m Lead (II), mercury (I), and silver (I) ions are

precipitated as chlorides
m Tungsten and thallium may also be included
m Forms precipitates in acid solution containing
chloride ion
m Form sparingly soluble compounds with
chloride ion
m Represented by the following equations:
Pb2+(aq) + 2 Cl- (6M HCl) ĺ PbCl2 (s)
Hg2+(aq) + 2 Cl- (6M HCl) ĺ Hg2Cl2(s)
Ag+ (aq) + Cl- (6M HCl) ĺ AgCl(s)
=

   

 It does not introduce cations that would interfere

with analysis

2 It creates/ maintains an acidic solution

-the hydroxides or oxides would precipitate if
alkaline
-if not strongly acidic, oxochlorides of bismuth and
antimony will also precipitate
=    
   

 Too much chloride ions lead to the formation of

stable chloride complexes of other cations

2 Too much chloride ions lead to the formation of

soluble chloride complexes
-Formation of chloro complexes that would
redissolve precipitates
ï   


m Partially separated from mercurous chloride

and silver chloride because of its increase in
solubility in hot water

m
ot all are precipitated, may remain as white

residue

 

m jetected by its reaction with chromate ion in
aq HOAc forming the yellow ppt PbCrO4(s)
m Acetic acid is added because it reduces the
concentration of CrO42- so other chromates
will not ppt
m Addition of
aOH produces soluble HPbO2-
and the reaction reverses and PbCrO4(s) is
reformed
@ 
Reaction:
Pb2+ (aq) + CrO42-(aq) ĺ PbCrO4(s)

Reaction2:
PbCrO4(s) + 3 OH(aq) ļ HPbO2-(aq) + CrO42-(aq) + H20

 


m Relies on disproportionation of Hg2+ to

(aq)

elemental mercury and mercury (II)

ï   

m Concentration is lowered by formation of
sparingly soluble white mercury(II)
amidochloride
" due to the direct reaction of mercury(I) [or
mercury(II)] ions with ammonia molecules
m Mercury(I) disproportionates in alkaline
solutions
" Finely divided black elemental mercury is formed
@ 

Hg2Cl2(s) + 2
H3(aq) ĺ Hg0(l) + Hg
H2Cl(s) +

H4+(aq) + Cl-(aq)

ï 
m ïilver ion is now present as the diammine
complex [Ag(
H3)2]+
m This also has ammonium ion from the
ionization of
H3 if acid is added, OH-
decreases, lowering ammonia concentration
" This destroys the diammine complex and
increasing the concentration of Ag+
" AgCl reprecipitates
m Aqua regia ( part H
O3 + 3 parts HCl ) is
needed to dissolve the ppt when there are
large quantities of Hg22+ present
" Provides both oxidizing agent (H
O3) and
complexing agent (HCl)
@ 
Reaction:
2 Hg
H2Cl(s) + 6 Cl-(aq) + 2
O-3(aq) + 4 H3O+(aq)
ĺ 2[HgCl4]2-(aq) + 2
O(g) + 2
2(g) + 8H2O

Reaction2:
3 Hg(l) + 2 Cl-(aq) + 2
O-3(aq) + 8 H3O+(aq)
ĺ 3[HgCl4]2-(aq) + 2
O(g) + 2H2O
Reaction3:
3 Ag(s) + 6 Cl-(aq) +
O-3(aq) + 4 H3O+(aq)
ĺ 3[AgCl4]-(aq) +
O(g) + 6 H2O
m Äarium, ïtrontium, Calcium, and Magnesium
ions are precipitated as carbonates
m Alkaline earth family
m Colorless except when anion is colored
m Ions are so chemically similar that flame
tests are used
m Magnesium carbonate is somewhat more
soluble than other carbonates
" maybe kept in solution by increasing ammonium
concentration
m Represented by the following equations:
Äa2+(aq) + CO32+(aq) ĺ ÄaCO3(s)
ïr2+(aq) + CO32+(aq) ĺ ïrCO3(s)
Ca2+(aq) + CO32+(aq) ĺ CaCO3(s)
Mg2+(aq) + CO32+(aq) ĺ MgCO3(s)
m ïince it is difficult to prevent precipitation of
MgCO3, it is then encouraged Its
precipitation is formed in two ways:
 Ammonium ion concentration is kept low
by strong heating of the centrifuge
remaining from the group 3 cations
2 The group precipitate is formed from an
alcohol-water solution in which all alkaline
earth carbonates are soluble
m Carbonates are volatile compounds

  
m Äarium ± lime green
m ïtrontium ± crimson
m Calcium ± brick red
m Äarium ion is precipitated from the HOAc
solution as the yellow chromate:
ÄaCO3(s) + CrO42-(aq) ĺ ÄaCrO4(s)
m Presence of HOAc decreases the
concentration of the the chromate ion by
converting it to the orange dichromate ion
" ¬eeps chromate ion concentration low enough
so ïrCrO4(s) does not ppt
m The presence of barium ion is confirmed
observing green flame test color

@ 
Reaction:
m =hen sulfate ion is added to solution
containing strontium and calcium ions,
strontium sulfate ppt
" Calcium sulfate does not due to formation of
disulfatocalcate(II) ion
" Triethanolamine also forms a stable complex
with the calcium ion
m strontium sulfate is treated with
a(CO3)2 to
ïrCO3
m ïolid ïrCO3 is dissolved in HCl to produce
ïrCl2 for flame testing
m The oxalate in the HOAc medium will ppt Ca
oxalate, but not Mg due to the formation of
the bisoxalatomagnesate(II) ion
" This does not necessarily mean that Ca is
present
m Ca ppt slowly
To enhance it :
 Adjust the volume of the solution before
(
H4)2C2O2 is added
2 The ppt is formed from a 50% alcohol
solution
3 Cooling the solution

m Ca oxalate is dissolved in HCl to form

CaCl2 which forms a brick red flame
m Mg ion is ppt from ammoniacal solution as
Mg ammonium phosphate
m This is dissolved with dilute HCl forming the
Mg ion
m The ion is reprecipitated as Mg(OH)2
" This is hard to detect so Mg reagent, a
-
nitrobenzeneazoresorcinol is added to form a
³blue lake´