and K ), and the
ammonium ion. The ammonium ion is included in
Group IV since its properties resemble those of the
alkaline metals. Barium and calcium are separated
from the rest of the group by precipitation with
carbonate under slightly basic conditions. Sodium,
potassium, ammonium, and for the most part
magnesium ions do not precipitate under such
conditions. The cations in Group IV & V have less
distinctive chemical properties than the cations of the
other groups. So, their detection also depends on
physical behavior such as flame tests.
When exposed to a flame, certain elements emit light
of a characteristic color. As part of our analysis, flame
tests of known samples of the Group IV & V cations
are necessary in order to become familiar with the
characteristic color emitted by each one. Individual
known sample solutions can be flame tested directly
or the cation can be precipitated and a flame test
performed on the precipitate. In either case, a wire
loop is used to introduce the sample into the flame.
The loop of the flame test wire must first be
thoroughly cleaned of any trace contamination. Begin
by lighting a Bunsen Burner and adjusting the flame
so that it burns hot; that is it appears blue, not yellow.
Then dip the wire loop in 6M HCl (in a centrifuge
tube) and insert just the loop (not the copper handle)
into the hottest part of a Bunsen Burner flame; the tip
of the inner blue cone. If the wire is contaminated, the
flame will exhibit a color characteristic of the
contaminant. Repeat the process of dipping the wire
loop into the HCl and then inserting it into the flame
until no more contamination is apparent. Note that
upon sufficient heating the test wire itself will turn the
flame orange. After cleaning the wire, it can be used
to test a solution or a precipitate.
To test a solution, dip the wire loop into the solution
and then insert it into the flame, observing the color
that is emitted. For the known solutions, DO NOT
insert the wire loop directly into the reagent bottle.
1
Instead, place a small amount of the solution into a
centrifuge tube for use. Each metal cation may not
emit at the same burner temperature. Therefore,
when performing flame tests best results are often
obtained by slowly bringing the wire loop containing
the sample across the flame from the side. As the
wire moves across the flame, it is subjected to a
range of temperatures within the flame. This method
of bringing the loop slowly across the flame is more
important for the unknown samples, where
concentrations of the emitting elements tend to be
lower than in the known samples.
To test a solid, heat a clean wire and touch it to the
crystals. The crystals will adhere to the wire and then
the wire can be placed in the flame as described
above.
Reagents Available
6 M HCl 6 M NaOH 6 M NH3
6 M HC2H3O2 6 M HNO3 6 M H2SO4
1 M K2CrO4 1 M K 2C 2O 4 1 M Na2HPO4
Mg Reagent Tetraphenyl borate
Dilute, Known Solution that contains all the Group IV
cations as well as separate solutions of each Group
IV cation (useful for flame tests)
Safety
Some of the Group IV cations are toxic and 6 M HCl,
NH3 and NaOH, and H2SO4, and HNO3 are irritants.
Avoid contact and wash immediately if any is spilled
or splashed on you. Wear eye protection at all times.
As you perform the experiment, collect all waste
solutions in a waste beaker. This mixture should then
be discarded in the appropriate waste container. DO
NOT POUR ANY OF THE SOLUTIONS DOWN THE
DRAIN.
Unknowns and Knowns
A known solution containing all 6 Group IV & V
cations is provided for your use. Testing a known
sample is helpful in this analysis since doing so will
allow you to observe what a positive test looks like. It
is usually convenient to test a known sample
simultaneously with your unknown. Note that the
experimental conditions, such as pH, for the known
test must be the same as that for the unknown.
Chem 1B Dr. White Saddleback College 2

Outline of Procedure: Record all observations for each step in the procedure
Experimental Procedure: Chemistry, Comments, and Background Information:
1. 1. Preparation of the Sample
(a) If your sample only contains the Groups IV & V (a) Reducing the volume to 2 mL increases the concentration
ions - pour 5 mL of your sample into a 50-mL and improves the sensitivity of the subsequent analysis.
beaker and boil gently until the volume is reduced
to about 2 mL. Add 0.5 mL 6 M HCl and swirl the
beaker to dissolve any crystallized salts. Transfer
to a centrifuge tube. Continue to step 2.
(b) Precipitation may result if the slightly water soluble salts
(b) If this is the general unknown - transfer the of Groups I, II, and III cations are present. These salts must
solution remaining after the Group III analysis to a be removed to avoid any interferences with your Group IV/V
50-mL beaker and boil gently until the volume is cations.
reduced to about 2 mL. Transfer to a centrifuge
tube and centrifuge out any any solid matter, which
you may discard. Put the liquid back into a beaker
and add 1 mL 6 M HCl. Boil the solution to
essentially to dryness. Carefully (in the hood) heat
the dry solid to drive off the ammonium salts. Stop
heating the solid when the visible salts stop
evolving. Let the beaker cool and add 0.5 mL 6 M
HCl and 2 mL water. Warm the solution gently to
dissolve the remaining salts. Centrifuge and
discard any precipitate. Pour the solution into a
centrifuge tube.
2+ 2+ 2+
2. 2. Precipitation of Ba , Ca , and Mg
+
(a) To your Group IV/V cations prepared in step 1, (a) NH3 and NH4 create a buffer system that is used to keep
add 6 M NH3 until the solution is basic to litmus, the pH level moderately high (about pH of 9). A high pH
2-
then add 0.5 mL more. Next, add 1 mL 1 M level helps maintain a high concentration of CO3 ions and
2+ 2+ 2+
(NH4)2CO3 and stir. Put the centrifuge tube into hot this permits Ba , Ca , and especially Mg to precipitate
(but not boiling) water, turn the hot plate off, and from your solution as carbonate salts.
leave the centrifuge tube in the hot water for 2
minutes. Stir occasionally.

(b) Centrifuge and decant the supernatant into a

centrifuge tube (LABEL). Wash the precipitate with
2 mL water. Centrifuge out the precipitate and
discard the wash.
2+
3. 3. Confirmation of Ba
(a) Add 0.5 mL 6 M acetic acid to the precipitate (a) Acetic acid is added for 2 reasons. It is not acidic enough
from step 2b and stir to dissolve the solid. to destroy the BaCrO4 precipitate that may be formed upon
2+
the addition of K2CrO4. If Ba is present the acetic acid is
(b) Add 1 mL water and 2 drops 6 M NH3 and mix. acidic enough to destroy the BaCO3 precipitate:
+ 2+
Then add 0.5 mL 1 M K2CrO4 (not K2C2O4). A BaCO3 (s) + 2 H (aq) → Ba (aq) + CO2 (g) + H2O (l)
2+
yellow solid indicates the presence of Ba .
Centrifuge and decant the orange liquid into a
centrifuge tube (LABEL). Wash the solid with 3 mL
of water, stir, centrifuge, and discard the wash.

(c) Dissolve the solid from step 3b with 0.5 mL 6 M

HCl and then add 1 mL water. Next, add 0.5 mL 6
M H2SO4 and stir the solution for 30 seconds. A
white solid of BaSO4 also confirms the presence of
2+
Ba . Centrifuge this tube so establish its color and
amount. Discard.
2+
4. 4. Confirmation of Ca
(a) To the supernatant from step 3b, add 6 M NH3 (a) NH3 is added to create a basic solution. When K2C2O4 is
until the solution is basic to litmus. At this point the added, the basic solution can stabilize the formation of
Chem 1B Dr. White Saddleback College 3

solution should become yellow. Add 0.5 mL 1 M CaC2O4⋅H2O:

K2C2O4 (not K2CrO4), stir, scratch the side of the
centrifuge tube with a glass stirring rod, and let the
solution sit for about a minute. A white precipitate
2+
confirms the presence of Ca .
(b) Centrifuge out the solid and pour the
supernatant into a centrifuge tube (LABEL). Wash
the solid with 3 mL of water, mix, centrifuge, and
discard the wash.
2+ 2-
Ca (aq) + C2O4 (aq) + H2O (l)  CaC2O4⋅H2O (s)
+
If NH3 were not added, the H ion concentration would be
high enough to destroy the precipitate by removing oxalate
ions in the form of oxalic acid. The following equilibrium
would shift to the right and the precipitate would be
dissolved:
+ 2+
CaC2O4⋅H2O (s) + 2H (aq)  Ca + H2C2O4 (aq) + H2O (l)

(c) Dissolve the solid in 2 drops of 6 M HCl.

Perform the flame test several times on the
solution. A fleeting orange-red sparkly flame is due
2+
to Ca . This color appears before the yellow
sodium flame and the color lasts only a fraction of a
second. Compare your observations here with
those obtained with a 0.1 M Ca(NO3)2 solution
(found on the qual wall).
2+
5. 5. Confirmation of Mg
+
(a) To the supernatant from step 4b, add 0.5 mL 1 (a) Since NH4 ions are present (step 4a), the addition of
M Na2HPO4 (NOT NaH2PO4 – read carefully!). Stir Na2HPO4 brings about the precipitation of white magnesium
the solution, warm it gently in the hot water bath, ammonium phosphate hexahydrate:
2+ 2-
and let it stand for a minute. A white precipitate is Mg (aq) + NH3 (aq) + HPO4 (aq) + 6H2O (l) →
2+
highly indicative of the presence of Mg . MgNH4PO4⋅6H2O (s)
Centrifuge out the solid and discard the liquid.
Wash the solid with 3 mL of water, mix, cntrifuge,
and discard the wash.
If you don’t get a precipitate, try cooling the solution
in cold water and scratching the sides of the tube
with a glass stir rod. If there is still no precipitate,
add 2-3 drops of NH3, reheat and cool.

(b) Dissolve the precipitate in a few drops of 6 M

HCl. Add 1 mL water and 2-3 drops of magnesium
reagent, 4-(p-nitrophenylazo)resorcinol. Stir the
solution and then drop by drop, add 6 M NaOH until
2+
the solution is basic. If Mg is present, a medium
blue precipitate of Mg(OH)2 with adsorbed
magnesium reagent forms. Centrifuge out the
precipitate from the almost colorless solution for
better observations of the solid.
2+
6. 6. Alternate Confirmation of Mg
Repeat step 5 on one half the solution obtained in
2+ 2+
step 2b. If Mg is present, the Mg tests may be
negative in step 5 or 6, but NOT both.

+
7. 7. Confirmation of Na
Perform a flame test on the original sample using a
portion that has not been treated in any way (use a
spot plate). A strong yellow flame which persists
+
for several seconds confirms the presence of Na .
Compare the results with a sample of 0.5 M NaCl
solution. The test is very sensitive to trace
amounts of sodium, so be aware of contamination
and clean the platinum loop well (as described in
the introduction).
Chem 1B Dr. White Saddleback College 4

+
8. 8. Confirmation of K
(a) Perform a flame test on the original sample
using a portion that has not been treated in any
way (use a spot plate). The potassium flame is
violet and lasts only for a moment. The test is
much less sensitive than that for sodium and is
best observed with crystals obtained by
evaporating 1 mL of sample to dryness. Look for
the potassium flame through blue cobalt glass
which absorbs any sodium emission. Compare the
flame to that from a saturated KNO3 solution (found
on the qual wall).

(b) Since potassium is much less likely to be a

contaminant in your reagents than sodium, it is also
meaningful to perform the test on the other half of
the solution from step 2b. Boil that solution down
to a volume of only a few drops. Because the
+
solution may be quite concentrated in K , the flame
may be easier to see.
−
(c) Tetraphenyl borate (B(Ph)4 ) reacts with potassium to
(c) To 2 mL of the original sample, add 6 M NaOH form a water insoluble salt:
+ −
dropwise, with mixing until the solution is basic to K (aq) + B(Ph)4 (aq) → KB(Ph)4 (s)
litmus. Then centrifuge and decant the supernatant
away from the precipitate. To the supernatant, add
5 drops of 0.005 M sodium tetraphenyl borate
reagent and mix. Formation of a precipitate
+
indicates the presence of K .
+
9. 9. Confirmation of NH4
+ + -
Pour 1 mL of the original sample used in the Na NH4 reacts with the OH :
+ -
flame tests or fresh sample into a 50-mL beaker. NH4 (aq) + OH (aq)  NH3 (g) + H2O (l)
Moisten a piece of red litmus paper and put it on
the bottom of a small watch glass. Add 1 mL 6 M The NH3 turns the litmus paper blue. Be careful that the
NaOH to the sample in the beaker and swirl to stir. solution does not splash on the litmus paper since the
Cover the beaker with the watch glass and then solution is basic and will turn the litmus paper blue.
gently heat the solution to the boiling point. Do not
boil the liquid. Be careful that none of the solution
splatters onto the watch glass or litmus paper. If
ammonia is present, the litmus paper gradually
turns blue as it is exposed to NH3 gas. Remove
the watch glass and try and smell the ammonia.
Chem 1B Dr. White Saddleback College 5

Outline of Procedure for Group IV & V Cations (Group IV & V Flow Chart)
Chem 1B Dr. White Saddleback College 6

Experiment 20/21 - Group IV & V Cations: Data and Results

Draw a flow chart indicating the behavior of your unknown:

Conclusion: The cations present in unknown number________are ____________________.

Chem 1B Dr. White Saddleback College 7

Exp. 20/21: Pre-Lab Questions

1. In step 2, ammonium carbonate is added to precipitate 3 of the group IV/V cations. Write the net ionic
equations for the formation of these 3 carbonate precipitates:

2. Explain why flame tests are necessary in the Group IV/V analysis.

3. In your own words, explain how to perform a flame test.

4. Describe the colors emitted by calcium, sodium and potassium ions when placed in a flame.

+
5. Explain why the NH4 ion is tested for on the original sample and not on one of the supernatants.

6. In step 3, NH3 is added to the solution create a buffered solution with a pH of about 9. The purpose of this
is to keep maintain a high concentration of carbonate so that the carbonate salts will precipitate. Use the
following equation to explain why a high pH causes a high carbonate concentration.
H2CO3 (aq) + 2H2O (l)  CO3 (aq) + 2H3O
2- +
Chem 1B Dr. White Saddleback College 8

7. Group IV/V unknown exhibits the following behavior: Addition of NH3 and (NH4)2CO3 gives a white
precipitate that is soluble in acetic acid. There is no precipitate when the acid solution is treated with
K2CrO4 and no precipitate with K2C2O4 when the acid solution is made basic with NH3. A definite odor is
noticed when the original sample is treated with 6 M NaOH. A flame test reveals a strong yellow flame.
Which cations are present, absent, in doubt? Explain.

Present: _________________

Absent:_________________

Still in Doubt: _________________

Chem 1B Dr. White Saddleback College 9

Exp. 20/21: Follow-up Questions

For Numerical Problems, you must show all work for credit! Please box your final answer.

1. Many elements emit light of specific wavelengths when they are placed in a flame. Historically, chemists used
such emission “fingerprints” to determine whether certain elements were present in a sample. Some characteristic
wavelengths of emission for several elements are:
Ag 328.1 nm Fe 372.0 nm
Au 267.6 nm K 404.7 nm
Cu 324.8 nm Mg 285.2 nm
Ni 341.5 nm Na 589.6 nm
a) Which of these wavelengths are in the visible part of the spectrum? (Refer to your textbook or another
reference source to help you determine this.)

b) Which of the above wavelengths has the highest energy per photon? Which has the lowest energy?

14 -1
c) When burned, a sample of an unknown substance is found to emit light of frequency 7.41 x 10 s .
Which of the above elements is probably in the sample? Show work to support your answer.

d) When placed in a flame, copper emits light that appears green to our eyes, evidence that copper exhibits
at least one more emission line than the one that is listed above. Referring to your textbook, roughly
estimate the wavelength in nanometers of the green emission from copper.

3. A solution that has a pH of 3 is known to contain barium chloride. Ammonium oxalate is added, and no
precipitate forms. Ammonia is then added until the solution tests basic to pH paper and a precipitate is observed to
form. Explain these observations.

4. A flame test on a Cation Group IV/V unknown shows a bright yellow flame color but no violet flame color through
cobalt glass. Addition of (NH4)2CO3 fails to gave a precipitate. When the resulting solution is heated with NaOH, a
gas is evolved that turns red litmus blue. What does that tell you about the identity of the unknown? Explain.
Chem 1B Dr. White
Experiment 20/21: Separation and Identification of Group IV & Group V Cations
(Ba2+, Ca2+, Mg2+, Na+, K+, and NH4+)
Objectives
• To understand the chemical reactions involved in
the separation and identification of the Group IV (Ba
2+
2+ 2+ + +
and Ca ) & Group V cations, (Mg , Na , K , and
+
NH4 ).
• To successfully identify the Group IV & Group V
cation(s) present in an unknown solution.
• To complete a flow diagram summarizing the
behavior of your unknown.
Introduction
The cations left after separation of the Group III
2+ 2+
cations are those of the alkaline earth (Ba , Ca ,
2+ + +
and Mg ), alkali metals (Na and K ), and the
ammonium ion. The ammonium ion is included in
Group IV since its properties resemble those of the
alkaline metals. Barium and calcium are separated
from the rest of the group by precipitation with
carbonate under slightly basic conditions. Sodium,
potassium, ammonium, and for the most part
magnesium ions do not precipitate under such
conditions. The cations in Group IV & V have less
distinctive chemical properties than the cations of the
other groups. So, their detection also depends on
physical behavior such as flame tests.
When exposed to a flame, certain elements emit light
of a characteristic color. As part of our analysis, flame
tests of known samples of the Group IV & V cations
are necessary in order to become familiar with the
characteristic color emitted by each one. Individual
known sample solutions can be flame tested directly
or the cation can be precipitated and a flame test
performed on the precipitate. In either case, a wire
loop is used to introduce the sample into the flame.
The loop of the flame test wire must first be
thoroughly cleaned of any trace contamination. Begin
by lighting a Bunsen Burner and adjusting the flame
so that it burns hot; that is it appears blue, not yellow.
Then dip the wire loop in 6M HCl (in a centrifuge
tube) and insert just the loop (not the copper handle)
into the hottest part of a Bunsen Burner flame; the tip
of the inner blue cone. If the wire is contaminated, the
flame will exhibit a color characteristic of the
contaminant. Repeat the process of dipping the wire
loop into the HCl and then inserting it into the flame
until no more contamination is apparent. Note that
upon sufficient heating the test wire itself will turn the
flame orange. After cleaning the wire, it can be used
to test a solution or a precipitate.
To test a solution, dip the wire loop into the solution
and then insert it into the flame, observing the color
that is emitted. For the known solutions, DO NOT
insert the wire loop directly into the reagent bottle.
Saddleback College 1
Instead, place a small amount of the solution into a
centrifuge tube for use. Each metal cation may not
emit at the same burner temperature. Therefore,
when performing flame tests best results are often
obtained by slowly bringing the wire loop containing
the sample across the flame from the side. As the
wire moves across the flame, it is subjected to a
range of temperatures within the flame. This method
of bringing the loop slowly across the flame is more
important for the unknown samples, where
concentrations of the emitting elements tend to be
lower than in the known samples.
To test a solid, heat a clean wire and touch it to the
crystals. The crystals will adhere to the wire and then
the wire can be placed in the flame as described
above.
Reagents Available
6 M HCl 6 M NaOH 6 M NH3
6 M HC2H3O2 6 M HNO3 6 M H2SO4
1 M K2CrO4 1 M K 2C 2O 4 1 M Na2HPO4
Mg Reagent Tetraphenyl borate
Dilute, Known Solution that contains all the Group IV
cations as well as separate solutions of each Group
IV cation (useful for flame tests)
Safety
Some of the Group IV cations are toxic and 6 M HCl,
NH3 and NaOH, and H2SO4, and HNO3 are irritants.
Avoid contact and wash immediately if any is spilled
or splashed on you. Wear eye protection at all times.
As you perform the experiment, collect all waste
solutions in a waste beaker. This mixture should then
be discarded in the appropriate waste container. DO
NOT POUR ANY OF THE SOLUTIONS DOWN THE
DRAIN.
Unknowns and Knowns
A known solution containing all 6 Group IV & V
cations is provided for your use. Testing a known
sample is helpful in this analysis since doing so will
allow you to observe what a positive test looks like. It
is usually convenient to test a known sample
simultaneously with your unknown. Note that the
experimental conditions, such as pH, for the known
test must be the same as that for the unknown.