Experiment 9: Qualitative Analysis

Lorenzo Carlos Baquiran, Charles Ashley Jimenez, Giana Leigh Mamaradlo, Clarisa May Oranda
Groups 9 & 10, Chem 18.1 MAB2, Sir Gabriel Luis Neri
November 26, 2015
I.

Abstract

A qualitative test is designed to identify the presence of a certain species in a sample. In this procedure,
the unknown is systematically subjected to a number of different reagents, taking advantage of the different
chemical properties of ions, such as solubility in a solution or complex formation, to ascertain the species in
the unknown. By predetermining the results of a specific reaction when a specific ion is present, we are able
to identify the ions present in a solution. In the test for cations, groups are selectively precipitated using
different reagents. For example, group I cations are separated from groups II to V by subjecting the solution
of unknown to HCl. This procedure takes advantage of the fact that group I cations are the only cation group
to form insoluble chlorides. Confirmatory tests then follow which will point to only a single species. In the test
for anions, characteristic precipitates and complexes are formed with specific reagents.
II.
III.

Keywords: Qualitative, unknown, precipitation, complex formation, confirmatory test, cation, anion.
Introduction
insoluble. For the samples that are sparingly
soluble or insoluble in water, the solubility is tested
Qualitative analysis is the determination of the
in the following solvents until a suitable solvent is
presence or absence of a certain species in a
found. These solvents were tried in order. The
sample. Even before the development of more
solvents were: a) 6M HCl b) concentrated HCl, c)
advanced techniques such as spectroscopy,
6M HNO3, d) concentrated HNO3, e) aqua regia
chemists are already doing different methods of
(concentrated HCl-concentrated HNO3 mixture).
qualitative analysis; that is, the sample is treated
with various reagents to test for reactions
characteristic of certain ions in solution, such as
PREPARATION OF THE CATION TEST
complex formation or precipitation. In analysis of
SOLUTION
cations, the ones that are tested for are essentially
the manipulation of solubility equilibria and
A pinch of the sample was dissolved in the
complex formation. We can group certain cations
appropriate solvent. The resulting solution was
by their tendencies to precipitate under given
then used as the cation test solution.
conditions, effectively separating a group of ions
from others and permitting confirmatory tests. On
GROUP I CATIONS
the other hand, analysis for anions also involves
formation of precipitates or reactions with strong
To 2 mL of the test solution, 8 drops of 6M HCl
acid. Confirmatory tests are also possible for
is added. The solution is then put in a centrifuge to
anions due to characteristic reactions and
separate group I cations. The decantate is saved
complexes that each anion may form with a given
for the separation and identification of group II
set of reagents.
cations. Group I cations are the only cations that
form insoluble chlorides (white precipitate). This
IV.
Methodology and Discussion
allows us to separate group I cations from group 24. If no precipitate is formed, it means there are no
SOLUBILITY TEST
group I cations in the unknown.
The solubility of the sample was determined by
Ag+ + Cl- -> AgCl
treating a very small portion of the finely powdered
substance (not exceeding the size of a grain of
Pb+2 + 2Cl- -> PbCl2
rice) with 2 drops of water and then stirred for 25
to 30 seconds. If the solid dissolved completely,
2 Hg2+ + 2Cl- -> Hg2Cl2
this meant that the sample is soluble in water. For
the samples that did not dissolve, 5 more drops of
To the white precipitate, 2 mL of hot water is
water were added and it was stirred for another 30
added. The solution is put in a centrifuge and
seconds. If the salt dissolved, it is somewhat
decanted while still hot. Another 2 mL of hot water
soluble in water. For the samples that still did not
is added and the solution is once again put in a
dissolve, 10 more drops of water were added and
centrifuge and decanted. The precipitate, to be
it was stirred once again. If the sample dissolved
called 1-A, is set aside. If a precipitate forms in the
during that time, it is considered to be sparingly
centrifugate, it is put in a hot water bath until the
soluble in water. For the samples that still did not
precipitate dissolves. 2 drops of 1M K2CrO4 is then
dissolve, it is said to be very slightly soluble or
added to the clear hot solution. The solubility of

Chem 18. 1 General Chemistry Laboratory 2 Qualitative Analysis

Page 1 of 8

PbCl2 increases considerably in hot water, while

the solubility of AgCl remains constant. This allows
us to separate PbCl2 (supernatant liquid) from
AgCl (precipitate). The addition of KI or K2CrO4 is
a confirmatory test for the presence of the Lead
ion. The visible result should be a golden yellow
precipitate (PbCrO4).

PbCl2 -> Pb+2 + 2Cl-

Pb2+ + CrO42- -> PbCrO4

To precipitate 1-A, 5 drops of 6M NH3 and the

solution was stirred, centrifuged and decanted.
The decantate, which will now be referred to as 1B, is saved for later. The procedure is repeated on
the precipitate. Should the precipitate dissolve, the
resulting solution is combined with 1-B. If it only
dissolves partially, it is centrifuged and decanted.
The decantate is combined with 1-B and the
precipitate, which contains undissolved chlorides,
is discarded. Centrifugation and decantation of
liquid after the addition of ammonia is because
silver reacts with ammonia to form Ag(NH3)2+. The
addition of NH3 is a confirmatory test for the
presence of Mercury ion. Mercury(I) chloride has a
very characteristic reaction with ammonia. A black
or gray precipitate establishes the presence of the
mercury. In this qualitative analysis though, this
result is impossible, due to the unavailability of the
mercury as a reagent. 6M HNO3 is added to the
solution, then the solution centrifuged and
decanted until acidic to litmus. If silver is present in
the test sample, the result should be a white
precipitate. The acid consumes the NH3 in the
Ag(NH3)2+ complex. Cl- then reprecipitates with
Ag=, forming AgCl.

AgCl + 2NH3 -> Ag(NH3)2+ + Cl-

Ag(NH3)2+ + Cl- + H+ -> NH4+ + AgCl

GROUP II CATIONS
The decantate from the separation of group I
cations is checked to have a pH of 0.5. If it is not,
the pH is adjusted using NaOH or HCl dropwise. 2
mL of 5% thioacetamide is then added to the
solution and stirred. It is then put in a boiling water
bath for 10 minutes. If any group II cations are
present in the test sample, a precipitate, black or
yellow, should form. Hydrogen Sulfide is generated
by hydrolyzing thioacetamide. This process is
hastened by the acidity of the solution.

water is added and set aside. This solution will now

be referred to as 2-A. The pH of the decantate is
checked to still be 0.5. If not, adjust by using 0.5 M
NaOAC or 0.5M HOAc. The solution is heated in a
boiling water bath for 3 minutes, cooled,
centrifuged, and decanted. The decantate is saved
for the separation and identification of group III
cations. To the precipitate, 1 mL of NH4Cl and 1
mL of water is added, stirred and combined with 2A. The combined solution is stirred, centrifuged,
and decanted, with the liquid being discarded. The
precipitate is washed with 1 mL of water,
centrifuged and decanted, and once again, the
liquid discarded. To the precipitate, 15 drops of 6M
HNO3 was added, and the solution heated in a
water bath. Any precipitate formed could just be
sulfur and should be discarded. This step involves
the conversion of sulfides of the precipitate to
soluble nitrates by treatment with nitric acid.

2-3 drops of 6M HCl is added to the clear solution.

A white precipitate indicates the presence of lead
in the test sample. The solution is then centrifuged
and decanted.

Generally: M2+ + H2S <-> MS(s) + 2H+

The mixture is cooled, centrifuged and decanted.

To the precipitate, 2 mL of 1M NH4Cl and 2 mL of

Pb2+ + HCl -> H+ + PbCl2 (white

precipitate)

To the residue, 10 drops of NaOAc is added. The

solution may be heated, if needed, to dissolve the
precipitate. 1M K2CrO4 is added to the clear
solution.

PbCl2 + K2CrO4 -> KCl + PbCrO4

To the decantate, 6M NH3 is added until the

solution turns basic. A deep blue solution indicates
the presence of Cu2+ in the test sample.

Cu2+ (aq) + 4 NH3(aq) --> Cu(NH3)42+ (aq)

(blue)

The solution is divided into two. To the first portion,

6M CH3COOH is added until the color fades and
the solution is acidic. The acid consumes the NH3
in the complex, freeing the Cu2+. A drop of 0.2M
K4Fe(CN)6 is added. A red-brown precipitate
confirms the presence of Cu2+ in the test sample.

PbS(s) + 2NO3- (aq) + 4H+(aq) Pb2+(aq)

+ S(s) + 2NO2 (g) + 2H2O
CuS(s) + 2NO3- (aq) + 4H+ (aq) Cu2+ (aq)
+ S(s) + 2NO2 (g) + 2H2O
CdS(s) + 2NO3- (aq) + 4H+ (aq) Cd2+ (aq)
+ S(s) + 2NO2 (g) + 2H2O

2Cu(NH3)42+ (aq) + K4[Fe(CN)6](aq) -->

Cu2[Fe(CN)6](s) + 8NH3 (aq) + 4K+ (aq)

To the other half of the decantate, a pinch of solid

sodium hydrosulfite, Na2S2O4 is added if the
solution is blue. It is then put in a boiling water bath,
centrifuged, and the residue discarded. Sodium

Chem 18. 1 General Chemistry Laboratory 2 Qualitative Analysis

Page 2 of 8

hydrosulfite reduces the remaining Cu 2+ to Cu(s).

2 mL of 5% thioacetamide is added to the liquid
and heated in a water bath. Thioacetamide
reprecipitates Cd2+ as CdS(s), which is color
yellow.

Cd2+ + H2S <-> CdS(s) (yellow)+ 2H+

Group III Cations

Group III cations include the base-insoluble
sulfides and hydroxides. This group includes hard
acids (Al3+, Cr3+, Fe3+) which react with the hard
base OH- to produce hydroxide precipitates, and
borderline acids (Zn2+, Ni2+, Co2+, Co3+, and Mn2+)
with react with the very soft base S2- to form
insoluble sulfides.
To the decantate from the previous part, add 1
mL of 5% thioacetamide and heat the mixture in a
hot water bath for at least 5 minutes. Then add 1
mL of 15 M NH3 and stir up the precipitate. The
mixture will then be heated for 5 minutes in a water
bath. The precipitate shall be separated and
washed with few drops of H2O. Afterwards, 10
drops of 1M HCl will be added to the precipitate.
Stir it and separate the mixture immediately. Wash
the residue with four drops of 1 M HCl.
Another 3 drops of 12 M HCl and 1 drop of 16
M HNO3 will be added to the residue. Heat it again
in a water bath. If the residue remained, it may be
sulfur, and it will be discarded. The solution will the
be boiled and just sufficient 6M NH3 will be added
to make it slightly basic to litmus. Afterwards, the
solution must be diluted to 1 mL and, and divide it
into 3 parts.
To the first part, add 1 drop of
dimethylglyoxime, and allow it to stand for 1
minute. The second portion will the be acidified
with 1 M HCl and several crystals of NH4CNS.
Equal volume of acetone will be added, then
agitate the mixture. The third part will also be
acidified but this time with CH3COOH and several
large crystals of KNO3. The mixture must be warm.
The solution that was previously separated will
be trasfer into a casserole. Thereupon, 1 mL of 4
M HNO3 will be added, evaporating the solution a
moist residue. This residue will be dissolved with 1
mL of water and transferred into a test tube. For
the precipitate to form, addition of 4M NaOH must
be done. If no precipitate will be formed, separation

and identification of Group IV cations can be done.

Then add 10 drops more of NaOH in excess, 6
drops of freshly prepared 3% H2O2 to the mixture.
Wash residue with 10 drops of H2O which has been
added 1 drop of 4M NaOH. The residue must then
be treated with 1 mL of 4 M HNO3 and 2 drops of 1
M NaNO3. Stir the mixture and heat it in a water
bath. Separate any residue that will remain. Heat
the solution into boiling, cool it, then divide into
three parts. To the first portion of this solution,
small quantity of NaBIO3 and 2 drops of 4M HNO3
will be added; 10 drops of 0.2 M KSCN to the
second; 2 drops of 0.2 M K4Fe(CN)6.
GROUP IV CATIONS:
The solution from the first step of the
identification of Group III cations was evaporated
to dryness and ignited in a casserole. The residue
was dissolved in 1M HCl, and the solution was
turned alkaline by adding 6M NH3 with 1 more drop
in excess. 2 drops of 1M (NH4)2CO3 or more were
added for complete precipitation to occur.
Solutions that did not result to precipitation
proceeded to the identification of Group V cations.
For solutions with precipitates, the mixture was
warmed in a hot water bath and allowed to cool.
The precipitate was then separated and the
solution was reserved for the identification of
Group V cations. The precipitate was then
dissolved in a mixture of 2 drops of 4M HOAc and
4 drops of NH4OAc were also added. 1 drop of 1M
K2CrO4 was then added to the solution. For formed
precipitates, the mixture was separated and the
solution was reserved for the third step. The
precipitate was then dissolved in 2 drops of 12M
HCl. A flame test was then performed with this
solution and a drop of 6M H2SO4 was added to the
remainder of the solution. For the third step, 6M
NH3 was added to the solution until a color change
from orange to yellow was observed. A volume of
ethyl alcohol equal to the volume of the solution
was added. The mixture was separated and the
solution was reserved for the fourth step. The
precipitate was then dissolved in 2 drops of 12M
HCl and a flame test was performed in this
solution. The solution that was reserved from the
third stop was heated to boiling and 2 drops of
0.4M (NH4)2C2O4 were then added to the solution.
The precipitate was dissolved in 2 drops of 12 M
HCl and then a flame test was performed in this
solution.
DISCUSSION
GROUP IV CATIONS
Group 4 cations are also called the carbonate
group. They form insoluble carbonates. The
cations in this group are Ba2+, Ca2+ and Sr2+. .

Chem 18. 1 General Chemistry Laboratory 2 Qualitative Analysis

Page 3 of 8

Group 4 cations are also one of the hardest to

distinguish since they belong to the same group in
the periodic table. The only way to differentiate
them from each other and identify the cation
present is by conducting flame tests because each
cation produces a different color when conducted
with a flame test. (NH4)2CO3 or ammonium
carbonate was added in order to separate Group 4
cations and Group 5 cations since Group 4 cations
form insoluble carbonates. So, if group 4 cations
are present in the sample solution, precipitation will
occur. The precipitate was then dissolved in acetic
acid since group 4 cations are soluble in acid. The
addition of 1M K2CrO4 causes the Group 4 cations
to form chromates. The mixture was separated and
the solution was reserved for the third step. The
white precipitate that formed is assumed to be
BaCrO4 whereas the solution is assumed to either
be Sr2+ or Ca2+ since the acidic nature of the
solution keeps the concentration of the CrO 42-- low
enough to prevent the precipitation of SrCrO4. For
the precipitate, 12M HCl is used to dissolve the
barium precipitate and a flame test is then
performed to this solution. A green flame indicates
the presence of Ba2+ ions. 6M H2SO4 was added to
the remainder of the solution for precipitation to
occur again since barium cannot precipitate in the
presence of high hydronium concentration. A white
precipitate indicates the presence of Ba2+ ions. For
the solution that was reserved for the third step, the
addition of NH3 until the color change is observed,
converts all dichromate ions (orange) to chromate
ions (yellow) and this higher concentration of
CrO42- allows the precipitation of SrCrO4. The
solution was separated from the precipitate that
formed. Ethyl alcohol is also added to the
precipitate in order to aid in confirming which cation
is present when the flame test is being performed.
The precipitate was dissolved again in 12M HCl
and the flame test was performed. A crimson red
flame indicates the presence of Sr2 + ions. For the
solution that was separated, after being heated,
and 2 drops of 0.4M (NH4)2C2O4 were added to it.
The precipitate that formed from this was again
dissolved in HCl and a flame test was performed.
An orange-red flame indicates the presence of
Ca2+.
GROUP V CATIONS:
A drop of 0.4M (NH4)2C2O4 and a drop of 1M
(NH4)2SO4 was added to the solution from the first
step of the identification and separation of Group
IV cations. Any precipitate that formed was
separated from the solution and then discarded.
The solution that remained will be used in the next
step. 6M NH3 was added to 10 drops of the solution
until it became alkaline to litmus and then 1 more
drop was added in excess. 2 drops of 1M Na2HPO4
was added to the solution. The precipitate was
then separated from the mixture and the solution
was discarded for future use. The precipitate was

then dissolved in a mixture of 2 drops of 1M HOAc

and 3 drops of water. 1 drop of titan yellow and 6M
NaOH was added to the solution until the solution
became distinctly alkaline. A flame test was then
performed to 10 drops of the original sample, using
a portion that had not been used in any way. The
intensity and the duration of the flame of the
original sample was then compared to the flame to
that obtained from a sample of distilled water and
that from 0.1M NaCl solution. For the last step, 10
drops of the fresh sample was poured into a 50-mL
beaker. A piece of red litmus paper was moistened
and placed at the bottom of a small watch glass.
10 drops of 6M NaOH was then added to the
sample in the beaker and swirled to stir. The
beaker was then covered with the watch glass and
then gently heated. Its important to note that it was
never boiled and that extra care was given and no
solution came in contact with the litmus paper. The
color of the litmus paper was then observed.
DISCUSSION:
GROUP V CATIONS:
Group 5 cations are the alkali metals and NH4+.
These cations produce soluble hydroxides and
carbonates. The Group 5 cations are Mg2+, Na+, K+
and NH4+. Mg2+ is considered a group 5 cation
sometimes, since it also forms soluble carbonates
however it can also form insoluble hydroxides
when the pH is very basic. The addition of 0.4M
(NH4)2C2O4 and 1M (NH4)2SO4 to the solution from
the first step of the identification of group 4 cations
was done in order to precipitate out the group 4
cations that may still be present in the solution. The
precipitate was discarded and 6M NH3 was added
to 10 drops of the remaining solution with one more
drop in excess until it turned alkaline to litmus. 1M
Na2HPO4 was added to the solution in order to
identify the presence of Mg2+ ions. The white
precipitate that formed from this was separated
from the mixture and the solution was reserved for
future use. This precipitate was then dissolved in a
mixture of 2 drops of 1M HOAc and 3 drops of
water. Titan yellow is an indicator and this is added
to the solution along with 6M NaOH in order to
basify the solution. If Mg2+ ions are present in the
solution, yellow precipitate will then form. A flame
test will be conducted for the fresh original sample
and the intensity and the duration of its flame will
then compared to that of distilled water and NaCl
solution. An intense yellow flame indicates the
presence of Na+ ions and a pale violet flame
indicates the presence of K+ ions. For the last step,
the presence of NH4+ ions is determined when the
red litmus paper turns to blue.
PREPARATION
SOLUTION

Chem 18. 1 General Chemistry Laboratory 2 Qualitative Analysis

OF

THE

ANION

TEST

Page 4 of 8

For samples that were soluble in water, a pinch

of the sample was dissolved in 2ml of water. A few
drops of 3M Na2C2O3 were then added to the
solution. If no precipitate formed, a pinch of the
sample was then dissolved in 2 ml of water and
was used as the anion test solution. For samples
that were insoluble in water or for samples that
formed a precipitate with Na2C2O3, a pinch of the
unknown sample was placed in a micro test tube.
3ml of 3M Na2C2O3 was added and then it was
heated with stirring in a 5-minute water bath. The
solution was centrifuged and decanted. The
decantate contained the unknown anion and
Na2C2O3. The solid residue consisted of the
carbonate or hydroxide of the unknown cation. The
decantate was then used as the anion test solution.
PRELIMINARY TESTS FOR ANIONS
For the preliminary test for the anions, three
tests were employed, namely; the Sulfuric Acid
Test, the Chloride Group Test and the Sulfate
Group Test. Each test were performed separately
but the results all correlate with one another.
In the Sulfuric acid test, a small pinch of the
unknown salt was dropped inside a test tube. A
drop of concentrated sulfuric acid was allowed to
travel slowly at the walls of the test tube to the
bottom where the solid is. Upon contact, any form
of reaction (color change or gas production) was
noted. If there was not reaction, the test tube was
subjected to heat in a hot water bath. The residue
was discarded afterwards.
The chloride group test was performed by
using five drops of the original test solution and a
drop of 0.5M AgNO3. If there were precipitates, the
solution was centrifuged and the supernatant liquid
was discarded. The residue was then washed with
five drops of distilled water and decanted. Five
drops of 3M HNO3 solution was added and the
complete dissolution or retention of the precipitates
was noted. Once again, the solution was
centrifuged and was added with 6M NH4OH (NH3
substitute) until the solution becomes basic to red
litmus. Two drops of 0.5M AgNO3 was added and
the color of the resulting precipitate was observed.
For the sulfate group test, five drops of the test
solution was added with 3M NH4OH (NH3
substitute) until alkaline to litmus. Should any
precipitate form, the mixture would be centrifuged
and the solid would be discarded. Two drops of
0.3M BaCl3 and 0.3M CaCl2 solutions were then
added. If there was no precipitate, no further tests
are needed.

CONFIRMATORY TEST FOR ANIONS

After the preliminary tests, confirmatory tests
were done to verify the presence of the anion in the
salt. There are fifteen confirmatory tests, with one
confirmatory test for each possible anion.

The first confirmatory test was for thiocyanide

(CNS-) test. 5 drops of the test solution was added
with 1 drop 0.1 M Fe(NO3)3. A blood-red solution
confirms presence of CNS-.
Next was for iodide (I-). 6 drops of the test
solution was acidified with 6M HNO3, added 2
drops of 0.1M Fe(NO3)3 and 10 drops hexane
(CCl4 substitute). A purple hexane layer confirms
presence of I-.
If iodide is present, the hexane layer is
removed and added with a drop of Fe(NO3)3.
Shake the solution and repeat the process until
hexane is no longer colored violet. The aqueous
layer will be used to test for the presence of Br -.
Using five drops of the aqueous solution from
the test for iodide, it was combined with 5 drops 16
M HNO3 to test for bromide (Br -). The test tube was
dipped in boiling water for 30 seconds and cooled
in cold water. 3 drops of hexane (CCl4 substitute)
were added and it was shaked thoroughly.
Bromide is present if the hexane layer turns
yellowish or reddish brown. Discard hexane if the
sample tests positive for bromide. Extract the Brby adding fresh hexane and shaking the test tube.
For the test for chloride (Cl-), the Br - solution
was added with 10-15 drops H2O and 2 drops
AgNO3 and acidified with 6M HNO3. A white
precipitate (AgCl) will confirm the presence of
chloride.
A small amount of the original sample in a
beaker was added 10 drops 6 M HCl to test for the
presence of sulfide (S2-). Place a filter paper that
was moistened with lead acetate over convex
(bulging, curved outward) side of the watch glass,
and place the watch glass over beaker with the
paper inside. Warm the beaker gently. If the paper
turns black or silvery black, the sample contains
sulfide.
For carbonate (CO32-), this is unnecessary if no
effervescence was observed in the preliminary test
with H2SO4. Add 3 drops of 3 M HCl to a small
amount of sample in a test tube. Using a prepared
glass dropper with Ba(OH)2 suspended over the
solution, cover the test tube with the rubber bulb.
Warm the test tube and observe the droplet. The
sample contains carbonate if the droplet turns
cloudy of white.
To test for the presence of sulfate (SO42-), add
6 M HCl dropwise to 3 drops of the test solution
until solution turns acidic. Add 4 drops 6M HCl
followed by 1 drop BaCl 2 solution. White
precipitants indicate the presence of sulfate.
For chromate (CrO42-), it is unnecessary if
sample solution is colorless. To 3 drops of sample

Chem 18. 1 General Chemistry Laboratory 2 Qualitative Analysis

Page 5 of 8

solution, add 1 M HNO3 dropwise until acidic. Then,

add 3 drops 3 M HNO3 and 3 drops 3% H2O2
solution. Shake once and a blue color indicates the
presence of chromate.
For phosphate (PO43-), add 5 drops 16 M
HNO3 and 3 drops ammonium molybdate to 5
drops of the test solution and warm this in a hot
water bath. The presence of phosphate is indicated
by the yellow precipitate.

Table of anions that react with cold sulfuric acid:

Anion
Visible Result
CO32-

Colorless, odorless gas

C2O42-

Effervescence

2-

S
Cl-

Smells like rotten eggs

Steamy acidic fumes

Br-

Steamy brownish acidic fumes

I-

Purple fumes,
turns to a brown slurry

CrO42-

Orange solution

NO2-

Brownish acidic fumes

(C2O42-),

For the oxalate

2 drops of the test
solution is added with 1 drop 6M HOAc and 2 drops
0.2M CaCl2. If a precipitate forms, centrifugate it
and wash immediately with water. To the
precipitate, add 2 drops water, 2 drops 0.02M
KMnO4, and 2 drops 6M H2SO4. If the color of
permanganate fades within 30 seconds or less, the
sample contains oxalate.
For the acetate (CH3COO-), add 2 drops of 1:1
proportioned solution of H2SO4. Gently waft the
vapors and if the sample smells like vinegar,
acetate is present in the solution in large amounts.
If the sample does not smell of vinegar, add 2
drops alcohol and stir well and then warm gently. If
both the sample and the control have the sweetish
odor of ethyl acetate, it means that the sample
contains acetate.
For nitrate (NO3-), 2 drops of the test solution
in a 5 mL test tube was added with 10 drops
concentrated sulfuric acid and a grain of FeSO4.
Let stand for 1-2 minutes and if the sample forms
a brown ring, it contains nitrate.
For thiosulfate (S2O32-), 5 drops test solution
added with 3 drops 3M HCl. If a cream/ whitish
precipitate forms, thiosulfate is present.

Anion
CO32-

Equation for the Reaction

CO32- + H2SO4(l) HSO4- + HCO3HCO3 CO2 + H2O

C2O42-

C2O42 2CO2

S2-

S2- + H2SO4(l) HSO4- + H2S(g)

Cl-

Cl- + H2SO4(l) HSO4- + HCl(g)

Br-

Br- + H2SO4(l) HSO4- + HBr(g)

I-

I- + H2SO4(l) HSO4- + HI(g)

CrO42-

I- + H2SO4(l) HSO4- + HI(g)

NO2-

NO2- + H2SO4(l) HSO4-+ HNO2

Table of anions that react with hot sulfuric acid:

Anion

Visible Result

NO3CH2COO

Brownish acidic fumes

-

No visible reaction

(NO2-),

For nitrite
acidify 5 drops of the test
solution by adding 6M HOAc dropwise, then add
5 drops 0.1M K3Fe(CN)6. Let stand for one minute
and add 1 drop FeCl3. A deep red precipitate
indicates the presence of nitrite in the sample.
For permanganate (MnO4-), this confirmatory
test is unnecessary if the sample solution is
colorless. Using 2 drops of the test solution, add 2
drops H2O, 2 drops 0.02M Na2C2O4 and 2 drops
6M H2SO4. The disappearance of the color of the
solution within 30 seconds indicates the presence
of permanganate.
Discussion
Preliminary Tests for Anions
In the sulfuric acid test, the anion present in the
sample will dictate the reaction that will occur. The
table below explains the visible reaction for each
anion and the corresponding chemical equation for
each.

Anion

Equation for the Reaction

NO3-

NO3- + H2SO4(l) HSO4-+ HNO3

CH2COO-

CH3COO- + H2SO4(l) HSO4-+

CH3COOH

For the chloride group test, the presence of the

chloride group namely (CNS, Cl, Br, I, S) will result
in the formation of a complex with Ag(NO 3) in
HNO3. If there was no precipitate, it can further be
tested for the presence of CrO42- and PO43- by
adding 6M NH3 and the result would have a yellow
and red precipitate respectively.
For the sulfide group test, a basic solution will
result in the precipitation of the following sulfide
group ions; SO42-, CrO42-, PO43-, C2O42-. A yellow
precipitate may form which indicates the presence
of CrO42-. For precipitates that are not color yellow,
HCl was added and if it dissolved, SO42- is not
present.

Chem 18. 1 General Chemistry Laboratory 2 Qualitative Analysis

Page 6 of 8

5H2C2O4 + 2MnO4- + 6 H3O+ 2Mn2+ +

10CO2 + 14 H2O
Sulfuric acid added to a precipitate of
calcium oxalate formed produces soluble
oxalic acid. Oxalic acid reduces permanganate
to manganous ions. The color of the solution
changes from purple to colorless. Oxalate is
present in the sample if the color of the
permanganate fades within 30 seconds.

Confirmatory Test for Anions

6CNS- + Fe3+ Fe(CNS)63CNS- produces a blood-red
complex ion with the ferric ion.

colored

NO2- + H3O HNO2 + H2O

2HNO2 + 2 H3O+ + 2I- 2NO +I2 + 4H2O
The nitrous acid addition oxidizes the
iodide ion to iodine with no action upon the
bromide and the addition of Fe(NO3)3 to the
acid solution produces the nitrite ion. When
shaken with hexane or in CCl4, iodine
becomes violet in color which confirms the
presence of I-.

CH3COO- + H2SO4 CH3COOH + HSO4Dilute sulfuric acid added to the sample

produced the smell of vinegar.
3Fe2+ (aq) + NO3- (aq) + 4 H+ (aq) 3Fe3+ (aq) +
NO (aq) + 2 H2O (l)
Fe2+ (aq) + NO (aq) Fe(NO)2+ (aq)
Concentrated sulfuric acid and a grain of
ferrous sulfate were added to the test solution.
The brown ring that formed indicates the
presence of nitrates in the sample.

10Br-(aq) + 2MnO4- 5Br2 (aq) + Mn2+(aq) + 8H2O

The 2MnO4- ion oxidizes Br- ion to
elemental Br2 which is soluble in the hexane or
the CCl4 layer. The oxidation results to the
reddish brown layer.

S2O32- (aq) + 2 H+ (aq) SO2 (g) + S (s) + H2O

Hydrochloric acid added to the solution
resulted in the formation of a cream/white
precipitate which indicates the presence of

Ag(NH3)2+ + Cl- + 2H3O+ AgCl + 2NH4 +

2H2O
The silver complex with ammonia is easily
broken down in the acidic solution. A white
precipitate of AgCl results if chloride ions are
present.

HNO2 (aq) + Fe2+ (aq) + H+ (aq) Fe3+ (aq) + NO

(aq) + H2O
NO (aq) + Fe2+ (aq) Fe(NO)2+ (aq)
Acetic acid added to acidify the solution
together with the addition of ferric chloride
formed a deep red precipitate after standing for
1 minute.

H2S (g) + Pb2+ (aq) PbS (s) + 2H+ (aq)

Sulfide is present in the sample if the filter
paper contains black-silvery black precipitates.
BaCO3 + 2H3O+ Ba2+ + 3 H2O + CO2
CO2 + Ba(OH)2 BaCO3
The cloudy or white observation visible
result upon dropping Ba(OH)2 is the barium
carbonate precipitate formed from the reaction
between the CO2 gas and Ba(OH)2
SO4-(aq) + Ba2+(aq) BaSO4 (s)
Sulfate ion is very unreactive but
undergoes precipitation reaction with barium
or lead ion and a white precipitate indicates the
presence of sulfate.
BaCrO4 + H3O+ HCrO4- + Ba2+ + H2O
A yellow precipitate, BaCrO4, indicates
the presence of the chromate ion, which is
soluble in dilute HCl.
H2PO4- (aq) + 12 MoO4- + 22 H3O+ + 3NH4+
(aq) (NH4)3PO4(12MoO3) + 34 H2O
The phosphate ion reacts with ammonium
molybdate in a nitric acid solution to form
yellow
precipitate
of
ammonium
phosphomolybdate. This indicates the
presence of PO4.
CaC2O4 + H23O+ Ca2+ + H2C2O4 + 2H2O

5 C2O42- (aq) + 2 MnO4- (aq) + 8 H+ (aq) 10 CO2

2+
(g) + 2 Mn
(aq) + 4 H2O
Sodium oxalate and sulfuric acid added to
the diluted solution caused the solution to
become colorless indicating the presence of
permanganate.
V.

Conclusions and Recommendations

Given the information from above, the authors

of this paper conclude that qualitative analysis is
a valuable tool in determining the presence or
absence of cations and anions in solution or salt.
Qualitative analysis involves testing the unknown
using different chemical tests which indicates for
the presence or absence of different groups of
cations and anions. Once narrowed down,
confirmatory test may be used to test for the
presence of the specific anion or cation. It is
recommended that the different tests would be
repeated to gain more precise results. Also, it is
also recommended that the sample given is
separated because of the possibility of it to
undergo redox reaction with the contents of the
sample.

Chem 18. 1 General Chemistry Laboratory 2 Qualitative Analysis

Page 7 of 8

VI.
Brown,

References
Theodore
E.,
Lemay,
Eugene
H.,Bursten,Bruce E.,Murphy, Catherine
(2008). Chemistry: The Central Science
(11th ed.), New York: Prentice Hall, ISBN
0136006175

Petrucci, R.H., Harwood, W.S., & Herring, F.G.

(2002). General chemistry: Principles and
Modern Applications. 8th edition. New
Jersey, USA: Prentice-Hall
Shriner, R.L., et. Al. (1998). The Systematic
Identification of Organic Compounds. 8th
Edition. New York: John Wiley and Sons,
Inc.

Chem 18. 1 General Chemistry Laboratory 2 Qualitative Analysis

Page 8 of 8