EXPERIMENT 2

CATIONS

I. Course outcome

Demonstrates understanding of basic chemical principles relevant to pharmaceutical

inorganic chemistry
Analyze chemical compounds through qualitative methods that will exhibit basic
laboratory techniques and practices in the laboratory.

II. Intended learning outcome (ILO)

To systematically separate all five cation group and its subgroup for qualitative analysis.

To experimentally confirm the presence of cation group (I, II-A, II-B, III-A, III-B, IV, and V).

III. Introduction

Chemical analysis can be divided into two categories; qualitative analysis – what is present
and quantitative analysis – how much is present. In this lab you will learn and apply principles of
qualitative analysis for some of the more common metal ions (i.e. those elements that typically
form cations in aqueous solution.) This experiment is part of a classical analysis scheme
developed by chemists of past generations to identify unknowns.

In commercial practice the qual-scheme, as it is affectionately known, has largely been

surpassed by automated analytic instrumentation. However, the scheme retains real value in
teaching many of the chemical attributes of the elements and in the reinforcement of chemical
principles. The opportunity to conduct qualitative analyses in the laboratory will teach students
new techniques and help to refine those already learned. Most importantly it gives the students
some of the sense of discovery in collecting and assimilating the clues to determine the
“unknown” composition, as this is such a rewarding part of science.

IV. Materials and Reagents

Equipment/Apparatus
Centrifuge Casserole Hot plate
Pasteur pipette Litmus paper Spot plate
Silver coin
Chemicals
3M HCl Thioacetamide (C2H5NS) Na2O2 (s)
HNO3 Saturated NH4Cl 3M HAc
H2 S Conc H2SO4 Aluminon
3M KOH Saturated NH4Ac H2 O 2
Saturated NH4Cl Conc HAc NaBiO3 (s)
3M NH3 K2SnO2 3M NH4CNS
Na2O2 1M KCN NaF (s)
0.5M (NH4)2HPO4 alcoholic NH4CNS
Conc. NH3 0.5M AgNO3 dimethylglyoxime
water 2.5M NaAc 1M (NH4)2SO4
1M K2CrO4 NaOCl 0.25M (NH4)2C2O4
3 M HNO3 NaNO2 crystals p-
Conc HNO3 Rhodamine B nitrobenzeazorresorcinol
SnCl2 Magnesium ribbon
Conc HCl Saturated HgCl2
V. Procedure
A. ANALYSIS OF GROUP I CATION

1. Place 10 drops of cation group I solution sample to be analyzed in a test tube and add 4 drops
of 3 M HCl. Mix thoroughly and centrifuge. To the supernatant, add another drop of 3 M HCl to
test for completeness of precipitation. Centrifuge after.
2.Discard 3. Residue remaining in the test tube is washed with 10 drops of cold water and
centrifugate. 1 drop of 3 M HCl. Shake and centrifuge. Discard washing. White precipitate
obtained maybe PbCl2, AgCl, and Hg2Cl2
4. Add 6-7 drops of water in the residue and heat with stirring for 3 minutes in
water bath. Centrifuge quickly and place the mixture in a hot steam bath and
immediately remove centrifugate.
5. Centrifugate 6. Residue may contain AgCl and Hg2Cl2. Treat residue with 10
may contain drops of 3 M NH4OH, stir thoroughly, and centrifuge. A
Pb++. Add 4 blackening of the residue indicates the presence of the
drops of 1 M mercurous ion.
K2CrO4. Yellow 7. Centrifugate 8. Residue may contain Hg. Wash with 10
precipitate may contain drops of water and discard washings.
confirms +
Ag(NH3)2 Cl. Dissolve precipitate in 2 drops of
presence of lead Acidify concentrated HNO3. Dilute with 5 drops of
ion. centrifugate water. (If solution is not clear, centrifuge
with 3 M HNO3. the mixture, discard residue and retain
Formation of a centrifugate). Add 1-2 drops of SnCl2
white solution. White or gray precipitate
precipitate confirms presence of mercurous ion.
confirms
presence of
silver ion.
B. SYSTEMATIC SEPARATION OF CATION II SUBGROUP

1. Place 20 drops of the cation group II solution sample in a test tube and add 4 drops of 3 M
HNO3, heat in water bath for 3 mins. Make the solution barely alkaline with 3 M NH4OH, then
acidify by adding 3 M HCl. Concentrate to a volume of 2 mL in water bath. After which add 4
drops of conc. HCl. Add 10 drops of CH3CSNH2 solution and heat in boiling water bath for 5
mins. Add 4 mL of water and 10 drops of CH3CSNH2 solution, and heat again in boiling water
bath for 5 mins. Centrifuge.

2. Discard 3. Wash the residue with 20 drops of water containing 2 drops of CH3CSNH2
centrifugate. solution and 2 drops of saturated NH4Cl. Discard wash water. Add 16 drops
of 3 M KOH. Stir and heat in water bath for 3 mins. Centrifuge and
separate residue from centrifugate. For the residue add 16 drops of 3 M
KOH. Centrifuge, and combine two centrifugates.

4. Residue consists of sulfides 5. Centrifugate is a solution of soluble

of group II-A: HgS, CuS, PbS, complex ions of Group II-B cations, which
Bi2S3, and some free sulfur. are arsenic, antimony, and tin. This
This residue will be analyzed centrifugate will be analyzed for the
for analysis of group II-A analysis of Group II-B cation.
cation.
C. ANALYSIS OF GROUP II-A CATION

1. Residue consists of sulfides of group II-A. Wash the residue from subgroup separation with 10
drops of water to remove excess KOH, and discard washings. Add 10 drops of 3 M HNO3, heat
in water bath for 3 minutes, and centrifuge. If much residue is still formed, repeat treatment
with the centrifugate, and combine the formed residues together.

2. Residue 3. Centrifugate contains lead, bismuth, copper, and cadmium ions. Transfer to an
may be evap dish and add 3 drops of concentrated H2SO4. Evaporate until dense white
black HgS fumes appear and only 2 or 3 drops of liquid remain. Cool thoroughly, and
or white cautiously add 1 ml of water. Stir thoroughly and transfer to a test tube. Rinse
Hg(NO3)2, evap dish with 5 drops of water and add washings to the solution. Centrifuge.
HgS and S.
Dissolve 4. Residue may be 5. Centrifugate contains bismuth, copper and cadmium ions.
residue in 4 PbSO4. Wash Add concentrated NH4OH dropwise with stirring until
drops of with 4 drops of solution is basic, and then add 3 drops in excess.
aqua regia. water and Centrifuge.
Add 10 discard
drops of washings. Add 6. Residue may be bismuth 7. Centrifugate contains soluble
water and 10 drops of peroxide. Wash with 5 copper-ammonia and
boil in saturated drops of water and cadmium-ammonia complex
water bath NH4Ac and discard washings. To ions. Deep blue solution
for 2 heat with residue, add 10 or more confirms presence of copper
minutes. stirring, in drops of freshly ion. To test for cadmium ion,
Cool and water bath for prepared H2SnO2. add sufficient 1M KCN to
add 2 3 minutes. If Immediate blackening decolorize solution. Add 5
drops of resulting of precipitate indicates drops of thioacetamide
SnCl2 solution is not presence of bismuth ion. solution and place in boiling
solution. clear, water bath for 5 minutes.
White centrifuge and Yellow precipitate indicates
precipitate discard residue. presence of cadmium ion.
of Hg2Cl2 or Add 1 drop of
gray concentrated
precipitate HAc and 2
of Hg and drops of 1M
Hg2Cl2 K2CrO4. Yellow
confirms precipitate
presence of confirms
mercuric presence of
ion. lead ion.
D. ANALYSIS OF GROUP II-B CATIONS

1. Centrifugate contains soluble complex ions of Group IIB cations. To the centrifugate from subgroup
separation, add 3M HCl until solution is barely acid. Centrifuge. Wash residue with a mixture of 8 drops
of water and 4 drops of concentrated HCl; centrifuge, and add washing to centrifugate of concentrated
HCl treatment.
2. Discard 3. To the residue, add 10 drops of concentrated HCl, stir and heat in water bath for 1
centrifugate. min, and centrifuge. Remove and save the centrifugate on a different test tube.
4. To the residue, wash residue with a mixture of 8 drops of water and 4 drops of
concentrated HCl; centrifuge and add removed washings to the centrifugate saved on
step 3.
5. Residue may be 6. To the saved centrifugate plus washings. The centrifugate
As2S3, As2S5, and S. contains antimony and stannous ions. Divide into two unequal
A small amount of portions
HgS from group IIA 7. Small Portion. Make 2 tests 8. Large Portion. Test for tin as
may also appear for antimony as follows: follows:
here. Wash Test One. Add 1 drop of the Add an equal amount of volume
residue with hot solution to the surface of a clean of 3M HCl to this portion. Place a
water 3 times. Add silver coin. Place a very small piece of Mg ribbon, 4 cm long, in
4 drops of piece of tin on the coin so that
the solution is in contact with
the solution and allow to stand
concentrated until completely dissolved. Add 4
HNO3 and Heat for the tin and coin. Black deposit drops of saturated HgCl2 solution.
insoluble in NaOCl solution
5 minutes, in
indicates presence of antimony. White or gray precipitate
water bath. Add 5 Test two. Place a small piece of confirms presence of tin.
drops of 0.5 M crystal of NaNO2 into each of 2
AgNO3 and stir. (If depressions of a white spot
precipitation plate. Place 2 drops of 3M HCl
occurs, centrifuge upon each crystal and stir until
and discard oxides of nitrogen Have been
residue, which is removed. Add 2 drops of
AgCl from silver rhodamine B to each portion.
ions with Now add 1 drop of distilled
water to one depression and 1
unremoved
drop of unknown solution to the
chlorine ions.) To other. Compare the colors of
clear centrifugate, the 2 solutions. Conversion of
add 15 drops of red color rhodamine B to a
2.5 M NaAc lavender shade indicates
solution. presence of antimony.
Formation of a
reddish-brown
precipitate of
Ag3AsO4, confirms
presence of
arsenic.
E. SYSTEMATIC SEPARATION OF CATION III SUBGROUP

1. To the cation group III solution sample solution, add 4 drops of saturated NH4Cl; then add drop
by drop concentrated NH4OH until the solution is alkaline. Add 10 drops of thioacetamide
solution and place in boiling water bath for 5 mins. Centrifuge.

2. Discard centrifugate. 3. Residue contains sulfides and hydroxides of Group III. Treat
residue with 5 drops of conc. HCl and stir. Add 3 drops of conc
HNO3 and heat in water bath until precipitation is complete.
Make solution basic with 3M KOH, then add solid Na2O2 slowly
with stirring until approximately 200 mg has been added. Heat
in water bath for 3 mins and centrifuge. Wash residue with 10
drops of water. Centrifuge and add washings to centrifugate.

4. Centrifugate contains 5. Precipitate consists of hydrated

aluminate, chromate manganese dioxide and the
and zincate ions. This hydroxides of iron, cobalt and
centrifugate will be nickel. This precipitate will be
analyzed for the analyzed for the analysis of Group
analysis of Group III-A. III-B.
F. ANALYSIS OF GROUP III-A CATIONS

1. Centrifugate from the systemic separation of group III contains aluminate, chromate, and zincate
ions. Add 10 drops of saturated HAc, then 3M NH4CH3COO until acidic. Add 3M NH4OH until
solution is ammoniacal. Centrifuge

2. Residue may be 3. Centrifuge may contain CrO4- and Zn(NH3)4++. Add 1M Ba(Ac)2 until
aluminum hydroxide. precipitation is complete. Centrifuge.
Wash residue with 10
drops of water and 4. Residue may be BaCrO4 5. Centrifugate may contain
discard washings. Add and BaSO4. Add 10 drops Zn(NH3)4++ ion. Acidify solution
3M HCl, drop by drop, of 3M HCl, and warm for 1 with 3 M NH4CH3COO, add 5 drops
until residue dissolves. min in water bath. of thioacetamide solution and
Add 3 drops of Centrifuge and discard place in boiling water bath for 5
saturated NH4Ac and 3 white residue. Place 2 min. Formation of a white
drops of aluminon; add drops of the centrifugate precipitate confirms of zinc ion.
3M NH4OH until left on a piece of filter
ammoniacal. Allow paper. Add 2 drops of
mixture to stand 2 H2O2. Formation of a blue
minutes, then color which fades rapidly
centrifuge. Separation confirms presence of
of a red precipitate chromium ion.
confirms presence of
aluminum ion.
G. ANALYSIS OF GROUP III-B CATIONS

1. Residue from the systemic separation of group III may contain the hydroxides of iron, cobalt,
and nickel, and hydrated manganese dioxide. Wash the residue with 10 drops of water and
discard washings. Dissolve precipitate in concentrated HCl. Dilute resulting solution to
approximately 2 mL and divide into four portions.

2. First portion. Add 3. Second 4. Third portion. Add solid 5. Fourth portion. Add
0.2 grams of solid portion. Add NaF, with stirring, until solid NaF, with
sodium 2 drops of 3M undissolved NaF stirring, until
bismuthate. Stir, NH4CNS. remains. Let 10 drops of undissolved NaF
well, then Appearance alcoholic NH4CNS run remains. Make the
centrifuge. of deep red down the side of the test solution basic with
Reddish-purple coloration tube. Appearance of 3M NH4OH, then add
color in confirms blue-green color at 4 drops of
supernatant liquid presence junction of the two dimethylglyoxime.
confirms presence ferric ion. liquids confirms presence Formation of a red
of manganese ion. of cobalt ion. precipitate confirms
presence of nickel ion.
 H. ANALYSIS OF GROUP IV CATIONS

1. To a 1 mL clear cation group IV solution sample solution, add 10 drops of 0.5 M (NH4) 2HPO4 and
concentrated NH4OH until strongly ammoniacal. Centrifuge. Test for complete precipitation by adding a few
drops of (NH4)2HPO4 to centrifugate. Combine any residue which may form with that originally obtained.

2. Discard 3. Residue may consist of phosphates of barium, calcium, strontium, and magnesium. Wash
supernatant. once with 5 drops of water and discard washings. Treat residue with 5 drops of
concentrated NH4CH3COOand stir thoroughly. Dilute the solution to 2mL, then add 5 drops
of 1 M K2CrO4, and stir for 1 min. Centrifuge and test for complete precipitation.

4. Precipitate 5. Centrifugate may contain strontium, calcium and magnesium ions, and
may be excess chromate ions from above precipitation. Make solution strongly basic
BaCrO4. with NH4OH and centrifuge.
Add 6
drops of 6. Centrifugate 7. Precipitate may be phosphates of strontium, calcium, and
conc. HCl contains magnesium. Dissolve in 5 drops of concentrated
and heat chromate ions, NH4CH3COO; dilute with 5 drops of water. Add 5 drops of
in water etc. Discard. 1M (NH4)2SO4, heat to boiling in water bath, cool and
bath until centrifuge. Test for complete precipitation by adding 1
volume is drop of (NH4)2SO4 to clear centrifugate. Combine any
reduced to residue formed from the previously obtained residue.
half.
Confirm 8. Precipitate 9. Centrifugate may contain calcium and
presence may be magnesium ions. Add 5 drops of 0.25M
of barium SrSO4. (NH4)2C2O4 and heat to boiling in water
ion by Wash bath. White precipitate or clouding of
yellow- three solution indicates presence of calcium ion.
green times with Centrifuge
flame on hot water
flame test. and 10. Precipitate 11. Centrifuge may contain
discard may be magnesium ion. Add 1-2
washings. CaC2O4. drops of p-
Add 3 Add 2 drops nitrobenzeazorresorcinol
drops of of conc. and 3 mL of 3 M KOH.
conc HCl. HCl. Heat in water bath for 5
Confirm Confirm mins then centrifuge.
presence calcium ion Formation of blue
of by brick-red precipitate confirms
strontium flame in presence of magnesium
ion by flame test. ion.
crimson-
red flame
on flame
test.
I. ANALYSIS OF GROUP V CATIONS

1. Identification of Sodium and Potassium Ions

Transfer the cation group V solution sample solution to an evaporating dish and evaporate to
approximately 0.5 mL or 5 drops. Discard any precipitate that may form. Add 1 drop of
concentrated HCl and make flame test for sodium and potassium ions as follows:
Clean a platinum wire until it gives no color to a non-luminous flame. Dip end of wire in
above solution and return wire to flame. Intense yellow flame persisting for 5 sec confirms
presence of sodium ion.

In the absence of sodium ions, presence of potassium ions imparts a pale violet color to
flame when viewed with the naked eye. If yellow flame of sodium is present, it will be
necessary to view flame through a filter of cobalt glass. Repeat above test and examine
flame through two thicknesses of blue cobalt glass. Reddish-violet flame persisting for about
2 sec confirms presence of potassium ion.

2. Identification of Ammonium Ion.

Place 5 drops of NH4OH in a small beaker and add 5 drops of water. Make solution alkaline with 3
M KOH. Immediately cover beaker with a watch glass to which adheres a strip of moistened red
litmus paper on convex side. Warm solution gently for 1 min. Even shading of litmus paper from
red to blue confirms presence of ammonium ion.
Waste Management Procedure

B5: C399 E8: D499 H5: D499

B7: B203 E9: D499 I4: D403
B8: D499 G2: D499 I6: D499
D2: D499 G4: D405 I8: D499
D4: D499 G5: D499 I10: D499
D6: D499 H2: D499 I11: D499
D7: D499 H3: D499 J1: D499
E6: D402 H4: D499 J2: D499

VI. Answers to Questions

1. List down the members of each group of cations (Group I to V).
2. Give the common precipitating reagent for each group of cations.
3. Why is Group V cations often referred to as the soluble group?
4. Give the composition of Aqua Regia.
5. What are the limitations of flame test?
6. Why is HCl used in flame test?
7. Give the resulting flame color of the following cations in flame test:
a. Na+ e. Ca2+
b. K+ f. Ba2+
c. Li+
d. Sr2+
Name: Date:
Section and schedule: Score:
Group #:

REPORT SHEET
EXPERIMENT 2
CATIONS
I. Data and Results

A. Group I Cations
Cation Reagent Used Product Result

B. Group II Cations
a. Group II-A
Cation Reagent Used Product Result
 b. Group II-B
Cation Reagent Used Product Result

C. Group III Cations

a. Group III-A
Cation Reagent Used Product Result
 c. Group III-B
Cation Reagent Used Product Result

D. Group IV Cations

Cation Reagent Used Product Result

 E. Group V Cations
Cation Reagent Used Product Result

II. Conclusion:

III. Answers to research questions

IV. References