Experiment No: 09

ELEMENTARY INORGANIC
CHEMISTRY
FST1105

Name : H.M.D.S.Bandara

Registration No. : 19APF3747

Submission date :01/11/2022

Date :06th of September 2022
Practical number : 08
Practical name : Cation analysis group V and VI

Objective :
 To get an awareness of separating cations into different groups.
 To get a knowledge of chemical reactions and their balanced equations that take place during
the practical
 To follow a classic qualitative analysis scheme to separate and identify the ions in a known
mixture of Group III and IV cations
 To apply this scheme to identify the Group V and VI
 cations present in an unknown sample

Introduction :
The systematic analysis of cations is an integral part of the qualitative analysis.The qualitative analysis
of an inorganic mixture is started by first carrying out some preliminary tests. The Preliminary tests for
cations are Physical examination, Charcoal cavity test, Borax bead test and Flame test. These tests do
not give conclusive evidence yet they provide some information about the ions present in the mixture.In
the qualitative analysis of cations usually consists of three stages as First based on different solubility
properties the cations are separated into 5 groups through the successive addition of selective
precipitating reagents and second, within each group precipitated cations are separated through selective
dissolution processes. finally, the presence of each cation is verified through different identification tests.
The cations are classified into the following 5 groups. In this case only cation group V and VI are
considered. cations are calcium (II) Ca2+, strontium (II) Sr2+ and barium (II) Ba2+. Its group
reagent is 1M solution of ammonium carbonate (NH4)2CO3 in neutral or alkaline medium. The medium
needs to be neutral or alkaline because it is readily decomposed even by weak acids like acetic acid.These
three metallic cations all belong to Group IIA in the periodic table of elements and therefore their
chemical properties are very similar. They form soluble chlorides and sulphides and hence are separable
from groups 1, 2 and 3 cations. However, their carbonates precipitate in a mixture of ammonium
carbonate, ammonium chloride or ammonia solution..Group VI cations are Mg2+, K+ and NH4+. There
is not a common precipitating agent for the VI group of cations. NH4+ is also in the group VI because
the compounds containing NH4+ have similar properties with those with alkali metals These cations do
not react with hydrochloric acid HCl, hydrogen sulphide H2S, ammonium sulphide and ammonium
carbonate (NH4)2CO3.

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Methodology :

Materials :
 Spatulas
 Dropper
 Forceps
 Goggles
 Glass rod
 Watch glass

Apparatus :
 Bunsen burner
 Test tubes
 Beakers
 Funnel
 Boiling tubes
 Test tube holder
 Test tube rack
 Filter papers
 Litmus papers
 Delivery tube
Reagents :
 Dilute hydrochloric acid
 Distilled water
 Dilute acetic acid
 Ammonium sulfate
 Potassium chromate
 Cation mixture
 Ammonium carbonate
 Ammonium oxalate
 8-hydroxyquinoline solution
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  Magneson reagent
 Solid sodium hydroxide
 Sodium cobaltinitrite

Procedure :

Cleaning all the equipment with distilled water

Taking the filtrate from group IV

Adding a portion of (NH)2CO3 to the solution and observing.

Separating precipitate and getting precipitate for group V cation test and keeping filtrate to the further
analysis.

Adding dil.CH3COOH to the separated precipitate and heating

Adding small portion of K2CrO4 to the solution and observing.

Filtering precipitate and using precipitate to test Br+2 and testing filtrate for Sr+2 and Ca+2

Testing precipitate with flame test and observing flame color.

Adding (NH)4SO4 filtrate ,boiling and observing.

Separating the precipitate and filtrate

Testing precipitate with flame test and observing flame color

A
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 A

Adding ammonium oxalate small portion to the above filtrate and observing

Separating precipitate and testing with flame test then observing flame color.

Figure 1: Flow chart of testing of group V cations

Taking the sample which given for testing group VI cation analysis

Adding sodium hydroxide portion to the solution and boiling

Testing evolved gas using HCl dipped glass rode

heating solution until no more gas emitting and evaporating to dryness

adding few HCl drops to the solution dissolving residue.

dissolving a part of above residue in dil.HCl and dividing in to two parts

adding 8-hydroxyquinoline to the one Part and observing

adding Magneson reagent and solid sodium hydroxide to remaining part of solution and observing.

Dissolving another part of residue in distilled water

Adding sodium cobaltinitrite and observing

Figure 2: Flow chart for the testing group IV cations

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Observations :
Table 1: Observation table of the testing for group V cations

Test Observation Interference

Adding (NH4)2CO3 to test White precipitate was Ca+2,Sr+2,Ba+2 may be
sample observed . presence in the test
sample.
Adding dil/CH3COOH to White precipitate was Ca+2,Sr+2,Ba+2 may be
the precipitate and heat dissolved presence in the test
sample.
K2CrO4 was added to the Yellow color precipitate Ba+2 may be presence in
sample was observed. the test sample

Yellow precipitate was Apple green flame color was Ba+2 is presence in the
tested with flame test observed. solution.
Filtrate was added saturated White precipitate was Sr+2 may be present in the
solution of (NH4)2SO4 and observed test sample.
boiled
White precipitate was tested Crimson red color flam Sr+2 is presence in the test
with flame test color was observed sample.
Sodium oxalate was added White color precipitate was Ca+2 may be presence in
to the filtrate . observed. the test sample.
White precipitate was tested Brick red color flame was Ca+2 is presence in the test
with the flame test. observed. sample.

Table 2: Observation table of testing for group VI cation analysis

Test Observation Interference

Dil. HCl was added to the No any observation was
test sample. observed.

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NaOH was added to the test White color precipitate was
sample observed.
Sample was boiling Gas was evolved with a NH4+ may be presence in the
unpleasant odor. sample.

Evolved gas was tested Red litmus paper was turned Basic gas which NH3 is
with litmus paper in to blue color. evolved
Then NH4+ is presence in the
test sample .
Residue was dissolved in the
dil. HCl ,
I.8-Hydroxyquinoline was Yellow precipitate was Mg+2 is presence in the
added to the solution and observed. solution.
heat to boiling point

II. Mangeson regent and

solid sodium hydroxide Blue precipitate was
ware adde to the solution. observed.
Residue is dissolved in the Yellow precipitate was K+ may be presence in the
distilled water, observed. solution.
sodium cobaltnitrite was
adde to the solution

Yellow precipitate was Red color flame was K+ is presence in the

tested with flame test. observed solution.

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Discussion :
Group V cations are Ca2+, Sr2+ and Ba2+. Its group reagent is 1M solution of ammonium carbonate
(NH4)2CO3 in neutral or alkaline medium. The medium needs to be neutral or alkaline .Because it is
readily decomposed even by weak acids like acetic acid as following reaction,
CO32- (aq)+ CH3COOH(aq) ⇌ CO2 (g)↑ + H2O(l) + CH3COO-(aq)
(NH4)2CO3 is easily hydrolyzed. But in alkaline medium, the equilibrium shifts backwards and reagent
remains un-hydrolyzed.
CO32- (aq)+ H2O(l) ⇌ HCO3-(aq) + OH-(aq)
Then adding (NH4)2CO3 to test sample white precipitate may contain Barium carbonate BaCO3,
Strontium carbonate SrCO3 and Calcium carbonate CaCO3.
Ba2+ (aq) + CO32- (aq) ⟶ BaCO3 (s)↓
Ca2+ (aq) + CO32-(aq) ⟶ CaCO3 (s)↓
Sr2+(aq) + CO32- (aq)⟶ SrCO3 (s)↓
Carbonates of Ca2+, Sr2+ and Ba2+ are insoluble in water. but soluble in dilute mineral acid like acetic
acid. So, precipitate of V group cations can be dissolved in dilute acetic acid as following reactions .
BaCO3 (s) ↓ + H+ (aq) ⟶ Ba2+(aq) + H2O(l) + CO2(g)
CaCO3 (s)↓ + H+(aq) ⟶ Ca2+(aq) + H2O(l) + CO2(g)
SrCO (s)3↓ + H+ (aq) ⟶ Sr2+ (aq) + H2O(l) + CO2(g)

Group V cations form chromate salt on reacting with potassium chromate solution. These chromate salts
have different solubility. barium chromate is insoluble in dilute acetic acid while the strontium chromate
and calcium chromate are soluble. It can be separate Ba2+ from others by using this difference in
solubility.
Test a small amount of solution with potassium chromate K2CrO4 solution, a yellow precipitate indicates
Ba2+. Solubility product (ksp) of SrCrO4 and CaCrO4 is much higher than BaCrO4,therefore they
need much higher concentration of CrO42- ion to precipitate them. That’s why they can’t get precipitated
from dilute solution.

add slight excess of potassium chromate K2CrO4 solution until the solution becomes yellow colored.
Then precipitation is complete. The precipitate contains BaCrO4. Keep the filtrate for the test of Sr2+ and
Ca2+. Evaporate the solution to dryness and test with flame test. Apple Green or yellowish green flame
confirms Ba2+.

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Ba2+(aq) + CrO42- (aq) ⟶ BaCrO4 (s) ↓
Adding saturated solution of (NH4)2SO4 , and heat in a water bath for 5min. Sulphates of Sr2+ and
Ca2+ are formed after allowing few minutes. Strontium sulphate is insoluble in(NH4)2SO4 solution while
calcium sulphate is soluble .Therefore calcium sulphate goes in the filtrate.. Then the white
precipitate that get here is strontium sulphate . white precipitate test with applying to the flame test.
Then it gives Crimson flame confirms Sr2+ presence in the test sample .
Ca2+(aq) + SO42- (aq) ⟶ CaSO4(aq)
With the adding a little (NH4)2C2O4 solution and small amount of acetic acid CH3COOH, warm the
solution on a water bath. White precipitate of calcium oxalate is formed which is insoluble in water as
well as in acetic acid. This white precipitate of calcium oxalate CaC2O4 confirms Ca2+.
Ca2+ (aq) + C2O42- (aq) ⟶ CaC2O4(s)↓

In the cation group VI analysis ,presence of NH4+ in the sample, get more difficult to the analysis of
Na+ and K+. Because NH4+ is yellow in the flame test like Na+. Therefor it should first be checked
whether there is NH4+ in the sample. If NH4+ is not present in the sample there is no matter to analysis
of Na+ and K+ . it is is present in the solution first of all it should be determine and removed. The solution
is basified with a portion of NaOH. Then basified solution is heated in a water bath gas which has a
unpleasant odor is evolved. It can be identified as the ammonia by its smell. red litmus paper moistened
with distilled water is kept the mouth of tube. Then Red litmus paper turns blue, this shows the presence
of NH4+ ion. Then heat the solution until all the NH4+ ions remove from the sample.

OH- (aq)+ NH4+ (aq) + OH- (aq)  NH3 (g) + H2O (l)

Dissolve the residue in a few drops of dil HCl and add 2-3ml water. Add 8-hydroxyquinoline solution
and heat to boiling for 1-2minutes or till the odor of ammonia becomes noticeable. Then form a pale
yellow precipitate of magnesium oxine Mg(C9H6ON)2.4H2O which confirms the Mg2+ ion.
Mg+2 (aq) +2C9H7NOH(aq) Mg(C9H7NOH)2(aq).H2O (yellow)

Another part of residue is added 2-3 drops of magneson reagent and add 1 drop of sodium hydroxide
NaOH to make it alkaline. blue precipitate is formed . color density is depending on the concentration of
magnesium.
Mg+2(aq) +OH-(aq) Mg(OH)( blue)
It will get test for K+ and Na+ in the filtrate that got above. Dilute it up with adding distilled water. Then
following test are carried out. Add a little sodium sodium cobaltnitrite solution and a few drops of 2M
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acetic acid and Stir and then allow it to stand for few minutes. Then yellow precipitate of potassium
hexanitritocobaltate(III) is formed.
3K+ (aq)+ [Co(NO2)6]3- (aq)⟶ K3[Co(NO2)6] (s)↓

Then precipitate is applied to the fame test. Ii gives red color flame, it shows K+is present in the sample.
We have successfully separated the metal cations. Unlike cations, there is no well-defined system for
analysis of anions. In the coming posts of analytical chemistry, we will discuss the tests for anions.

Conclusion :
 Ca+2, Ba+2,Sr+2 , NH4+, K+, Mg+ is presence in the test sample.
 Different precipitate consist of different solubility then cation can be identify according their
solubility mostly in dilute acid and weak acids.
 Cations can not be determine accuracy then Confirmatory test such as flame test and borax
bead test and specific reagent should be carried out to confirm the cation.
 Observation can be wrong when including another cations which not belongs to these VI
groups, then those ions should be removed by appropriate methods.

Reference : :

 Estimation of hardness of water by EDTA method - University of Babylon (no date).

Available at: https://uobabylon.edu.iq/eprints/publication_2_2630_250.pdf (Accessed:
October 31, 2022).
 Flame test: Explanation, definition, Information & Summary (2019) Chemistry Dictionary.
Available at: https://chemdictionary.org/flame-test/ (Accessed: October 31, 2022).
 jerom, tom (2007) “What is qualitative analysis?,” Qualitative data analysis, pp. 30–54.
Available at: https://doi.org/10.4324/9780203412497_chapter_3.
 Libretexts (2020) 18.9: Qualitative cation analysis, Chemistry LibreTexts. Libretexts.
Available at:
https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_General_Chemistry
_(Petrucci_et_al.)/18%3A_Solubility_and_Complex-
Ion_Equilibria/18.9%3A_Qualitative_Cation_Analysis (Accessed: October 31, 2022).
 Svehla, G., 2011. Vogel's qualitative inorganic analysis. New Delhi: Pearson.

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