QUALITATIVE ANALYSIS

IDENTIFICATION OF THE ANION

 Preparation of the Unknown

PREPARATION OF THE
ANION TEST SOLUTION
FROM THE SOLUBILITY TEST DONE IN PART
A…

If sample is soluble in water:

Dissolve a pinch of the Add a few drops

sample in 2 mL water of 3M Na2CO3

No precipitate: Repeat step 1 and use as anion test solution.

W/ precipitate: Proceed to step 2.

FROM THE SOLUBILITY TEST DONE IN PART
A…

If sample is insoluble in water or

formed a precipitate w/ Na2CO3:

Place a Add 3 Heat with

stirring in
Centrif Use
pinch of mL of decantate
sample in
a water uge as the
a micro 3M bath for
about 5
and anion test
test tube Na2CO3 minutes decant solution
 Preliminary Tests

ANION ANALYSIS
TEST WITH SULFURIC ACID
Watch
Add out of
1 drop forconcentrated
formation
of prodout
sulfuric
Watch uct (a
togas
acidfor or a bi of
a small
formation
Add 1 drop of concentrated
solid sample
substance (1/4 sizeingrain
different
of prod
sulfuric uct
acid(a
togas or a bi of
a small
of rice)from the sample)
color
solid sample
substance (1/4 sizeingrain
different
of rice)from the sample)
color

If
no
ev
id
en
t
re
ac
ti
on
,
w
ar
m
th
e
te
st
tu
be
ge
nt
ly
.
TEST WITH SULFURIC ACID
 Anions that react with cold sulfuric acid:
ANIONS VISIBLE RESULT REACTION EQUATION
Carbonate Effervescence CO23- + H20 → CO2 + H20

Oxalate Evolution of CO and CO2 C2O42- + 2H+ → H20 + CO + CO2

Sulfide Rotten egg odor S2- + H+ → H2S

Chloride Pungent odor; Blue litmus to red Cl- + H2SO4 → HCl + HSO4-

Bromide Reddish brown solution KBr + H2SO4 → HBr + HSO4- + K+

2KBr + 2H2SO4 → Br2 + SO2 + SO42- + 2K+ + 2H2O

Iodide Violet powder – starch powder blue 3I- + 2H2SO4 → I3- + SO42- + 2H20 + SO2
I- + H2SO4 → HI + HSO4-
9I- + 4H2SO4 → 3I3- + S + 3SO42- + 4H2O
12I- + 5H2SO4 → 4I3- + H2S + 4SO42- + 4H2O

Chromate Orange- red solution 2CrO42- + 2 H+ ↔ Cr2O72- + H2O

Nitrite Evolution of brown fumes NO2- + H+ → HNO2

2 HNO2→ H2O + N2O3
3 HNO2→ HNO3 + 2 NO + H2O
2NO + O2→ 2 NO2
TEST WITH SULFURIC ACID
 Anions that react with hot sulfuric acid:
ANIONS VISIBLE RESULT REACTION EQUATION
Nitrate Reddish brown vapor 2CrO42- + 2 H+ ↔ Cr2O72- + H2O
NO2; pungent acid vapor
of nitric acid with fumes
Acetate Vinegar-like odor NO2- + H+ → HNO2
2 HNO2→ H2O + N2O3
3 HNO2→ HNO3 + 2 NO + H2O
2NO + O2→ 2 NO2
THE CHLORIDE GROUP TEST
Add 1 drop of 0.5 AgNO3 to 5 drops of test
solution

If a precipitate forms it could be one of the following:

Anion Precipitate
CNS- White
CO32- White
Br- Cream colored
I- Light yellow
PO43- Yellow
CrO42- Red
S2 - Black
 THE CHLORIDE GROUP TEST
Centrifuge
Addrofesidue and
Wash r esidue with 5
5distilled
drops
drops
Centrifuge
Wash and5
with
Add
discard
of 3M
water.
drops 5distilled
drops
HNO
ofDiscard wash
discard
solution.
liquid.
water. Discard wash3
of 3M
solution.
liquid. HNO3

**If
**If
all
all
dis
dis
sol
sol
ves
ves
CN
CN
SS--,,
Cl
Cl--,,
Br
Br--,,
II--,,
SS-2 -2

are
are
abs
abs
ent
ent
**If
**If
not
not
all
all
dis
dis
sol
sol
ves
ves
,,
on
on
e
e
or
or
mo
mo
re
re
of
of
the
the
se
se
cou
cou
ld
ld
be
be
pre
pre
sen
sen
tt
 THE CHLORIDE GROUP TEST
Centrifuge
Add
Add6twoM ammonia
dropsand
solution
Centrifuge
Add dropwiseand
Add6M
0.5
discard
until
M AgNO
two ammonia
drops
litmus3
reddropwise
solution
discard
0.5 M
solution
solution.
turns
until
AgNO
blue.
red litmus3
solution
solution.
turns blue.

Ye
llo
w
pr
ec
ipi
ta
te
:
Ph
os
ph
at
e
Re
d
pr
ec
ipi
ta
te
:
Ch
ro
m
at
e
Ad
Add
Ad
d 3M
Centrifuge
drops
d 3M
BaCl
Add
discard
the
drops
BaCl
of
to
the
2
THE SULFATE GROUP TEST
2 NH
2 and
Centrifuge
solution
2 and
0.3M
litmus
discard
solution
oflitmus
to 0.3M CaCl
3 dropwise
drops
ofNH
test
0.3Mto 5
3 dropwise
drops two
solid.
of testtest
CaCl
solid.
and
solution
0.3M
and
until
to 5
drops
alkaline
solution
two until
2 drops
test alkaline
2

**No
**No
pre
pre
cipi
cipi
tate
tate
::
STO
STO
P!
P!
No
No
sulf
sulf
ate
ate
gro
gro
up
up
pres
pres
ent
ent
(SO
(SO44
2-,
2-
,
CrO
CrO
2-,
2-
4 ,
4
PO
PO4433
--,
,
C
C22O O44
2-)
2-
)
**Ye
**Ye
llow
llow
pre
pre
cipi
cipi
tate
tate
::
CrO
CrO
2-
42-
4
**No
**No
n-
n-
yell
yell
ow
ow
pre
pre
cipi
cipi
tate
tate
::
pro
pro
cee
cee
d
d to
to
nex
nex
tt
step
step
Add
Add
more
THE SULFATE GROUP TEST
solution
litmus
more
litmus
five
Add 6 M HCl
Add 6 Mfive
solution HCl
until blue
drops
turns
until
red
drops
turns
blue
red

If
pr
e
ci
pi
ta
te
di
ss
ol
v
es
,
S
O
2-
2-
4
4
is
a
b
se
nt
.
 Confirmatory Tests

ANION ANALYSIS
Summary/Notes on Confirmatory Tests
ANION CONFIRMATORY TEST
CNS-
I-
Br-
Cl-
S2-
CO32- Omit if no effervescense observed in test with Sulfuric
Acid
SO42-
CrO42- Omit if unknown solution is colorless
PO43-
C2O42-
CH3COO-
NO3-
S2O32-
NO2-
MnO4- Omit if unknown solution is colorless
CNS-
Add 1 drop of 0.1 M Fe(NO3)3 to 5 drops of
test solution

Blood-red solution confirms presence of

CNS-

Discussion:
The chemical equation for this confirmatory step is:
CNS-(aq) + Fe3+ (aq) → FeSCN2+ (aq)

The addition of Fe(NO3)3 causes the CNS- ion to react with the Fe3+ ion
to form a dark red complex ion in the form of FeSCN2+.
I-
Acidify 6 drops of the test solution with 6M HNO 3

Add 2 drops of 0.1M Fe(NO3)3 and 10 drops of CCl4. Shake.

**No purple layer: No iodide; proceed to Bromide test

**Purple layer: Iodide is present

Add fresh CCl4 and Fe(NO3)3 until violet colors dissappear

Use aqueous layer for Bromide test

I-
Discussion:
In solutions, I- ions are easily oxidized. A water
sol’n of KI, for example, turns yellow with time
because the ion is readily oxidized by the air.
In the confirmatory test, the I - ion was oxidized
by the Fe+ ion, which is a moderately strong
oxidizing agent under acidic solutions. Also, I -
is easily extracted with CCl4.
This is the chemical equation involved in the I -
confirmatory test:
2I-(aq) + 2Fe+(aq) → I2 + 2Fe2+(aq)
Br-
5 drops of test solution from procedure 2 (Iodide test) + equal volume of 16M HNO 3

Submerge test tube in boiling water for 30 seconds and cool in cold water

Add 2 drops 0.02M KMnO4 + 3 drops CCl4 and shake

If the CCl4 layer becomes yellowish or reddish brown, Br - is present in the sample.

Discard the CCl4 layer and then extract the remaining Br- by adding fresh CCl4 and
shaking.Use aqueous layer for Bromide test
Br-
Discussion:
The chemical equation for the
confirmatory test is:
10 Br-(aq) + 2MnO4-(aq) + 16H+(aq) → 5Br2(aq) + Mn2+(aq) + 8H2O

The MnO4- ion oxidizes Br- ion to

elemental Br2 which is soluble in the CCl4
layer. This is why it could be extracted easily
through the CCl4 layer. The oxidation results
to the reddish brown layer.
Cl-
Acidify the solution from confirmatory test of Br- with 6M HNO3

Add 10 to 15 drops of water + 2 drops AgNO3

If there is a white precipitate, Cl- is present

Discussion:
The chemical equation for this step is:
Cl-(aq) + Ag+(aq) → AgCl(s)
In the test, the Cl- ion reacted with the Ag+ ion from the AgNO3 and
formed an insoluble salt, AgCl.
S2-
In a small beaker, add 10 drops of 6M HCl solution to a small bit of the original sample

Moisten a small piece of filter paper with PbOAc sol’n and place it on the convex side of the
watch glass

Place the watch glass over the beaker with the moist paper inside the beaker

Warm the beaker gently and watch the paper

If the paper turns black or silvery black in color, S - is present in the sample.
S2-
Discussion:
H2S(g) + Pb2+(aq) → PbS(s) + 2H+
Some sulfides dissolve in non-oxidizing
acids like HCl forming solutions which
contain H2S. Hydrogen sulfide occurs as a gas
at room temperature and is only slightly
soluble in water. However, it is not a very
stable substance. It could be easily oxidized
by air or oxidizing agents like HNO3, Fe3+,
Cr2O72-, NO2-, Pb2+.
CO32-
Put a small bit of the sample into a test tube and add 3 drops 3M
HCl

Quickly drop a medicine dropper with short glass tube into the Ba(OH)2 and insert the drop
of Ba(OH)2 into the test tube such that the rubber bulb covers the top of the test tube

Warm the bottom of the test tube (but not to boiling)

If the droplet of Ba(OH)2 becomes more cloudy or white, CO32- is

present
CO32-
Discussion:
The chemical equation for this confirmatory step is:
CO2(g) + Ba2+(aq) → BaCO3(s) + H2O
Generally, carbonate salts are insoluble in water except
those of the alkali metals and ammonium ion. However,
all carbonates dissolve in solutions of acids because of the
formation of carbonic acid. Addition of acids to solid
carbonates and carbonate solutions causes effervescence
due to the evolution of gas.
The cloudy or white observation in the droplet of Ba(OH) 2
is actually the barium carbonate precipitate, BaCO 3(s)—
formed from the contact of CO2 gas with the Ba(OH)2
solution.
SO42-
To 3 drops of test solution, add 6M HCl drop by drop until the solution turns acidic

Add four more drops

Add a drop of BaCl2.

A white ppt indicates the presence of SO42-

Discussion:
The chemical reaction is: SO42-(aq) + Ba2+(aq) → BaSO4(s)
Sulfate ion is very unreactive compared to the other anions. It is not readily
reduced or oxidized. However, sulfate ion undergoes ppt reaction with Ba 2+ or Pb2+
ion.
In this confirmatory test, the SO 42- ion reacts with the Ba2+ ion forming a white
ppt which is insoluble n sol’ns of strong acids or any other common reagent.
CrO42-
Add 1M HNO3 drop by drop to 3 drops of test sol’n in a test tube,
until it turns acid in litmus test.

Add 3 drops of 3M HNO3 and enough either to make a layer above

the water, ¼ to ½ inch thick

Add 3 drops of 3% H2O2 sol’n, shake once quickly.

A blue color in the solution indicates the presence of chromate.

CrO42-
Discussion:
The chemical reactions involved in the confirmatory test are:
2CrO42- + 2H+ ↔ Cr2O72- + H2O
Cr2O72-(aq) + 4H2O2(aq) + 2H+(aq) → 2CrO5(aq) + H20
In the analysis of anions, chromate ion is the only colored anion
—bright yellow in aqeous sol’ns. Most chromates are insolube in
water but will dissolve in strong acids. Under acidic conditions,
it reacts to form the dichromate ion which is orange in nature.
In the confirmatory test, the Cr2O72- ion reacts with peroxide to
form a dark blue solution still containing the peroxide.
However, the chromium peroxide formed from the reaction of
the dichromate with peroxide is very unstable. Its color fades
quickly from dark blue to a somewhat violet color of the Cr3+
ion.
PO43-
Add 5 drops of 16 M HNO3 + 3 drops of ammnioum molybdate reagent to five drops of
test solution

Warm in water bath

If a yellow precipitate forms, phosphate is present in the solution.

Discussion:
The equation below demonstrates the chemical reaction for ths confirmatory test:
H3PO4- (aq) + 12 MoO42- (aq) + 3 NH4+ (aq) + 22 H+ → (NH4)3PO4 · 12 MoO3 (s) +
(aq)
12 H2O
Phosphates of the alkali metals are soluble. Most other phosphates, such as FePO 4,
CrPO4, BiPO4, Ca3(PO4)2 and AgPO4 are only sparingly soluble. Phosphate ion also forms a
bright yellow precipitate with ammonium molybdate—ammonium phosphomolydate.
C2O42-
Add a drop of 6 M CH3COOH and 2 drops of 0.2 M CaCl2 solution to 2 drops of test solution

If a precipitate forms, it may be calcium oxalate.

Centrifuge and wash once with drops of water.

Centrifuge again and discard wash water.

To the precipitate, add the ff:

2 drops H2O + 2 drops of 0.02 M KMnO4 + 2 drops 6 M H2SO4

If the color of the permanganate fades w/in 30 sec, oxalate is present.

C2O42-
Discussion:
Oxalates, though unresponsive in neutral
and basic solutions, tend to slowly oxidize in
acidic mediums. This oxidation process is due
to strong oxidizing agents like MnO4- ion. The
reaction converts the oxalate ion to carbon
dioxide and bleaches the purple
permanganate ion.
The reaction is:
5 C2O42- (aq) + 2 MnO4- (aq) + 8 H+ (aq)→ 10 CO2 (g) + 2 Mn2+ (aq) + 4 H2O
CH3COO-
Place a small amount of original sample in a small beaker

Add 2 drops of 1:1 ratio of sulfuric acid and water

If the smell of the mixture is like vinegar, then acetate is present. If not proceed to the succeeding steps.

Add 2 drops of alcohol and stir well.

Warm gently but not to boiling. AFTER heating, smell cautiously

If the same sweetish odor of ethyl acetate can be detected coming from the sample as from the control, then the sample
contains acetate.
CH3COO-
Discussion:
One of the natures of acetate is that it
has the odor of vinegar whenever H2SO4 is
added or any solid containing acetate. Also,
warming the solution could also enhance the
odor.
NO3-
Place of 2 drops of test solution in a 5 mL test tube. Add 10 drops of conc H 2SO4 + a grain
of FeSO4.

Let stand for 1- 2 minutes.

A brown ring indicates the presence of nitrate sample.

Discussion:
Nitrate ions only respond to a specific test reagent, consisting of
acidified iron (II) sulfate. Nitrate ion will oxidize iron (II) to iron (III), and
brown nitrogen (IV) oxide gas will evolved. The chemical reactions are a
follows:
3Fe2+ (aq) + NO3- (aq)
+ 4 H+ (aq) → 3Fe3+ (aq) + NO (aq) + 2 H2O (l)

Fe2+ (aq) + NO (aq) ↔ Fe(NO)2+ (aq)

S2O32-

5 drops of test solution + 3 drops 3 M HCl

If a cream/whitish precipitate formed,

thiosulfate.

Discussion:
Thiosulfates are unstable in acidic solutions. They will decompose to
sufite and sulfur as shown below:
S2O32- (aq) + 2 H+ (aq) → SO2 (g) + S (s) + H2O
NO2-
5 drops of test solution + 6 M HOAc
Add drop by drop until it is acidic to litmus.

Add 5 drops of 0.1 M K3Fe(CN)6

Let stand for a minute then add 1 drop of FeCl3

A deep red precipitate indicates the presence of nitrite in the sample.

Discussion:
The following are the chemical reactions involved in the confirmatory test:
HNO2 (aq) + Fe2+ (aq) + H+ (aq) → Fe3+ (aq) + NO (aq) + H2O
NO (aq) + Fe2+ (aq) ↔ Fe(NO)2+ (aq)
Nitrites when subjected to acidic solutions are converted to nitrous acid,
HNO2.
 MnO4-
2 drops test solution + 2 drops 0.02 M Na2C2O4 + 2 drops 6 M
H2SO4

The disappearance of the color of the solution within 30 seconds

is the indication of the presence of the permanganate ion.

Discussion:
Oxalates, though unresponsive in neutral and basic solutions, tend to slowly
oxidize in acidic mediums. This oxidation process is due to strong oxidizing agents
like MnO4- ion. The reaction converts the oxalate ion to carbon dioxide and
bleaches the purple permanganate ion.
The reaction is:
5 C2O42- (aq) + 2 MnO4- (aq) + 8 H+ (aq)→ 10 CO2 (g) + 2 Mn2+ (aq) + 4 H2O
 Qualitative Analysis

CONCLUSION AND
RECOMMENDATIONS
 Qualitative analysis is an effective culminating activity for
chemistry laboratory subjects. It includes and combines
both laboratory techniques and chemical reactions which
will test one’s knowledge of the subject involved.

 In the experiment that we are about to perform, water

baths, centrifugation, and decantation are the three
main processes which we will repeatedly execute. The
three given methods will help us determine the cations
and anions present in the unknown. They will also receive
some aid from the numerous chemicals that are to be
added to the unknown. A change in color and the
evolution of gas are just some of the indicators that we
are to take note of. This will give us a clearer and more
specific idea of the solution that we are to be assigned
with. It will narrow the wide array of choices that are
possible for identity of the unknown. Lastly, performing
the experiment accurately and systematically will pilot
towards a more successful analysis and recognition of the
given.
-THE END-