Cations IV V and Anions I V

QUALITATIVE ANALYSIS OF
GROUP IV CATIONS
INTRODUCTION
Cation Group IV is composed of the ion of the alkaline earth metals and magnesium. Although these ions form a large
number of slightly soluble salts with various anions, the only anion which will produce satisfactory precipitation of all four
cations in aqueous solution is the PHOSPHATE. The centrifugate from Group III is made strongly ammoniacal and, upon
addition of the phosphate ion, the alkaline earth ions are precipitated as the TERTIARY PHOSPHATES and the magnesium
ion as MAGNESIUM AMMONIUM PHOSPHATE.
Please READ Chapter 15: Group IV Cations (Qualitative Analysis by E.S Gilreath pp. 215-219)
At the end of this activity, the student should be able to:

1. Describe the principles involved in the separation and identification of Group IV cations.
2. Understand chemical reactions involved in the analysis of Group IV cations.
3. Appreciate the intricate process of qualitative analysis.
Since the cation in this group can be found within the same group in the periodic table, they have the same valence
and resemble each other closely in their chemical reactions.
Element Chemical Relative Atomic Reactivity Pharmaceutical Application

Symbol Mass
Magnesium Be 24.31 Treatment for eclampsia and as a laxative
Increasing
Calcium Ca 40.31 As component of toothpaste and antacid

Strontium Sr 87.62 For study of neurotransmitter release
Barium Ba 137.34 In enemas
The atoms have 2 electrons in their outer shell; Going down the group, elements react
hence, the elements are good reducing agents more readily with both water and oxygen.
because these electrons are easily lost in reactions. They all tarnish in air but barium reacts so
Each resulting ion has a charge of +2 and is more violently with both water and oxygen that
stable because its new outer shell is complete. it is stored in oil.
CPMata,RPhMSPharm,RSLumang-ay,RPhMSPharm©2020JBadillaRPH©2020 65
Saint Louis University – Department of Pharmacy

The close chemical relationship of calcium, strontium, The values of solubility product constants of each of
and barium prevents a clean separation from each the cations with the three precipitating anions are too
other by precipitation methods. close to permit separation and identification by means
of precipitation alone; thus, flame test is employed for
confirmation.
Should be clear and has a volume of approximately 1 ml, if

Centrifugate from
not, concentrate in an evaporating dish and discard any
Group III precipitation
precipitate that forms.
(+) 10 drops of 0.5F

(NH4)2HPO4 and conc.
NH3
Centrifuge
To facilitate precipitation of the phosphates of Ba, Ca, and Sr

(+) few drops of as gelatinous precipitates. These precipitates will cause the
(NH4)2HPO4 coprecipitation of Mg to take place rapidly. If precipitation of
Mg is slow, rubbing the sides of the test tube with the stirring
rod hastens the process.
Centrifuge
Centrifugate Precipitate
Contains Contains
Group V Group IV
Cation Cation

Precipitate containing
Group IV Cation
Wash
(+) 5 drops of water
Barium chromate cannot be precipitated in the presence of an

(+) 5 drops of conc. HAc appreciable hydronium-ion concentration; thus, acetic acid is
used in place of stronger acid.
Stir
Dilute to 2 ml
(+) 5 drops of 1F K2CrO4
Stir
Centrifuge
Precipitate Centrifugate (+) NH3 until To remove the highly colored

strongly basic chromate or dichromate ion.
To reduce
(+) 6 drops of HCl chromate ion into
chromic ion. Centrifuge
Heat
Volume is halved
Precipitate Centrifugate
Conduct Flame test

(+) 5 drops of conc. Discard
HAc
How is flame
Yellow green flame test
confirms the conducted?
(+) 5 drops of water
presence of Barium
ion
(+) 5 drops of 1F
WATCH Testing for
(NH4)2SO4
Positive Ions Part 1
on the Pharm 114L
folder for the
Heat to boiling process!
Cool
Centrifuge
Saint Louis University – Department of
Pharmacy
Continuation
Wash (3x)
(+) Hot water (+) 1 drop of (NH4)2S04
(+) 3 drops of HCl (+) 5 drops of 0.25F

(NH4)2C2O4
Conduct flame test To allow the precipitation of

Heat to boiling
Calcium oxalate.
Crimson Red flame

Centrifuge
confirms the presence
of Strontium ion
(+) 2 drops HCl (+) 1-2 drops of p-

nitrobenzeneazo-
resorcinol
Conduct flame test

To ensure the
(+) 3 ml of 3F KOH precipitation of
MgOH.
Brick Red flame confirms
the presence of Calcium
ion To drive off the
Heat for 5 minutes
NH3 gas.
Centrifuge
Blue precipitate confirms

the presence of
Magnesium ion

Pharmacy
CHEMICAL REACTIONS INVOLVED IN THE SEPARATION AND IDENTIFICATION OF
CATIONS OF GROUP IV
Precipitation of Group IV Cations
Dibasic ammonium phosphate precipitates barium, strontium, and calcium ions from ammoniacal solutions
as white, gelatinous tertiary phosphates while magnesium ions as white, crystalline magnesium ammonium
phosphate.
3 Ba2+ + 2HPO4- + 2NH3- Ba3(PO4)2 + 2NH4+
3 Sr2+ + 2HPO4- + 2NH3- Sr3(PO4)2 + 2NH4+
3 Ca2+ + 2HPO4- + 2NH3- Ca3(PO4)2 + 2NH4+
Mg2+ + HPO4- + NH3- + 6H2O MgNH4PO4 + 6H2O
Solutions of Group IV Precipitate
In the absence of a large excess of acetate ions, acetic acid dissolves the phosphate of barium, strontium,
calcium, and magnesium.
Ba3(PO4)2 + 4HAc 3Ba2+ + 2H2PO4 + 4Ac-
Ca3(PO4)2 + 4HAc 3Ca2+ + 2H2PO4 + 4Ac-
Sr3(PO4)2 + 4HAc 3Sr2+ + 2H2PO4 + 4Ac-
MgNH4PO4 6 2O + 2HAc Mg2+ + H2PO4- + NH4+ + 2Ac- + 6H2O
Separation and Identification of Barium Ion
Potassium chromate precipitates yellow barium

chromate from an acetic acid solution of barium ions. Ba2+ + CrO4- BaCrO4

Pharmacy
Barium chromate is not sufficiently volatile to give a satisfactory flame test for the barium ion. If BaCrO4 is
evaporate with concentrated HCl, the chromate ion is reduced to the chromic ion, and Barium ions enter
solution.
2BaCrO4 + 16H3O+ + 6Cl- 2Ba2+ + 2Cr3+ + 3Cl2 + 24H2O
Separation and Identification of Strontium Ion
Ammonium sulfate precipitates white SrSO4 from an

Sr2+ + SO4- SrSO4
acetic acid solution of strontium ions which is sufficiently
soluble in concentrated HCl to give a flame test for
strontium ion.
Separation and Identification of Calcium Ion
Ammonium oxalate precipitates white CaC2O4- from

an acetic acid solution of calcium ions. Ca2+ + C2O4- CaC2O4
Calcium oxalate, although insoluble in acetic acid, dissolves readily in hydrochloric acid.
CaC2O4 + H3O+ Ca2+ + HC2O4- + H2O
Precipitation and Identification of Magnesium Ion
Potassium hydroxide precipitates white, gelatinous

magnesium hydroxide from a solution of magnesium Mg2+ + 2OH- Mg(OH)2
ions.
Or Mg(H2O)62+ + 2OH- Mg(H2O)4(OH)2 + 2H2O
The precipitate has the property of adsorbing dyes to form colored lakes. One such dye is p-
nitrobenzeneazoresorcinol, which produces a blue colored lake with magnesium hydroxide. The formation
of this lake is specific for magnesium ion in the presence of other cations of Group IV and is used as a
confirmatory test for the magnesium ion.

Pharmacy
GROUP V CATIONS
INTRODUCTION
The centrifugate from Group IV contains commonly occurring cations which are not precipitated by the
chloride, sulfide, and phosphate ions under the conditions for precipitation of the first four Groups of cation.
This group is sometimes called the soluble group and includes sodium, potassium, and ammonium ions. The
salts of these cations, with few exceptions, are soluble. This accounts for the fact that there is no precipitating
agent in this group.
Please READ Chapter 16: Group V Cations (Qualitative Analysis by E.S Gilreath pp. 220-223)

1. Identify and describe the principles involved in the separation and identification of Group V cations.
2. Understand chemical reactions involved in the analysis of Group V cations.
DIRECTION: Identify the cations being depicted in the pictures.
In this group, the low concentration of cations in the diluted solutions could give a disappointing result.
However, identification of their flame spectra could differentiate and identify them from each other.
In some precipitation test for the identification of the cations of Group V, the widely used precipitating
reagents are zinc uranyl acetate and sodium cobaltinitrite; though, in semi-micro analysis, the use of these
reagents are not recommended.

Pharmacy
5 drops of the
original solution
Place
Small beaker
(+) drops of water
NOTE: A high concentration of OH- ions will decrease the

(+) 3F KOH until
concentration of NH4+ ions to produce a larger concentration of
basic
NH3 ions.
Cover with watch

glass to which a
red litmus paper is
adhering to the
convex side.
Warm for 1 minute Ammonia ions molecules are less soluble in warm water than cold.
Change of
coloration from red
to blue confirms
the presence of
Ammonium ion

Pharmacy
Centrifugate from
Group IV
Transfer
Evaporating dish
Heat
Concentrate to 0.5
Discard any precipitate that forms
ml
(+) 1 drop of conc.

HCl
Conduct flame test K compounds are

An intense yellow more volatile than
flame lasting for 5 Na; thus, its flame
seconds or more spectrum is of
should indicate the shorter duration
Sodium Potassium
presence of Sodium than Na. Cobalt
ion, if not, consider glass must be used
the result as during the
negative. Yellow flame Reddish-violet identification of the
confirms the flame confirms the color flame of K.
presence of presence of
Sodium ion Potassium ion
CHEMICAL REACTIONS INVOLVED IN THE ANALYSIS OF CATIONS OF GROUP V
The lack of sensitivity of chemical test for sodium and potassium under semi-micro qualitative analysis is due
to the fact that most salts of both cations are too soluble to be adequate for precipitation tests. Therefore,
flame test is more satisfactory than any precipitation tests for sodium and potassium.
There are few insoluble compounds of sodium and potassium but the
precipitating reagents for such compounds are not specific for the ions;
example,
Na2H2Sb2O7 and K3Co(NO2)6

Pharmacy
Identification of Sodium and Potassium Ions
The most widely used precipitation test for Sodium ion is the formation of sodium zinc uranyl acetate. The
addition of zinc uranyl acetate to an acetic acid solution of sodium ions
produces a yellow crystalline precipitate after 5 minutes standing. NOTE:
Interfering ions which may produce
similar precipitate include: aluminum,
ammonium, barium, calcium,
Na+ + Zn2+ + 3UO2 + 9Ac- NaZn(UO2)3(Ac)9 cadmium, cobalt, copper, magnesium,
mercury, manganese, nickel,
potassium, strontium, and zinc.
One of the most common precipitation tests for potassium ions is the formation of potassium-sodium
cobaltinitrite. The addition of cobaltinitrite to a solution of potassium ions, acidified with acetic acid,
produces a yellow precipitate of potassium-sodium cobaltinitrite, after long standing.
NOTE:
2K+ + Na+ + Co(NO2)63- NaK2Co(NO2)6 The ammonium ion produces similar
precipitate with this reagent.
Identification of Ammonium Ion
Sodium hydroxide or potassium hydroxide liberates ammonia when added to a solution of ammonium ions.
Ammonia gas is less soluble in hot than cold solution; therefore, heating drive the reaction in the direction
which releases ammonia.
The liberated ammonia may be

NH4+ + OH- NH3 + H2O identified by odor or by its reaction
with moistened red litmus paper.

Pharmacy
ACTIVITY 4
Analysis of Anions
Before you proceed with the next activity and try to

review the basic principles involved in cations
analysis as they are also applied in anion analysis.
God bless your midterms journey!

SYSTEMATIC ANALYSIS OF
ANIONS
The anions are negatively charged ions produced by the ionization of acids and salts. In the anion procedure,
the ions are separated into groups based upon the solubilities of the calcium, barium, cadmium and silver salts. These
groups are as follows:
Group I includes ions whose calcium salts are insoluble in slightly basic solution.
Group II includes ions whose calcium salts are soluble but whose barium salts are insoluble in slightly basic solution.
Group III is composed of anions whose calcium and barium salts are soluble but whose cadmium salts are insoluble in
slightly basic solution.
Group IV is composed of anion whose calcium, barium and cadmium salts are soluble but whose silver salts are insoluble
in a solutions slightly acid with nitric acid.
Group V contains anions whose calcium, barium, cadmium and silver salts are soluble in water and acids.
Learning objectives:
At the end of the activity, you should know how to:
1. Apply the manipulations in semi-micro analysis.

2. Identify the anions present in unknown solutions.
3. Follow procedures in a systematic way.
4. Identify and describe the principles involved in the qualitative analysis of cations.
Main Reference: (Please check e-copy in your Pharm 114L folder e-books)
(Refer to Chapter 17-20 of Qualitative Analysis by E.S. Gilreath p.224-244)

GROUP I ANIONS
INTRODUCTION
Generally, the anions are negatively charged ions produced by the ionization pf acids and salts. With the exception of
fluoride, chloride, bromide, iodide, and sulfide ions, the anions are composed of two or more elements bound in
chemical combination which vary in stability and reactivity.
The anions of Group I are distinguished from the other groups in that their calcium salts are insoluble in neutral or slightly
basic solution. The acetate ion has the advantage over other salts in a way that it does not interfere with any succeeding
separations.

1. Identify and describe the principles involved in the separation and identification of Group I anions.
2. Understand chemical reactions involved in the analysis of Group I anions.
ACTIVITY 4.1: Arrange the jumbled letters; afterwards, provide one (1) pharmaceutical application of the anions
determined. (Please detach and submit as part of Activity 4 output)
Group I Anion Pharmaceutical Application (give 1 only)

LFETUSI
EERSAINT
ASEAETNR
ETHHSAPOP
XTALOEA
IROLUDEF
BARACOTEN
NOTE:
The pH of the original solution should be adjusted with dilute

Potassium Hydroxide (KOH) and dilute Acetic acid (CH3COOH)
until the resulting solution is barely alkaline.

Mix 10 drops of 3F HCl Mix 2 ml of test
and 10 drops H2O solution and 2 ml H2O
To oxidize the
sulfite, sulfide, Heat for 2 minutes
(+) 0.1g of KClO3 and thiosulfate
To remove heavy-metal
ions into sulfate
cations that would
ion or free sulfur. (+) 2 ml 1.5F Na2CO3
interfere in the analysis.
(+) 10 drops of the test
solution Heat for 10 minutes
Centrifuge
Vigorous effervescence
confirms the presence of
Carbonate ion
Contains anions in the Discarded, contains

form of soluble OH- and CO3- of
sodium salts heavy metals
(+) 2F Ca(Ac)2 drop Until precipitation is

by drop complete
Centrifuge
Contains anions of Group Contains insoluble calcium

II-V salts of Group I Anion
To remove
contaminants,
Wash 3x with H2O
especially traces of
CrO4- ions
Add as long as the
precipitate appears to be (+) 15 drops 3F HAc
dissolving.
Centrifuge
Contains anions of Group

Contains anions of Group IB:
IA: sulfite, arsenite, arsenate,
carbonate and fluoride.
or phosphate.

Centrifugate
containing Group IA
Divide into 4 portions
First Portion Second Portion Third Portion Fourth Portion
(+) 2 drops (+) 2 drops 3F (+) 5 drops

(+) 2 drops 3F HCl
conc. HCl HCl conc. HNO3
(+) 5 drops Ba(Ac)2 (+) 2 drops H2O Heat for 2 min. (+) 0.2 g tartaric
acid
Centrifuge Heat to boiling (+) few crystals of KI

(+) 5 drops
ammonium
Centrifugate Precipitate (+) 5 drops of Brown solution molybdate
thioacetamide confirms the
(+) 5 drops presence of
Discard
H2O2 Arsenate Warm for 1 min.
Yellow
precipitate
White confirms the (+) 10 drops CCl4 Yellow
precipitate presence of precipitate
confirms Arsenite confirms
presence of Pink coloration presence of
Sulfite indicates presence Phosphate
of Arsenate
Heat for 1 Disappearance of pink

First (+) 2 drops of
min. while color confirms the
Portion 0.01F KMnO4
stirring presence of Oxalate
2 portions
Centrifugate
containing
Divide into
Group IB
Transfer
in a (+) 1 drop Glass etching
Second watch Cool
conc. H2SO4 confirms the
Portion glass for 20
then heat for presence of
then min.
5 minutes Chloride
heat until
dry

CHEMICAL REACTIONS INVOLVED IN THE ANALYSIS OF GROUP I ANIONS
Precipitation of Group I Anions
The anions of Group I are precipitated from slightly alkaline solution by calcium acetate solution.
Provide the pertinent chemical reaction in the precipitation

of Group I anion using calcium acetate solution. Why is it necessary to
precipitate Group I
Anions in their
calcium salts prior to
individual ion identification?
Please refer to pp. 229 of

Qualitative Analysis by E.S Gilreath
Identification of Carbonate Ion
Dilute HCl decomposes carbonates with an

effervescence due to the evolution of carbon CaCO3 + 2H3O Ca2+ + 3H2O + CO2
dioxide.
This test identifies the carbonate ion by the liberation of gas. Other anions which produce gases in acid solution, such
as the sulfite, thiosulfate, and sulfide, are oxidized by the addition of KClO3. In their oxidized form such anions produce
NO GASES to interfere with the carbonate test.
Action of Dilute Acetic Acid upon Group I Anion Precipitate
All the insoluble calcium salts of Group I anions dissolve in dilute acetic acid EXCEPT calcium fluoride and calcium
oxalate.
CaCO3 + 2HAc Ca2+ + H2O + CO2 + 2Ac-
CaSO3 + 2HAc Ca2+ + H2SO3 + 2Ac-
Ca(AsO2)2 + 2H2O + 2HAc Ca2+ + 2H3AsO3 + 2Ac-
Ca3(AsO4)2 + 4HAc 3Ca2+ + 2H2AsO4- + 4Ac-
Ca3(PO4)2 + 4HAc 3Ca2+ + 2H2PO4- + 4Ac-

Identification of Sulfite Ion
The sulfite ion is oxidized by hydrogen peroxide to the sulfate. The latter is precipitated as BaSO 4, insoluble in strong acids.
H2SO3 + H2O2 + H2O SO4- + 2H3O-
SO4- + Ba2+ BaSO4

Test for Arsenite Ion
Hydrogen sulfide produces an immediate

precipitate of yellow As2S3 when passed 2H3AsO3 + 3H3S As2S3 + 6H2O
into a solution of arsenite ions.
Under the same condition, the arsenite

ion gives a yellow precipitate of arsenic 2H2AsO4- + 5H2S + 2H3O+ As2S5 + 10H2O
sulfide which precipitates slowly.
Detection of Arsenate Ion
The arsenate ion is reduced by the iodide

ion, in an acid solution, with the liberation H2AsO4- + 3H3O+ + 2I- H3AsO3 + I2 + 4H2O
of iodine.
Identification of Phosphate Ion
The phosphate ion reacts with ammonium molybdate in a nitric acid solution to form a yellow, voluminous precipitate of
ammonium phosphomolybdate.
H2PO4- + 12MoO4- + 22H3O+ + 3NH4+ (NH4)3PO4·12MoO3 + 34H2O
Confirmation of the Presence of Oxalate Ion
Sulfuric acid added to a precipitate of CaC2O4 produces soluble oxalic acid. Oxalic acid, in the presence of a high
concentration of hydronium ions, reduces permanganate ions to manganous ions. The color of the solution changes
from purple to colorless.
CaC2O4 + 2H3O+ Ca2+ + H2C2O4 + 2H2O
5H2C2O4 + 2MnO4- + 6H3O- 2Mn2+ + 10CO2 + 14H2O
Identification of Fluoride Ion
Concentrated sulfuric acid liberates

volatile hydrogen fluoride from a CaF2 + 2H3O+ Ca2+ + 2H2O + 2HF
precipitate of calcium fluoride.
Hydrogen fluoride attacks silica, or any SiO2 + 4HF SiF4 + 2H2O

silicate, evolving silicon tetrafluoride.

GROUP III ANIONS

INTRODUCTION
This Group are those whose calcium and barium salts are soluble but whose cadmium salts are insoluble in mineral or
slightly basic solutions. The precipitation of the sulfide, ferrocyanide, and ferricyanide ions by cadmium ions is fairly
complete.

1. Identify and describe the principles involved in the separation and identification of Group III anions.
2. Understand chemical reactions involved in the analysis of Group III anions.
DIRECTION: Answer what is being asked.
What elements are present in an egg which belongs to Group III anions
1. _________________________
2. _________________________
The test for the sulfide depends upon the formation of a metallic
sulfide. The sulfide is then converted to H2S, which may be
detected by its action on lead acetate paper to produce black
lead sulfide.
The tests for ferrocyanide and ferricyanide ions depend upon

the blue precipitates formed with the ferric and ferrous ions. This
precipitates are called Prussian blue, Fe4[Fe(CN)6]3, and
Turnbull’s blue, Fe3[Fe(CN)6]2.

Centrifugate containing
Group III Anion
Until precipitation is complete. Precipitation (usually

(+) 1F Ca(Ac)2 dropwise
colored) confirms the presence of Group III Anion.
Centrifuge
The color of the precipitate may

signal its composition:
Centrifugate Precipitate Sulfide: bright yellow
Ferrocyanide: pale yellow
Ferricyanide: orange
Centrifugate contains Centrifugate contains
Group IV-V Anions Group III Anions
Wash 2x with hot To remove the contamination of

H2O thiocyanate ion.
Divide into 3
portions
First Portion Second Portion Third Portion
Transfer in a test Transfer in a spot Transfer in a spot

tube plate plate
(+) 3 drops 3F HCl (+) 1 drop 3F HCl (+) 1 drop 3F HCl
(+) 1 drop 1F FeCl3 (+) 3 drop H2O

Cover the mouth
with filter paper
moistened with
0.5 Pb(Ac)2 (+) small crystal of
Dark blue precipitate
ferrous sulfate
confirms the
presence of
Brown/black Ferrocyanide
Dark blue precipitate
coloration of the test confirms the
paper indicates the presence of
presence of Sulfide Ferricyanide

CHEMICAL REACTIONS INVOLVED IN THE ANALYSIS OF GROUP III
ANIONS
Precipitation of Group III Anion
The three anions present in this group are precipitated as S- + Cd2+ CdS
the insoluble cadmium salts.
Fe(CN)64- + 2Cd2+ Cd2Fe(CN)6 2Fe(CN)63- + 3Cd2+ Cd3[Fe(CN)6]2
Detection of Sulfide Ion
Cadmium sulfide dissolves in dilute hydrochloric acid. CdS + 2H3O+ Cd2+ + H2S + 2H2O
The hydrogen sulfide liberated in this reaction causes the

blackening of filter paper moistened with lead acetate CdS + 2H3O+ Cd2+ + H2S + 2H2O
solution, due to the formation of lead sulfide.
Identification of Ferrocyanide Ion
Cadmium ferrocyanide dissolves in dilute hydrochloric acid.
Cd2Fe(CN)6 + 2H3O+ H2Fe(CN)6- + 2Cd2+ + 2H2O
The ferrocyanide ion produced by this reaction reacts with ferric ions to form a dark blue precipitate, sometimes called
Prussian blue.
3H2Fe(CN)6- + 4Fe3+ + 6H2O Fe4[Fe(CN)6]3 + 6H3O+
Confirmatory Test for Ferricyanide Ion
Cadmium ferricyanide dissolves in dilute hydrochloric acid.
Cd3[Fe(CN)6]2 + 2H3O+ 2HFe(CN)6- + 3Cd2+ + 2H2O
The ferricyanide ion forms a dark blue precipitate, turnbull’s bue, with ferrous ion.
2HFe(CN)6- + Fe2+ + 2H2O Fe3[Fe(CN)6]2 + 2H3O+

There is some evidence that Turnbull’s Blue is identical with Prussian Blue. It is possible that the ferricyanide
oxidizes the ferrous ion to ferric ion.
HFe(CN)6- + Fe2+ + H3O+ H2Fe(CN)6- + Fe3+ + H2O
3H2Fe(CN)6- + 4Fe3+ + 6H2O Fe4[Fe(CN)6]3 + 6H3O+
The product of this redox reaction will react to give ferric ferrocyanide.
It is also possible for the ferrocyanide to reduce ferric ions and to precipitate as ferrous ferricyanide. Therefore,
the composition of the blue precipitate obtained in the ferrocyanide and ferricyanide tests may be identical,
and the formula for the precipitate may not be either Fe4[Fe(CN)6]3 or Fe3[Fe(CN)6]2.
Reaction of Ferricyanide Ion with Sulfide Ion
These two ions are incompatible in solution and will react

2Fe(CN)63- + S- 2Fe(CN)64- + S
as follows,

GROUP IV ANIONS
INTRODUCTION
The anions of this Group are distinguished from those of the other groups by the insolubility of their silver salts in acid
solutions. The group reagent is silver acetate, which is only soluble to the extent of approximately 0.07F. This necessitates
a larger volume of the reagent for group precipitation.

1. Identify and describe the principles involved in the separation and identification of Group IV anions.
2. Understand chemical reactions involved in the analysis of Group IV anions.
DIRECTION: Identify the anion (names are jumbled on the first column). Then provide one (1) pharmaceutical
application of the anions identified.
Group IV Anion Pharmaceutical Application

EDCOHRIL
AHATTEOYINC
ASEAETNR
DIEIDO
MERDIBO
SILVER THIOSULFATE
Unstable in acid solution and undergoes a series of characteristic color
changes which serve to identify this ion during group precipitation.
SILVER (EDCOHRIL)
Has the largest solubility product; thus, more soluble in ammonia than
other members of the group
SILVER (AHATTEOYINC)
Reacts with solution of ferric chloride to give the characteristic color
complex ion, Fe(CNS)63-

Group IV Anion
(+) 5 drops of AgAc

solution
Formation of white precipitate indicates the presence of

Acidify with 3F HNO3 Group IV anion. The change in coloration into yellow,
orange, and brown indicates the presence of Thiosulfate.
Until
precipitation is (+) sat. AgAc solution
complete
Acidify with acetic acid
Centrifuge
The color of the precipitate may indicate its
composition:
Black: Ag2S
Centrifugate Precipitate White: AgCl or AgCNS
Cream: AgBr
Contains Group V Contains Group IV Yellow: AgI
Anions Anions
Continue washing until

(+) H2O containing few
washings no longer give
drops of 3F HNO3
precipitate with dilute HCl
Wash once with distilled

water
(+) 10 drops of
ammoniacal AgNO3
Centrifuge
(+) 3F HNO3 until (next page for

acidic continuation)
White precipitate
indicates the presence of
Chloride

Precipitate
Divide into 2 portions
One-third Portion Two-third Portion
Transfer into a spot

(+) 10 drops of H2O
plate
(+) 1 drop 3F HCl Acidify with 3F HAc
Zinc reduces Ag allowing

(+) 1 drop 1F FeCl3 (+) 1 g zinc dust it to deposit liberating Br-
and I-
Red coloration confirms Stir for 5 minutes

the presence of
Thiocyanate
Centrifuge
Separate water layer and (+) 10 drops of CCl4 and

discard the colored CCl4 Discard
few crystals of NaNO2
layer
Dilute to 2 ml and shake

Transfer in an evaporating vigorously
dish
Violet color in CCl4 layer Continue washing the solution with

(+) 5 drops 1.5F H2SO4 indicates the presence of fresh CCl4 until CCl4 remains
Iodide colorless. Combine the water layer
removed from the washings.
Evaporate until volume is
halved
(+) 10 drops of conc. HNO3
(+) 10 drops of CCl4

Yellow or Orange
coloration in the CCl4 layer
Heat for not more than 20 Remove and agitate indicates the presence of
seconds vigorously Bromide

CHEMICAL REACTIONS INVOLVED IN THE ANALYSIS OF GROUP IV ANIONS
Precipitation of Group IV Anions
The anions of this group are precipitate by silver acetate in S2O3- + 2Ag+ Ag2S2O3
a solution.
I- + Ag+ AgI Cl- + Ag+ AgCl
Br- + Ag+ AgBr CNS- + Ag+ AgCNS
Identification of Thiosulfate Ion
The group precipitating agent, the silver ion in an acid

solution, produces a white precipitate with the thiosulfate 2Ag+ + S2O3- Ag2S2O3
ion.
Silver thiosulfate is unstable and breaks down into

silver sulfide at room temperature. The Ag2S2O3 + 2H2O Ag2S + H3O+ + HSO4-
precipitate may undergo color changes from
white through yellow, orange, brown to black.
Solvent action of Ammoniacal Silver Nitrate
In a solution of ammonia, Ag2S and AgI are insoluble, AgBr is slightly soluble, AgCNS fairly soluble, and AgCl quite soluble.
If silver ions are added to ammonia water, the solubilities of the aforementioned precipitates are decreased because of
the common-ion effect of the complex ion, Ag(NH3)2+. The
solubilities are so decreased that only AgCl dissolves AgCl + 2NH3 Ag(NH3)2+ + Cl-
appreciably, thus permitting a separation of the chloride
ion from the other anions of Group IV.
Confirmatory Test for Chloride Ion
The silver complex with ammonia is readily broken down in acid solution. If chloride ions are present, a white precipitate
of AgCl results. This precipitate is insoluble in nitric acid.
Ag(NH3)2 + Cl- + 2H3O+ AgCl + 2NH4+ + 2H2O
Identification of Thiocyanate Ion
If a portion of the Group IV anion precipitate containing

AgCNS, is treated with hydrochloric acid and ferric AgCNS + Cl- AgCl + CNS-
chloride solution, a red coloration is produced. In this test
AgCNS dissolves to some extent in HCl, depending upon
the concentration of the chloride ion. Fe3+ + 6CNS- Fe(CNS)63-
The thiocyanate ion produces a colored complex ion
with the ferric ion.

Action of Zinc upon Residue of Group IV Analysis
If an acid solution containing this residue is treated with zinc dust, metallic silver precipitates from solution. Zinc being
higher in the potential series, replaces silver ions in its compounds. In this redox reaction the anions are brought into
solution, although the thiocyanate is destroyed in the process.
With Ag2S, produced by the hydrolysis of the thiosulfate ion, zinc releases hydrogen sulfide.
Ag2S + Zn + 2H3O+ Zn2+ + 2Ag + H2S + 2H2O
Zinc, in acid solution, decomposes the thiocyanate ion to form hydrogen cyanide and hydrogen sulfide.
3Zn + 2AgCNS + 6H3O+ 2Ag + 3Zn2+ + 2H2S + 2HCN + 6H2O
With AgBr and AgI, zinc precipitate Ag, converting the anions into soluble salts.
2AgBr + Zn 2Ag + 2Br- + Zn2+ 2AgI + Zn 2Ag + 2I- + Zn2+
Identification of Iodide Ion
The centrifuge from the treatment of the residue with zinc

in an acid solution contains the iodide and bromide ions.
NO2- + H3O+ HNO2 + H2O
Nitrous acid oxidizes the iodide ion to iodine with no
action upon the bromide. The addition of sodium nitrite
to the acid solution produces nitrous acid.
Free iodine imparts a brown color to the water solution. When shaken with CCl4, the iodine is concentrated in the CCl4
layer in which it is more soluble. Iodine in CCl4 solution is violet in color.
2HNO2 + 2H3O+ + 2I- 2NO + I2 + 4H2O
Identification of Bromide Ion
Since the final identification for the bromide ion depends upon the brown color of a solution of bromine in CCl 4, it is
necessary to remove all iodine from the solution. The violet color of iodine will mask the brown color of bromine. Two or
three extractions with CCl4 are sufficient for this removal
Concentrates HNO3 oxidizes the bromide ion to bromine. The latter is identified by extractions with CCl4 to which it imparts
a yellow or orange color.
6Br- + 2NO3- + 8H3O+ 3Br2 + 2NO + 12H2O

GROUP IV ANIONS
INTRODUCTION
This group includes those anions, the nitrite, nitrate, chlorate, and borate ions, which are not precipitated in the first four
groups. This group is designated as the water-soluble group, since most of the common salts of these anions are soluble
in water EXCEPT borate ion, where the salts are not readily soluble in water, and which may be completely precipitated
as the metaborate.

1. Identify and describe the principles involved in the separation and identification of Group V anions.
2. Understand chemical reactions involved in the analysis of Group V anions.
ACTIVITY 4.4 : Enumerate one (1) compound which contains the group V anion. Provide two (2) pharmaceutical
used of the chosen compound. Please detach and submit as part of the output for Activity 4.
COMPOUND
GROUP V Since there is no satisfactory
(Chemical Name & PHARMACEUTICAL USE
ANION inorganic test for (No.2) ion, it is
formula)
1. necessary to resort to the use of
organic reagent.
Chlorate
2. Many organic dyes in sulfuric acid
solution changes color in the
1. presence of (No.2) anion.
The (No.3) anion is identified in the

Borate presence of other members by its
2.
specific oxidizing action upon
urea, in which nitrogen and
1.
carbon dioxide are evolved.
Nitrite
2.
1.
Nitrate
2.

First Portion Second Portion
(+) 5 drops of Transfer into an

conc. HNO3 evaporating dish
(+) 2 drops 0.5F (+) 5 drops

AgNO3 conc. H2SO4
Allow to stand Evaporate to

for 2 minutes almost dryness
Centrifuge (+) 3 drops of

carminic acid
Warm slightly
(+) few Discard
crystals of
Change from red
NaNO2
to bluish violet
Centrifugate containing coloration
Group V Anion indicates the
White presence of
precipitate Borate ion
indicates the
Divide
presence of
into 4
Chlorate ion
portions
Third Portion Fourth Portion
(+) equal volume of Test 1 Test 2

urea in HCl solution
Put one drop in a Place a small crystal of
spot plate Fe(SO4)2 in a spot plate
Vigorous evolution of
gas indicates the
presence of Nitrite ion (+) 2 drops conc. (+) 1 drop of the
H2SO4 fourth portion
(+) 1 drop a- (+) 1 drop conc.

napthylamine H2SO4
Appearance of purple Formation of brown ring

ring after 3 minutes around the crystal
indicates the presence indicates the presence
of Nitrate ion of Nitrate ion

CHEMICAL REACTIONS INVOLVED IN THE ANALYSIS OF GROUP V ANIONS
Identification of Chlorate Ion

The chlorate ion is reduced by nitrous acid to the chloride ion which is then precipitated as silver chloride
ClO3- + 3HNO2 + 3H2O Cl- + 3NO3- + 3H3O+
Cl- + Ag+ AgCl
Identification of Borate Ion
Certain hydroxyanthraquinone, dissolved in concentrated sulfuric acid, NOTE:

give characteristic color change with boric acid. The dye, carminic Oxidizing agents interfere with these test;
acid, changes from red to bluish-violet in the presence of boric acid. therefore, the other anions must be
removed or destroyed
The chlorate ion is converted to perchloric acid which volatilizes.
3HClO3 HClO4 + 2ClO2 + H2O
When heated with concentrated sulfuric acid, the nitrate ion

4HNO3 2H2O + 4NO2 + O2
is in the form of nitric acid, which boils off at 86oC with some
decomposition into NO2, H2O, and O2.
When heated in the presence of concentrated sulfuric acid,

the nitrite ion, in the form of nitrous acid, is decomposed into 2HNO2 H2O + NO2 + NO
H2O, NO2, and NO, all of which are volatile.
Detection of Nitrite Ion
The nitrite ion in dilute hydrochloric acid solution reacts with urea to evolve nitrogen and carbon dioxide as redox
products.
CO(NH2)2 + 7H2O CO2 + N2 + 6H3O+ + 6e
6e + 2NO2- + 8H3O+ N2 + 12H2O
CO(NH2)2 + 2NO2- + 2H3O+ CO2 + 2N2 + 5H2O
Destruction of Nitrite Ion
In the brown-ring test, the nitrate ion cannot be identified in

the presence of nitrite ion, since the two ions give the same NO2- + NH4+ N2 + 2H2O
test. Therefore, the nitrite ion must be removed. In an acid
solution, the nitrite ion reacts with ammonium salt to produce nitrogen gas. Ammonium sulfate is used for this purpose.
Identification of Nitrate Ion
In the absence of nitrite ion, the presence of the nitrate ion is confirmed by the reduction of nitric acid by ferrous ions in
high concentration of sulfuric acid. Nitric oxide, from the reduction of nitric acid, combines with excess ferrous ions to
produce the unstable brown complex, Fe(H2O)5NO2+.
3Fe(H2O)62+ + NO3- + 4H3O+ 3Fe(H2O)63+ + NO + 6H2O
Fe(H2O)62+ + NO Fe(H2O)6NO2+ + H2O

GROUP II ANIONS
INTRODUCTION
The analysis of this group involve no difficulties. The presence of the chromate is indicated by a yellow color. If the
centrifugate from Group I is colorless the test for the chromate ion may be omitted. However, the presence of a yellow
color in the centrifugate does not confirm the presence of chromate ion, since the ferrocyanide and ferricyanide from
Group III anions may also impart similar color to the solution.
Please READ Chapter 18: Group V Cations (Qualitative Analysis by E.S Gilreath pp. 231-232

1. Identify and describe the principles involved in the separation and identification of Group II anions.
2. Understand chemical reactions involved in the analysis of Group II anions.
This group of anions contain only two (2) which is precipitated by the reagent barium acetate, C4H6BaO4.
ACTIVITY 4.2 : Name the following compounds then provide at least 3 pharmaceutical or industrial uses of each. Please
detach and submit as part of output of Activity 4.
NAME:
Uses:
Chromium is known to
enhance the action of
insulin, a hormone critical to
the metabolism and storage
of carbohydrate, fats, and
proteins.
NAME: Though rare, humans can

Uses: have CHROMIUM
DEFICIENCY which can lead
to impaired insulin function,
inhibition of protein synthesis,
and energy production, and
to type 2 diabetes and heart
disease.

Group II Anion
(+) 1F Ba(Ac)2 dropwise
Centrifuge
Contains Group III-V Contains Group II

Anion Anion
(+) 10 drops H2O
(+) 5 drops of HCl
Centrifuge
To dissolve Group I
Buffers the solution to
anions which may
permit the (+) 2 drops 2.5F (+) 10 drops 3F
have been
precipitation of sodium acetate HCl
incompletely
BaCrO4
removed.
Yellow precipitate
White precipitate
confirms the
confirms the
presence of
presence of Sulfate
Chromate

CHEMICAL REACTIONS INVOLVED IN THE ANALYSIS OF
GROUP II ANIONS
Precipitation of Group II Anions
The anions of Group II are precipitated from slightly SO4- + Ba2+ BaSO4
basic solution by the addition of barium acetate
solution.
CrO4- + Ba2+ BaCrO4
Identification of Sulfate Ion
A white precipitate, produced by the addition of

barium ion and insoluble in strong acids, confirms the
presence of the sulfate ion. SO4- + Ba2+ BaSO4
Detection of Chromate Ion
A yellow group precipitate for Group II anions

indicates the presence of chromate ion. The
BaCrO4 + H3O+ HCrO4- + Ba2+ + H2O
yellow precipitate is barium chromate which is
soluble in dilute hydrochloric acid.
The addition of sodium acetate solution to the

acid chromate solution lowers the hydronium-
ion concentration sufficiently to permit the
Ba2+ + HCrO4- + Ac- HAc + BaCrO4
reprecipitation of barium chromate.
The presence of the chromate ion may be

confirmed by the addition of hydrogen
HCrO4- + 2H2O2 + H3O+ CrO5 + 4H2O
peroxide to the dilute acid solution. This
reaction produces a blue -colored compound,
CrO5, which is so unstable that it fades rapidly.

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QUALITATIVE ANALYSIS OF

At the end of this activity, the student should be able to:

Element Chemical Relative Atomic Reactivity Pharmaceutical Application

Calcium Ca 40.31 As component of toothpaste and antacid

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Should be clear and has a volume of approximately 1 ml, if

(+) 10 drops of 0.5F

To facilitate precipitation of the phosphates of Ba, Ca, and Sr

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(+) 5 drops of water

Barium chromate cannot be precipitated in the presence of an

(+) 5 drops of 1F K2CrO4

Precipitate Centrifugate (+) NH3 until To remove the highly colored

Conduct Flame test

(+) Hot water (+) 1 drop of (NH4)2S04

(+) 3 drops of HCl (+) 5 drops of 0.25F

Conduct flame test To allow the precipitation of

Crimson Red flame

(+) 2 drops HCl (+) 1-2 drops of p-

Conduct flame test

Blue precipitate confirms

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Precipitation of Group IV Cations

3 Ba2+ + 2HPO4- + 2NH3- Ba3(PO4)2 + 2NH4+

3 Sr2+ + 2HPO4- + 2NH3- Sr3(PO4)2 + 2NH4+

3 Ca2+ + 2HPO4- + 2NH3- Ca3(PO4)2 + 2NH4+

Mg2+ + HPO4- + NH3- + 6H2O MgNH4PO4 + 6H2O

Solutions of Group IV Precipitate

Ba3(PO4)2 + 4HAc 3Ba2+ + 2H2PO4 + 4Ac-

Ca3(PO4)2 + 4HAc 3Ca2+ + 2H2PO4 + 4Ac-

Sr3(PO4)2 + 4HAc 3Sr2+ + 2H2PO4 + 4Ac-

MgNH4PO4 6 2O + 2HAc Mg2+ + H2PO4- + NH4+ + 2Ac- + 6H2O

Separation and Identification of Barium Ion

Potassium chromate precipitates yellow barium

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2BaCrO4 + 16H3O+ + 6Cl- 2Ba2+ + 2Cr3+ + 3Cl2 + 24H2O

Separation and Identification of Strontium Ion

Ammonium sulfate precipitates white SrSO4 from an

Separation and Identification of Calcium Ion

Ammonium oxalate precipitates white CaC2O4- from

CaC2O4 + H3O+ Ca2+ + HC2O4- + H2O

Precipitation and Identification of Magnesium Ion

Potassium hydroxide precipitates white, gelatinous

Or Mg(H2O)62+ + 2OH- Mg(H2O)4(OH)2 + 2H2O

Saint Louis University – Department of

At the end of this activity, the student should be able to:

DIRECTION: Identify the cations being depicted in the pictures.

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(+) drops of water

NOTE: A high concentration of OH- ions will decrease the

Cover with watch

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(+) 1 drop of conc.

Conduct flame test K compounds are

CHEMICAL REACTIONS INVOLVED IN THE ANALYSIS OF CATIONS OF GROUP V

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Identification of Ammonium Ion

The liberated ammonia may be