Cation Analysis

Dr.rer.nat. Tanti Tatang Irianti, M.Sc., Apt.

intanti@ugm.ac.id
Element Separation and Analysis
Systematics of Cation Analysis
• Cations are classified based on differences in the solubility of
chloride, sulfide, and carbonate salts, namely:
• Group I (HCl Group) →↓ with dilute HCl : 𝑃𝑏 2+ , 𝐴𝑔+ , 𝐻𝑔22+
• Group II (Group H2S) → not ↓ with dilute HCl, but ↓ with 𝐻2 𝑆 (acidic
atmosphere), namely: Hg(II), Cu, Bi, Cd, As(III), As(V), Sb(III) , Sb(V), Sn(II),
and Sn(IV).
• Group. IIA : Hg(II), Cu, Bi, and Cd (insoluble in ammonium polysulfide).
• Group. IIB : The remaining cations are As(III), As(V), Sb(III), Sb(V), Sn(II), and Sn(IV)
(soluble in ammonium polysulfide)
Continued….Element Separation and Analysis
• Group III (Group (𝑁𝐻4 )2 𝑆)→ not ↓ with dilute HCl & 𝐻2 𝑆 (acidic
atmosphere), but ↓ with (𝑁𝐻4 )2 𝑆 solution (neutral atmosphere or in
ammoniacal medium), namely: Co(II), Ni(II) , Fe(II), Fe(III), Cr(III), Cr(III), Al,
Zn, and Mn(II)
• Group IV (Group (𝑁𝐻4 )2 𝐶𝑂3 ) → not ↓ with HCl , 𝐻2 𝑆 or (𝑁𝐻4 )2 𝑆, but ↓
with (𝑁𝐻4 )2 𝐶𝑂3 solution, namely: Ca, Ba, Sr
• Group V (Remaining Group) → no ↓ with the reagents mentioned above,
namely: Na, K, Mg, 𝑁𝐻 4+ , Li
Dropping botte reaction’s tubes aquadest bottle dropping
pipette
Cation Analysis (Group I)

HCl dilute until just saturated

Cation Sample (± 5 - 10 mL)

Outline of Systematic Separation of
Cations by Group
Sample + Dilite HCl

Precipitate (Group I) Solution + 𝐻2 𝑆 (pH 0,5)

Precipitate (Group II + Solution + (𝑁𝐻4 𝑂𝐻 +

Am. Polysulfide) 𝑁𝐻4 𝐶𝑙) + 𝑁𝐻4 𝑂𝐻

Solution +(𝑁𝐻4 𝑂𝐻 +
Precipitate (Group II A) Precipitate (Group III A)
𝑁𝐻4 𝐶𝑙) +(𝑁𝐻4 )2 𝑆 pH ≥ 9

Solution + (𝑁𝐻4 )2 𝐶𝑂3 pH

Solution (Group II B) Precipitate (Group III B)
9

Precipitate (Group IV)

Solution Group V
(Residue)
pH Adjustment on Cation Separation
1. Separation of Group II and III with S
• Group II precipitates at pH 0.5
• Group III precipitates at pH 9
2. Separation of Group III and IV with S → pH must be set not too high so that the Group IV
does not precipitate, namely by adding buffer 𝑁𝐻4 𝑂𝐻 + 𝑁𝐻4 𝐶𝑙
3. Separation of Group IV and V with 𝐶𝑂3
• pH should not be made too high for Mg Group V doesn't settle
• On the other hand, a low pH will cause 𝐶𝑂3 to break down into 𝐶𝑂2.

- If too acidic ---------- does not settle

- If too alkaline --------- 𝑀𝑔(𝑂𝐻)2 also precipitates
Identification Reactions to Multiple
Cations
1. Aluminium, 𝐴𝑙 3+

White

2. Ammonium
can be recognized by the smell
red litmus paper turns blue when wet

Yellow
Identification Reactions to Multiple
Cations
3. Antimony, 𝑆𝑏 3+
Orange
soluble in NaOH solution and in (𝑁𝐻4 )2 𝑆 solution

Black
insoluble in dichlorinated soda solution

Zinc is readily soluble in dilute hydrochloric acid

and dilute sulfuric acid by giving off hydrogen
Identification Reactions to Multiple
Cations
4. Barium, 𝐵𝑎2+
White
not soluble in HClp and 𝐻𝑁𝑂3 p
gives a yellowish green flame color

5. Ferrum (II), 𝐹𝑒 2+
Dark blue
insoluble in concentrated HCl

6. Ferrum (III), 𝐹𝑒 3+
Dark blue
insoluble in concentrated HCl
Identification Reactions to Multiple
Cations
7. Bismuth, 𝐵𝑖 3+
Black

Orange solution

White

Dark brown
8. Kalium, 𝐾+
Memberikan nyala ungu

Black

White
Identification Reactions to Multiple
Cations
9. 𝐴𝑔+
White

Brown

10. 𝑃𝑏2+
White

White
P02. Anion Analysis