EXPERIMENT 5:

DETERMINATION OF CATIONS AND ANIONS.

Ralph John Emerson Molino

Instructor 4
Institute of Chemistry
University of the Philippines Diliman
CHEMISTRY.................
Study of matter, its COMPOSITION, properties, the changes it undergoes and
the energy associated with these changes.

For today!
Composition: Simple Cations and Anions!

Composition studied QUALITATIVELY!

And not quantitatively (unlike Titration)

We just want to know if a specific ion is there!

QUALITATIVE DETECTION………..
…………………THROUGH REACTIONS
Two Kinds of Reactions: * * *
Elimination Tests: Narrow down your choices * *
* *
to a couple few.
* * * *

Confirmatory Tests: Reaction specific for each Elimination

Species. ***
Confirmatory
For Verification.
*
ELIMINATION AND CONFIRMATORY TESTS
Why Elimination Tests are needed?

Confirmatory Tests might be component specific but for a list of many

possible species present, doing many confirmatory tests is not
convenient.

Elimination Tests are needed so that fewer confirmatory tests will be

down.

Time and Resources Convenient!

Cation Test- Elimination Test, RESULTS.
Cation Analysis, Elimination Test
NaOH + x’s NaOH NH3 + x’s NH3

Cu2+ Blue Ppt Blue Ppt Blue Ppt Deep Blue Soln

Fe3+ Brown Ppt Brown Ppt Brown Ppt Brown Ppt

Zn2+ White Ppt Colorless White Ppt Colorless

Soln Soln
Ca2+ White Ppt White Ppt Colorless Colorless
Soln Soln
NH4+ Colorless Soln Colorless Soln Colorless Colorless Soln
Soln
Cation Analysis- Elimination Test, Reactions.
NaOH + x’s NaOH Reactions:
2+ −
Blue Ppt Blue Ppt 𝐶𝑢(𝑎𝑞) + 2𝑂𝐻(𝑎𝑞) → 𝐶𝑢(𝑂𝐻)2 (𝑠)
Cu2+
3+ −
Brown Ppt Brown Ppt 𝐹𝑒(𝑎𝑞) + 3𝑂𝐻(𝑎𝑞) → 𝐹𝑒(𝑂𝐻)3 (𝑠)
Fe3+
Zn2+ White Ppt Colorless 2+
𝑍𝑛(𝑎𝑞) −
+ 2𝑂𝐻(𝑎𝑞) → 𝑍𝑛(𝑂𝐻)2 (𝑠)
Soln −
𝑍𝑛(𝑂𝐻)2 (𝑠) + 2𝑂𝐻(𝑎𝑞) → 𝑍𝑛(𝑂𝐻)2−
4(𝑎𝑞)
2+ −
White Ppt White Ppt 𝐶𝑎(𝑎𝑞) + 2𝑂𝐻(𝑎𝑞) → 𝐶𝑎(𝑂𝐻)2 (𝑠)
Ca2+
Colorless Soln Colorless Soln No Reaction
NH4+
Most Hydroxides are Insoluble
Overview: Complexation Reactions
Anytime a metal ion 𝑀𝑛+ react with many a ligands.
Ligands (L)- any species with lone pair
A Coordination
Compound.
𝑀 𝑧+ + n𝐿(𝑎𝑞) → 𝑀(𝐿)𝑛𝑧+
Metal – Ion Many a Ligand Coordination Compound

MAJORITY OF
Possible Ligands: COORDINATION
COMPOUNDS ARE
Coordination Compound: COLORED!
Soluble: If it has a net charge if Ligand is not able to neutralize the metal’s charge
Insoluble: A precipitate if metal ion’s charge is neutralized by the Ligands.
Cation Analysis- Elimination Test, Reactions.
Ammonia is able to produce OH- in solution because:
NH3(aq) + H2O(l)  NH4 +(aq) + OH- (aq)
NH3 + x’s NH3 Reactions:
2+
Cu2+ Blue Ppt Blue Soln 𝐶𝑢(𝑎𝑞) + 2𝑂𝐻(𝑎𝑞) → 𝐶𝑢(𝑂𝐻)2 𝑠
with x’s NH3: 𝐶𝑢(𝑂𝐻)2 (𝑠) + 2𝑁𝐻3(𝑎𝑞) → 𝐶𝑢(𝑁𝐻3 )2+
(𝑎𝑞) + 2𝑂𝐻
−

3+ −
Fe3+ Brown Ppt Brown Ppt 𝐹𝑒(𝑎𝑞) + 3𝑂𝐻(𝑎𝑞) → 𝐹𝑒(𝑂𝐻)3 (𝑠)

2+ −
Zn2+ White Ppt Colorless 𝑍𝑛(𝑎𝑞) + 2𝑂𝐻(𝑎𝑞) → 𝑍𝑛(𝑂𝐻)2(𝑠)
Soln with x’s NH3: 𝑍𝑛(𝑂𝐻)2 (𝑠) + 4𝑁𝐻3(𝑎𝑞) → 𝑍𝑛(𝑁𝐻3 )2+
4(𝑎𝑞) + 2𝑂𝐻
−

Ca2+ Colorless Soln Colorless Soln No Reaction

NH4+ Colorless Soln Colorless Soln No Reaction

Precipitates 𝐶𝑢(𝑂𝐻)2 𝑎𝑛𝑑 𝑍𝑛(𝑂𝐻)2 are weaker than 𝐹𝑒(𝑂𝐻)3 their OHs can be displaced by the many N𝐻3 ligands,
forming soluble, charged complexes.
Cation Test: Confirmatory Tests
Cation Tests, Confirmatory Results:

𝐹𝑒 3+ + 𝑆𝐶𝑁 − → 𝐹𝑒(𝑆𝐶𝑁)2+
Blood Red Soln
 Cation Tests, Confirmatory Results:

Left: 𝐶𝑢2+ + 𝑥 ′ 𝑠 𝑁𝐻3 → 𝐶𝑢(𝑁𝐻3 )2+ (𝑎𝑞) Left: 𝐶𝑢2+ + 𝑥 ′ 𝑠 𝑁𝐻3 → 𝐶𝑢(𝑁𝐻3 )2+ (𝑎𝑞)
Deep Blue Soln Deep Blue Soln
Right: 𝑍𝑛2+ + 𝐾 + 𝐹𝑒(𝐶𝑁)−3
6 -> 𝐾 + ZnFe(CN)−6 𝑎𝑞 Right: 𝑍𝑛2+ +𝐾 + 𝐹𝑒(𝐶𝑁)−4
6 -> 𝐾2+ ZnFe(CN)−
6 𝑎𝑞
Yellow Ppt White Ppt.
Cation Tests, Confirmatory Results:

𝐶𝑎2+ + 𝐶2 𝑂42− → 𝐶𝑎𝐶2 𝑂4 𝑁𝐻4 + + 𝑂𝐻 − → 𝑁𝐻3 + 𝐻2 𝑂

White Ppt Basic Gas
Red Litmus Paper to Blue
Elimination Tests: Anions.
𝐶𝑂32− , 𝑆𝑂42− , 𝑃𝑂43− , 𝐼 − , 𝐵𝑟 − , 𝑆𝐶𝑁 − , 𝑁𝑂3−
𝐵𝑎(𝑁𝑂3 )2 (𝑎𝑞)

ppt’ation no ppt’ation

𝐵𝑎2+ + 𝐶𝑂32− → 𝐵𝑎𝐶𝑂3 (𝑠)

𝐼 − , 𝐵𝑟 − , 𝑆𝐶𝑁 − , 𝑁𝑂3−
𝐵𝑎2+ + 𝑆𝑂42− → 𝐵𝑎SO4 (𝑠)
𝐵𝑎2+ + 𝑃𝑂43− → 𝐵𝑎3 (𝑃O4 )2 (𝑠)

Confirmatory Tests: C2 and C3

Confirmatory Tests: D1 to D3
Anion Tests: Confirmatory Results.
D1-D3: Basis, dissolution of precipitates:

𝐵𝑎𝐶𝑂3 (𝑠) + 2𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) → 𝐵𝑎(𝐶𝐻3 𝐶𝑂𝑂)2 𝑎𝑞 + 2𝐻2 𝐶𝑂3 𝑎𝑞

𝐻2 𝐶𝑂3 (𝑎𝑞) → 𝐶𝑂2(𝑔) + 𝐻2 𝑂(𝑙)

Dissolution with Efffervesence.
𝐵𝑎𝑆𝑂4 (𝑠) + 2𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) → 𝐵𝑎(𝐶𝐻3 𝐶𝑂𝑂)2 𝑎𝑞 + 2𝐻2 𝑆𝑂4 𝑎𝑞

Dissolution without Effervesence

𝐵𝑎3 (𝑃O4 )2 𝑠
+ 3𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) → 𝑁𝑉𝑅
No Dissolution.
Anion Tests: Confirmatory Results for C-2.
Reagent: Fe(N𝑂3 )3 𝑖𝑛 𝐻𝑁𝑂3 𝑎𝑛𝑑 𝑇𝑜𝑙𝑢𝑒𝑛𝑒
Redox Transformation:
HNO3 : To carry out the reaction in
acidic medium.
Toluene: To capture the new product formed from the redox
transformation of the anion.
Only 𝐼 − will react:
𝐹𝑒 3+ → 𝐹𝑒 2+ 𝑌𝑒𝑙𝑙𝑜𝑤 𝐴𝑞𝑢𝑒𝑜𝑢𝑠
2𝐼 − 𝑎𝑞 → 𝐼2 𝑜𝑟𝑔 Will move up to produce Pink
Organic Layer.
𝑆𝐶𝑁 − will have no redox reaction with 𝐹𝑒 3+ 𝑰− 𝑺𝑪𝑵− 𝑩𝒓− 𝑵𝑶−
𝟑
Nothing will move up, Organic Layer will remain colorless. Confirmatory Results for C-2

Both 𝑆𝐶𝑁 − and 𝐹𝑒 3+ are in the aqueous layer. They will not react via redox but through a COMPLEXATION
REACTION  FORMATION OF BLOOD RED COMPLEX.
Anion Tests: Confirmatory Results. C-3
Reagent:
𝐾𝑀𝑛𝑂4 𝑖𝑛 𝐻𝑁𝑂3 𝑎𝑛𝑑 𝑇𝑜𝑙𝑢𝑒𝑛𝑒.
𝐾𝑀𝑛𝑂4 𝑖𝑠 𝑎 𝑠𝑡𝑟𝑜𝑛𝑔𝑒𝑟 𝑜𝑥𝑖𝑑𝑖𝑧𝑖𝑛𝑔 𝑎𝑔𝑒𝑛𝑡 𝑡ℎ𝑎𝑛 𝐹𝑒(𝑁𝑂3 )3
Mn there is at a +7.

Will React: 𝐼 − , 𝐵𝑟 −
𝑀𝑛𝑂4− → 𝑀𝑛2+ 𝑌𝑒𝑙𝑙𝑜𝑤 𝐴𝑞𝑢𝑒𝑜𝑢𝑠
2𝐼 − 𝑎𝑞 → 𝐼2 𝑜𝑟𝑔 Pink Organic

𝑀𝑛𝑂4− → 𝑀𝑛2+ 𝑌𝑒𝑙𝑙𝑜𝑤 𝐴𝑞𝑢𝑒𝑜𝑢𝑠

2𝐵𝑟 − 𝑎𝑞 → 𝐵𝑟2 𝑜𝑟𝑔 Yellow Organic

𝑆𝐶𝑁 − and N𝑂3− will not give off its electrons to Mn because they contain
Electronegative Atoms. Their toluene layer will remain colorless. And their aqueous layer will have the
flesh or pink color (excess permanganate reagent)
Anion Tests: Confirmatory Results.
• Nitrate Test:

(+) Result: Formation of a brown ring.