CATION I

1. Group 1 is composed of chlorides are relatively soluble in dilute acids.

2. The insoluble chlorides of Group I are lead chloride, mercurous,

chloride, and silver chloride.

3. Solubility products
PbCl2 : 1x10-4
Hg2Cl2 : 2x10-18
AgCl : 1.56x10-10

4. Solubility
PbCl2 : 0.04F
Hg2Cl2 : 7.5x10-7F
AgCl : 1.3x10-5F

5. Name and Formula of Group I Cations

PbCl2 – Lead chloride
Hg2Cl2 – Mercurous chloride
AgCl – Silver Chloride

6. In Group I cations, lead chloride is always incompletely precipitated

and in low concentration may not be precipitated at all.

7. In Group I, PbCl2 is separated from other because of an increase

solubility in hot water.

8. The solubility of PbCl2 is

0.673 g/100ml at 0°
3.34g g100 ml at 100°
9. True – Provided that the water stays hot, all the PbCl2 is seldom
removed. (Special case: causes white residue causes confusion with
//silver and mercury// chloride)

10. True – Ammonia water has a limiting value to form complex ion. If
the amount of AgCl is very large some of it may not dissolve.

11. Ammonia water reacts AgCl + a medium for auto-redox action of

Hg2Cl2

12. Ammonia water and medium for auto-redox action of Hg2Cl2 will
yield mercury and mercuric aminochloride. (insoluble)

13. Metallic mercury in finely divided state is black in color. Blackening =

presence of Hg2Cl2

14. Group I cation analysis has three principal steps.

15. Cation I Procedure

15.1 First, precipitated with dilute HCl washed with cold water to
remove the cation groups.
15.2 Second, Lead Chloride is removed by leaching with hot water.
15.3 Third, separation of AgCl from Hg2Cl2 with ammonia water.

16. Cation I
White precipitate indicates either presence of chlorides or
oxychlorides of antimony and bismuth.
17. Cation I
Precipitation of oxychlorides of antimony and bismuth is due to
hydrolysis

18. Cation I
Adding 1 drop of concentrated HCl will dissolve the oxychlorides of
antimony and bismuth, whereas Group I cations will not.
Remember: Remove first two drop of the solution containing some of the p.
et. add 1 drop concentrated HCl.

19. Cation I
True - The reaction between the Bi oxychlorides is reversible.

20.
True - Oxychlorides precipitate is dependent on low concentration of
hydrogen ions.

21. Cation I
Slight excess in HCl will cause complete Chloride precipitation due to
common-ion effect. Prevents formation of BiOCl and SbOCl.

22. Cation I
Large concentration of HCl will increase the solubilities of precipitated
chlorides through formations of soluble complex ions.

23. Cation I
Precipitate remaining the test tube is washed with 10 drops cold water
with HCl to reduce solubility of Lead Chloride → soluble ion complex.
24. Cation I
Lead Chloride is soluble in hot water but reprecipitates if allowed to be
cooled. (Often missed)

25. Micropipette is used and should be preheated on its tip with hot
water/steam bath.

26. Cation I
Ammoniacal sol. left with Hg and HgNH3Cl for appreciable length of time
will cause Ag complex ion react with metallic mercury.

27. Cation I
The solution must be acid to convert the Ag(NH3)2+ to AgCl otherwise no
precipitate will form.

28. Cation I
Presence of mercurous ion, residue in ammonia must be black/
discolored→colloidal mercury

29. Cation I
Lead, Silver, and mercurous ions give white precipitate with the chloride
solution in an acid solution.

30. Cation I
An incomplete separation of PbCl2 from the group precipitate is affected
with hot water.
31. True – PbCrO4 is much less soluble than PbCl2.

32. Cation I
AgCl and HgCl2 is treated with ammonia will leave mercury and mercuric
aminochloride which a black in color.

33. Cation I
Ammonia acts upon mercurous chloride → internal redox reaction. One
mercurous ion (Ag+) is reduced to mercury/ oxidized to mercuric state.

34. Cation I
Mercuric aminochloride is white and finely divides mercury is black.

35. Cation I
Centrifugate → Residue are Ag(NH3)2+ and Cl- ions. If made with nitric
acid the complex is destroyed and AgCl precipitates.

36. Cation I
ADDITIONAL confirmation is obtained from mercurous ion through
dissolving in nitric acid and testing with stannous chloride.

37. True – Nitric acid dissolves Hg and HgNH2Cl.

38. Cation I
Chloride ions
Low concentration of Cl- ions → HgCl2
High concentration of Cl- ions → HgCl4-

39. Cation I
Acid solutions containing HgCl2 & HgCl4-give precipitates with stannous
ions. Its colors is/are white, gray, or black.

40. Cation I
Stannous chloride reduces HgCl2 to black and finely divided mercury. Gray
mixture of Hg2Cl2 and Hg2++ is obtained.
 CATION II
1. Cation II
There are eight cations which precipitates as sulfides from a solution which
is 0.3F respect to hydronium ions.

2. Cation II
Name the eight cations which precipitated in sulfides in Cations II
1. cupric ions
2. mercuric ions
3. lead ions
4. bismuth ions
5. cadmium ions
6. arsenic ions
7. antimony ions
8. tin ions

3. True – In the Fresenius scheme of analysis 13 cations of the heavy

metals are precipitated as sulfides (fairly insoluble)

4. Cation II
The sulfides which will precipitate in 0.3F HCl (acid) are Group II
5. Cation II
The sulfides which are soluble in 0.3F HCl (acid) are Group III

6. Cation II
Group II A sulfides are HgS, CuS, Bi2S3, PbS, and CdS.

7. Cation II
Group III sulfides are ZnS, CoS, NiS, FeS, and MnS.

8. Cation II
The real significance of hydronium ion is to control the sulfide ion
concentration.

9. Cation II
Concentration of ions before precipitation is 0.01F for a divalent ion to be
precipitated by a sulfide-ion concentration.

10. Cation II
Concentration of ions before precipitation is 0.01F for a divalent ion to be
precipitated by a sulfide-ion concentration.

11. Cation II
Separation of two or more ions by precipitating agents requires equilibrium
ratio of 2 or more ions to be quite large is called fractional precipitation.
12. Cation II
PbS and CdS do not precipitate completely in Group II, may appear in
small concentrations in Group III.

13. Cation II
ZnS, CoS, and NiS may precipitate in Group II, precipitate largely in Group
III.

14. Cation II
Eight sulfides which make up Group II are HgS, CuS, Bi2S3, PbS, CdS,
As2S3, SnS2, and Sb2S3.

15. Which are acidic in nature in the following? PbS, CdS, Sb2S3, HgS,
CuS, Bi2S3, As2S3, and SnS2
Ans: As2S3, SnS2, and Sb2S3

16. Which exhibit basic properties in the following? PbS, CdS, Sb2S3, HgS,
CuS, Bi2S3, As2S3, and SnS2
Ans: HgS, CuS, Bi2S3, PbS, CdS

17. Cation II
Group II precipitate is treated with KOH (potassium hydroxide). Thus, the
sulfides of arsenic, antimony, and tin will dissolve.

18. Cation II
Group II precipitate is treated with KOH (potassium hydroxide). Thus, the
sulfides of arsenic, antimony, and tin will dissolve.
19. Cation II
Sulfide ion + KOH will cause a partial solution of HgS to form complex ions
HgS2-

20. True – Group IIA are insoluble in KOH.

21. True – Group IIB are soluble in KOH.

22. Cation II Procedure

22.1 First, group is precipitated then subdivided into subgroups by the
action of potassium hydroxide solution.
22.2 Analysis of IIA
22.3 Analysis of IIB

23. Cation IIA and IIB

23.1 Add 2 drops of 3F HNO3 → heat in water bath / 3 mins
23.2 Make barely alkaline with 3F NH3
23.3 Add 3F HCl until its acid

24. Cation IIA and IIB

Add 2ml of water and 5 additional drops of Thioacetamide solution, and
heat again in boiling water for 5 mins.

25. True - The cetrifugate in separation into subgroups contains Groups III-
V. Reserve for later analysis.
26. Cation IIA and IIB
Name the precipitate + color consists in sulfides of cations of Group II
1. As2S6 - yellow
2. As2S5 - yellow
3. SnS2 - yellow
4. CdS - yellow
5. HgS - black
6. PbS - black
7. CuS – black
8. Bi2S3 – brown-black
9. SnS – brown
10. Sb2S3 – orange-red
11. Sb2S5 – orange

27. Cation IIA and IIB

Add 8 drops of 3F KOH. Stir and heat in water bath for 3 mins. Cetrifugate
→ treat with 8 drops of 3F KOH.

28. Cation IIA and IIB

Residue – HgS, CuS, CdS, PbS, and Bi2S3
Centrifugate – Arsenic, antimony, and tin
29. Cation IIA and IIB
Oxidize any stannous ions which may be present in stannic state,
otherwise 3F KOH will be incomplete regard to tin.

30. Cation IIA and IIB

Not appreciably soluble in KOH – SnS
Soluble in KOH – SnS2

31. Cation IIA and IIB

Solution may be Ammoniacal but dissolves in HCl or converted into
sulfides by H2S treatment which follows.

32. Cation IIA and IIB

Solution may be Ammoniacal but dissolves in HCl or converted into
sulfides by H2S treatment which follows.

33. Cation IIA and IIB

The precipitation of arsenic by means of H2S is very slow except in a hot
acid solution.

34. Cation IIA and IIB

We use 0.3F in acidifying and diluting the solution in respect of hydronium
ions.
If the solution is too acid, precipitations may be incomplete/prevented. Ex:
Stannic, lead, and cadmium ions.
35. Cation IIA and IIB
We use 0.3F in acidifying and diluting the solution in respect of hydronium
ions.
If the solution is not sufficiently acid, cations of Group III may precipitate
along with sulfides. Ex: Zinc, nickel, and cobalt.

36. Cation IIA and IIB

Color precipitate indication → cation present
Color: Black ppt. – presence of mercuric, bismuth, copper or lead ions

37. Cation IIA and IIB

Color precipitate indication → cation present
Color: Yellow ppt. – arsenic, cadmium, or tin

38. Cation IIA and IIB

Color precipitate indication → cation present
Color: Orange – antimony

39. Cation IIA and IIB

Color precipitate indication → cation present
Color: White to Black – mercury

40. Cation IIA and IIB

Color: White suspension – sulfur
41. Cation IIA and IIB
If H2S is not expelled from the centrifugate, atmospheric oxidation will
convert S- to SO4-

42. Cation IIA and IIB

The H2S in the water retards oxidation of the precipitated sulfides to
sulfates.

43. Cation IIA and IIB

The NH4Cl is added to aid breaking up any colloidal dispersion which may
be present.

44. Cation IIA

Cu, Bi, Cd, and Pb are dissolved due to oxidation of the sulfides ion by the
nitrate ion, in acid solution to free sulfur.

45. True – The lack of a black precipitate after treating HgS with 3FHNO3
does not confirm the absence of mercuric ion.

46. Cation IIA

Aqua regia dissolves HgS via oxidation of Sulfide ion and complexing ion
of the chloride.

47. Cation IIA

Aqua regia liberates chlorine; oxidize stannous ions → stannic ions.
48. Cation IIA
Only stannous ions will give the characteristics for mercuric ion.

49. Cation IIA

The appearance of dense white fumes of SO3 indicates that HNO3 has
been distilled from the solution.

50. Cation IIA

Before precipitating lead as PbCrO4, it is necessary that the solution is
acidic; otherwise bismuth precipitate as chromate.

51. Cation IIA

Bismuth hydroxide is reduced to metallic bismuth which colored in black

52. Cation IIA

The blue color of copper-amonia complex is confirmatory test for cupric
ion.

53. Cation IIA

In small concentrations of cupric ion, add HAc and a drop of potassium
ferrocyanide.

54. Cation IIA

A reddish-brown color precipitate of cupric cyanide confirms presence of
cupric ion.
55. Cation IIA
The potassium cyanide is added to form stable complex ion, and prevent
interference w/ cadmium test. (If Cu is absent, don’t try)

56. Cation IIA

Group II A Analysis

Confirmatory Color Ion

SnCl2 White-gray Mercuric Ion

1F K2CrO4 Yellow Lead Ion

K2SnO2 Black Bismuth Ion

Cu(NH3)4++
Deep blue Copper Ion
Cd(NH3)4++

CH3CSNH2 Yellow Cadmium Ion

57. Cation IIB

The alkaline centrifugate of Group IIB form soluble complex thio or oxytio
anions.

58. Cation IIB

Group IIB form soluble complex thio or oxytio anions. Acidifying will destroy
complex ions and GIIB precipitate as sulfides.
59. Cation IIB
Heat expel H2S. Prolonged heating of the solution is avoided to prevent
partial solution of As2S2 or As2S5.

60. Cation IIB

3F KOH dissolves mercuric sulfide → HgS2-. The residue is washed to
remove chloride ion.

61. Cation IIB

Ag coin - Arsenic ion is in the solution it will be deposited as metallic
arsenic.

62. True - Metallic arsenic is soluble in NaOCl solution with metallic

antimony.

63. Cation IIB

Ag coin – The presence of H2S will darken the coin.
Mercuric/ cupric ions →black deposit

64. Cation IIB

Ag coin – gentle rubbing with soft cloth will cause black mercury to be
silvery in appearance and copper to be copper-red color.

65. Cation IIB

Sodium nitrite oxidizes antimony ions to the pentavalent state.
66. Cation IIB
An excess of sodium nitrite will produce the same color change.

67. Cation IIB

Magnesium metal is added to reduce antimony to the metal and stannic
ions → stannous ions.

68. Cation IIB

Magnesium ribbon left undissolved, a positive test will be obtained.

69. Chem Reacts

Oxidation of stannous ions to stannic ions is accomplished by heating with
nitric acid.

70. Chem Reacts

Mercuric ions give a white, brown, or black-colored precipitate with
hydrogen sulfide.

71. Chem Reacts

71.1 Cu ions precipitate as black CuS w/ hydrogen sulfide
71.2 Bi ions precipitate as dark brown Bi2S3 w/ hydrogen sulfide
71.3 Pb ions precipitate as black PbS w/ hydrogen sulfide

72. Chem Reacts

72.1 Cadmium ions ppt. w/ hydrogen sulfide → cadmium sulfides
72.2 Cold + slightly acid = yellow
 72.3 Hot + acid = orange to red

73. Chem Reacts

Arsenious acid and the arsenate ion give yellow precipitates with hydrogen
sulfide.

74. Chem Reacts

Stannous ions produces brown precipitate of SnS with H2S.

75. Chem Reacts

The stannic ion can exist only as complex chlorostannate (SnCl4-). This
ion yields a yellow precipitate of SnS2 with hydrogen sulfide.

76. True – KOH solution dissolves sulfides of arsenic, antimony, and

tertravalent; incompletely dissolves mercuric sulfide.

77. True – All the sulfides of Group IIA are oxidized by dilute nitric acid
except HgS.

78. True – HgS dissolves in aqua regia.

79. Chem Reacts

Mercuric ion confirmed by stannous chloride → color white precipitate
80. Chem Reacts
Lead ion is precipitated as PbSO4 in the presence of bismuth, copper, and
cadmium.

81. Chem Reacts

A large excess of hydronium ions is avoided to prevent formation of
soluble Pb[HSO4]2-

82. Chem Reacts

Lead sulfate dissolves in excess acetate ions to form lead acetate.

83. Chem Reacts

Lead sulfate dissolves in excess acetate ions to form lead acetate. Forms
color yellow.

84. Chem Reacts

Separation of bismuth ions convert two ionsinto the tetramine complex.

85. Chem Reacts

Bismuth ion is colored black by the stannite ion.

86. True – Cupric ferrocyanide is a reddish-brown ppt/ insoluble in dilute

acids; soluble in ammonia

87. True – cyanide ion complex actions overcomes the two ions of copper
and cadmium.
88. Chem Reacts
Cupric cyanide is unstable and decomposes into cuprous cyanide.

89. Chem Reacts

Not stable precipitation of yellow CdS is solved by treatment with H2S.

90. Chem Reacts

Alkaline that is acidified destroys complex ions

91. Chem Reacts

Concentrated hydrochloric acid dissolves antimonous sulfide and stannic
sulfide.

92. Chem Reacts

Although insoluble in HCl, arsenious triusulfides dissolves in concentrated
nitric acid.

93. Chem Reacts

Sodium acetate is added to buffer the acidity of the nitric acid solution to
the arsenate ion.

94. True – Arsenate precipitates reddish-brown silver arsenate.

95. Chem Reacts
Addition of Mg converts chloroantimonite ion → metallic Sb

96. Chem Reacts

Addition of Mg converts chlorostannate ion → stannous ion

97. True – Addition of mercuric chloride that contains stannous ions

produces white or gray ppt of Hg2Cl2 or Hg.