CHEM 3L Group 4 Cation 1

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
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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
Saint
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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
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Pharmacy
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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
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CHEM 3L Group 4 Cation 1

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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

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

(+) 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

Saint Louis University – Department of

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

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