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Qualitative Analysis
of the Group I Cations
Introduction
The separation of the three Group I cations Ag+ ,Pb2+ and Hg22+ from other cations in later groups
depends on the fact that chlorides of Group I cations are insoluble in acidic solution. This is a rather
unusual occurrence, as you can see from the general solubility rules given on page 374. All other
cations (Groups IIV) form soluble chlorides and remain in solution.
SEPARATION OF GROUP I CATIONS
The precipitate consisting of white, insoluble AgCl, PbCl2 and Hg2Cl2 forms when 6M HC1 is
added to 10 or so drops of the solution. Only a slight excess of hydrochloric acid is added to obtain
the precipitate.
Ag+(ac) + Cl-(ac) === AgCl(s)
Ks = 1.8x10-10
(29-1)
(a)
Ks = 1.7x10-5
(29-1)
(b)
Ks = 1.4x10-18
(29-1)
(c)
Although Equation (29-1) and similar equations that can be written for Pb2+ and Hg22+ suggest that
the equilibrium can be shifted as far to the right as desired by adding sufficient Cl- ions, the
solubilities of the chlorides begin to increase after a large enough [Cl-] is reached, because of
complex ion formation:
AgCl(s) + Cl-(ac) === AgCl2-(ac)
(29-2)
(a)
(29-2)
(b)
(29-2)
(c)
Even a slight excess of Cl- will cause the essentially complete removal of these cations as their
chlorides. In the solutions used here, [Ag+] = 0.02 before the addition of HCl. At the conclusion of
the Group I precipitation, sufficient Cl- is still present so that [Cl-] = 0.35. The maximum amount of
Ag+ that can remain in solution then is given by
[Ag+] (0.35) = K= 1.8x10-10
(29-3)
which gives [Ag+] = 5x10-10 M. Thus [Ag+] has been reduced from 0.02 M to 5x10-10 M this is
certainly complete enough removal of Ag+ for practical purposes.
Although Hg22+ is also completely precipitated under these conditions, PbCl2 is sufficiently soluble
that a high enough [Pb2+] remains in solution to give a PbS precipitate with Group II.
(29-4)
After the precipitates are heated and stirred and the PbCl2 has dissolved, the AgCl and Hg2Cl2 must
be quickly centrifuged to the bottom of the test tube. The supernatant liquid containing Pb2+ is
drawn off before the solution cools and the PbCl2 reprecipitates.
The presence of Pb2+ is confirmed by adding K2Cr04. A yellow precipitate of lead chromate
(Ksp=2x10-16) forms if Pb2+ is present:
Pb2+(ac) + CrO42-(ac) === PbCrO4(s)
(29-5)
The precipitate of AgCl and Hg2Cl2 is treated with concentrate NH3 (15 M), and the silver and
mercurous ions are confirmed by the different behaviors of these chlorides with NH3.
Silver chloride (AgCl) dissolves in NH3 by forming the complex ion Ag(NH3)2+:
AgCl(s) + 2NH3(ac) === Ag(NH3)2+ + Cl-(ac)
(29-6)
This same effect was noted in experiment 28 when insoluble compounds were dissolved by forming
complexes.
Mercurous chloride undergoes a disproportionation reaction with NH3. In a disproportionation
reaction, there is simultaneous oxidation and reduction of different atoms of one kind. In this case,
mercurous ions Hg22+ are oxidized to the mercuric ion Hg2+ and reduced to metallic mercury Hg(l):
Hg2Cl2(s) + 2NH3(ac) === Hg(NH2)Cl(s) + Hg(l) + NH4Cl(ac)
(29-7)
The Hg2+ forms a white precipitate of Hg(NH2)Cl(s) (mercuric amidochloride), while the metallic
mercury in finely divided form is black. The mixture of these two precipitates appears gray. The
appearance of this gray color is taken as confirmation of the presence of Hg22+.
The supernatant liquid contains Ag(NH3)2+ ions, and their presence is confirmed by acidifying this
solution with HNO3. Protons combine with NH3 to form NH4+ , destroying the silver ammine
complex in the process:
Ag(NH3)2+(ac) + H3O+(ac) === Ag+(ac) + 2NH4+(ac) + 2H2O(l)
(29-8)
The Ag+ ions then form a precipitate of white AgCl (which confirms the presence of Ag+) by
reacting with the Cl- ions in solution:
Ag+(ac) + Cl-(ac) === AgCl(s)
(29-9)
A possible complication can result if a large amount of mercury is present. The metallic mercury
formed via the reaction given in equation (29-7) may reduce AgCl to metallic silver:
2AgCl(s) + 2Hg(l) === 2Ag(s) + Hg2Cl2(s)
(29-10)
If this happens, the silver will remain with the gray mercury precipitate, instead of dissolving via
the reaction of equation (29-6). Then no positive confirmatory test for Ag+ will be seen. If you do
not detect the presence of Ag+ via the reactions of equations (29-8) and (29-9), you should try to
find it in the gray precipitate.
The precipitate is treated with aqua regia, a mixture of conc. HCl and conc. HNO3, which dissolves
almost any salt. The Hg(NH2)Cl(s) and Hg(l) are oxidized and converted to chloro complexes:
2Hg(NH2)Cl(s) + 6NO3-(ac) + 6Cl-(ac) + 8H3O+(ac) === 2HgCl42- + N2(g) + 6NO2(g) + 14H2O (29-11 )
Hg(l) + 2NO3-(ac) + 4Cl-(ac) + 4H3O+(ac) === HgCl42-(ac) +2NO2(g) + 6H2O(l)
(29-1 2)
Ag is oxidized and converted to a chloro complex by the large excess of concentrate HCl:
Ag + NO3-(ac) + 2Cl-(ac) + 2H3O+(ac) === AgCl2-(ac) + NO2(g) + 3H2O(l)
(29-13)
The solution is evaporated to remove any excess aqua regia. When the remaining solution is diluted
with water, [Cl-] is decreased sufficiently that white AgCl precipitates; equilibrium [equation
(29-14)] is shifted to the right when [CI-] is lowered.
AgCl2-(ac) === AgCl(s) + Cl-(ac)
(29-14)
The HgCl42- ion remains in solution. If desired, its presence can be confirmed after centrifuging by
adding Sn(II) chloride solution, which produces a gray precipitate by first reducing HgCl42- to white
Hg2Cl2 and then to black Hg:
2HgCl42-(ac) + Sn2+(ac) === Hg2Cl2(s) + SnCl(6)2-(ac)
(29-15)
(29-16)
CHEMICALS NEEDED
(Solutions without specified concentration are prepared as indicated in Appendix V.)
Ag+ ( 2 mg/ml )
Hg22+ (10 mg/ml)
Pb2+ (15 mg/ml)
6M NH3
15 M NH3
6M HC2H3O2 (acetic acid)
litmus paper
K2CrO4 solution
6M HCl
12 M HCl
6M HNO3
16M HNO3
SnCl2 solution
DIAGRAMA DE FLUJO
Muestra contiene iones de
Ag+, Pb2+, Hg22+
2+
2+
2+
3+
2+
2+
Pb , Hg , Cu , Bi , Cd , Sn , Sn(IV), As(III),
As(V), Sb(III), Sb(V)
grupo III
grupo IV
grupo V
Centrifugar
precipitado
Centrifugar
La separacin de los tres Grupo I cationes Ag +, Pb2 + y + HG22 de otros cationes en grupos
posteriores depende del hecho de que los cloruros de cationes del grupo I son insolubles en
solucin cida. Esto es una ocurrencia bastante inusual, como se puede ver en las reglas de
solubilidad generales dadas en la pgina 374 Todos los otros cationes (grupos II-V) formar cloruros
solubles
y
permanecen
en
solucin.
El precipitado que consiste en blanco, AgCl insoluble, PbCl2 y formas Hg2Cl2 cuando se aade 6M
HC1 al 10 o as las gotas de la solucin. Slo se aade un ligero exceso de cido clorhdrico para
obtener el precipitado.
Ks = 1.8x10-10
(29-1)
(a)
Ks = 1.7x10-5
(29-1)
(b)
Ks = 1.4x10-18
(29-1)
(c)
Aunque la ecuacin (29-1) y ecuaciones similares que se puede escribir para Pb2 + y HG22 +
sugieren que el equilibrio se puede desplazar lo ms a la derecha segn se desee mediante la
adicin de iones Cl-suficientes, las solubilidades de los cloruros de comienzan a aumentar despus
de un gran suficiente [Cl] es alcanzado, debido a la formacin de iones complejos:
AgCl (s) + Cl-(ac) === AgCl2- (ac) (29-2) (a)
PbCl2 (s) + Cl-(ac) === PbCl3- (ac) (29-2) (b)
Hg2Cl2 (s) + 2Cl- (ac) === HgCl42- (ac) + Hg (l) (29-2) (c)
Incluso un ligero exceso de Cl provocar la eliminacin esencialmente completa de estos cationes
como sus cloruros. En las soluciones que se utilizan aqu, [Ag +] = 0,02 antes de la adicin de HCl. A
la conclusin de la precipitacin Grupo I, Cl suficiente todava est presente de modo que [Cl] =
0,35. La cantidad mxima de Ag + que puede permanecer en solucin se calcula mediante
[Ag +] (0.35) = K = 1.8x10-10 (29-3)
lo que da [Ag +] = 5x10-10 M. Por lo tanto [Ag +] se ha reducido de 0,02 M a 5x10-10 M este es, sin
duda lo suficientemente completa eliminacin de Ag + a efectos prcticos.
Aunque HG22 + tambin se precipit completamente en estas condiciones, PbCl2 es
suficientemente soluble que un alto suficiente [Pb2 +] permanece en solucin para dar un PbS
precipitar con el Grupo II.
BIBLIOGRAFA
JOHN ALEXANDER J. Y OTROS; La qumica en el laboratorio; Harcourt Brace
Jovanovich; 1976; EEUU.