Experiment 2

Qualitative Analyis: Cations- Group 1

I. Objectives
At the end of the experiment, the students will be able to:

● Know the precipitation reactions.

● Know the precipitate formed after the experiment.

● Know how reactants exchange ions to form a precipitate.

II. Materials
● Ag+ (aq) + Cl-(aq) → AgCl(s) White caseous precipitate
● Hg22+(aq) + 2 Cl-(aq) → Hg2Cl2(s) White crystal precipitate
● Pb2+(aq) + 2 Cl-(aq) → PbCl2(s) White amorphous precipitate
+ 2-
● Ag (aq) + CrO4 (aq) → Ag2CrO4(s)     Red precipitate
● Hg22+(aq) + CrO42-(aq) → Hg2CrO4(s)   Yellow-brown precipitate
● Pb2+(aq) + CrO42-(aq) → PbCrO4(s)       Yellow precipitate

III. Apparatus
● 8 Small test tubes
● Bunsen burner
● Glass Stirring Rod
● Beaker
● Red Litmus Paper
● Blue Litmus Paper
● Centrifuge
● Dropper Pipets
● Wash Bottle filled with deionized water
Introduction

  In qualitative analysis, the ions in a mixture are separated by selective precipitation. Selective
precipitation involves the addition of a carefully selected reagent to an aqueous mixture of ions,
resulting in the precipitation of one or more of the ions, while leaving the rest in solution. Once
each ion is isolated, its identity can be confirmed by using a chemical reaction specific to that
ion. Cations are typically divided into Groups, where each group shares a common reagent that
can be used for selective precipitation.

  If a dilute solution of HCl is added to a solution containing ALL of the common metal ions, a
white precipitate will be formed.  This precipitate will contain AgCl(s), Hg2Cl2(s), and PbCl2(s). 
If this solution is centrifuged to collect the solid material at the bottom of a test tube, the
supernatant liquid can be removed (decanted).  The remaining solid can be washed with distilled
water so that the ONLY metal ions that remain are Ag+, Hg22+, and Pb2+.  The reactions that occur
are:
Ag+(aq) + Cl-(aq) -> AgCl(s)
Hg22+(aq) + 2 Cl-(aq) -> Hg2Cl2(s)
Pb2+(aq) + 2 Cl-(aq) -> PbCl2(s)

The reactions are conducted in acidic solution, to avoid the possibility that these and other metal
ions might be precipitated as hydroxides or oxides.  This reaction of this group of ions with
chloride ions allows them to be separated from all other metal ions.  Silver, mercurous, and
plumbous ions have been designated as the Group I Cations.

    If addition of dilute HCl to a solution of metal cations results in a precipitate, this is conclusive
evidence that at least one - and possibly all - of the Group I Cations were are present in the
original solution.  Additional tests are necessary to determine which of these three cations are
present in the precipitate. While these three chlorides are relatively insoluble in cold water, lead
chloride is found to be quite soluble in hot water.  Therefore, cold water may be added to the
precipitate containing any or all of the three chlorides without any of them re-dissolving. 
However, heating this mixture will cause lead chloride to dissolve, if any is present.  While still
hot, the tube can be centrifuged and the supernatant solution can be decanted into another test
tube.  If any lead ion is present, addition of cold HCl solution to the liquid will cause white lead
chloride to precipitate.
    Silver ion has a special property which distinguishes it from the other two cations of Group I. 
When mixed with ammonia in basic solution, complex ions are formed (these complexes are not
formed in acidic solution in which the ammonia exists as ammonium ion):

Ag+(aq) + NH3(aq) = Ag(NH3)+(aq)

Ag(NH3)+(aq) + NH3(aq) = Ag(NH3)2+(aq)

The formation of these complex ions lowers the concentration of free silver ion, allowing
precipitated silver chloride to dissolve:

AgCl(s) + x NH3(aq) -> Ag(NH3)x+(aq)  + Cl-(aq)  ;   x = 1 to 2  .

Thus, when the Group I cations are precipitated with HCl, ammonia may be added to the
precipitate until litmus indicate that the solution is basic.  If the precipitate contains silver ion, it
will dissolve and may be removed from the others by centrifuging and decanting the supernatant
solution.  Addition of HCl to this solution until litmus indicates that the solution is acidic will re-
precipitate silver ion, if present. Mercurous chloride may be distinguished from the other two
Group I chlorides by its ability to resist re-dissolving by either heating or the addition of
ammonia. Once the Group I cations have been separated by heating and the addition of
ammonia, their presence(s) may be confirmed by their precipitates with chromate ion:

Ag+(aq) + CrO42-(aq) -> Ag2CrO4(s)     Red precipitate

Hg2 (aq) + CrO42-(aq) -> Hg2CrO4(s)   Yellow-brown precipitate
2+

Pb2+(aq) + CrO42-(aq) -> PbCrO4(s)       Yellow precipitate

 
In this virtual laboratory, you will explore the precipitation reactions, reactants exchange ions to
form a precipitate. A precipitate is an insoluble ionic compound that does not dissolve in water.
If a possible product is insoluble, a precipitation reaction should occur. We can predict whether
such compound will form by consulting the solubility rule. Kindly visit this link in order to start
your learning journey (http://web.mst.edu/~gbert/qual/qual.html).

V. GUIDE QUESTIONS:

1. Write the balanced equations for the different reactions of the known.

BALANCED EQUATION UPON ADDING HCL

Ag+(aq) + HCl- (aq) → AgCl(s)+ H(aq)

Ag-1 Ag-1
H-1 H-1
Cl-1 Cl- 1
Pb(aq)+2HCl(aq) → PbCl2(s)+ H2(aq)
Pb- 1 Pb-1
H- 2 H- 2
Cl-2 Cl-2
Hg2(aq)+2HCl(aq) → Hg2Cl(s)+H2(aq)
 Hg- 2 Hg- 2
H- 2 H- 2
Cl- 2 Cl- 2
BALANCED EQUATION UPON ADDING NH3

AgCl(s) +2NH3(aq) → Ag(NH3)2(aq)+ Cl(aq)

Ag- 1 Ag-1
Cl- 1 Cl- 1
NH- 6 NH- 6

Hg(2) Cl2(aq)+ 2NH3(aq) → Hg(aq)+HgNH2Cl(aq)+NH4(aq)+Cl(aq)

Hg-2 Hg-2
Cl- 2 Cl- 2
NH- 6 NH- 6
PbCl2(s)+2NH3(aq) →Pb(aq)+NH2Cl(aq)+ NH4(aq)+Cl(aq)
Pb – 1 Pb-1
Cl- 2 Cl- 2
NH- 6 NH- 6
BALANCED EQUATION UPON ADDING Na2CrO4

2Ag(aq)+NaCrO4(aq) →Ag2CrO4(s)+2Na(aq)
Ag- 2 Ag- 2
Na- 2 Na- 2
Cr- 1 Cr- 1
O- 4 O- 4
Pb(aq)+Na2CrO4(aq) → PbCrO4(s)+2Na(aq)
Pb- 1 Pb- 1
Na- 2 Na- 2
Cr- 1 Cr- 1
O- 4 O- 4
Hg2(aq)+Na2CrO4(aq) →Hg2CrO4+2Na(aq)
Hg- 2 Hg- 2
Na- 2 Na- 2
Cr- 1 Cr- 1
O- 4 O- 4

2. Write the net ionic equations for the different reactions of the known.
NET IONIC EQUATION UPON ADDING HCl
2Ag+(aq) + HCl- (aq2) → 2AgCl(s)+ H2+(aq)
Hg2++Cl- →Hg2Cl2
Pb+(aq)+2Cl→ PbCl2(s)

NET IONIC EQUATION UPON ADDING NH3

AgCl(s)+2NH3 (aq) →(Ag(NH3)2)(aq)+ Cl-(aq)
 Hg2Cl2(s)+2NH3(aq) → Hg(s)+HgNaNH2Cl-(aq)
PbCl2(s)+2NH3(aq) →Pb(aq)+NH2Cl(aq)+NH4(aq)+Cl-(aq)

BALANCED EQUATION UPON ADDING Na2CrO4

2Ag+(aq)+Na+Cr+O4(aq) →Ag2CrO4(s)+2Na+(aq)
Pb(aq)+Na2CrO4(aq) → PbCrO4(s)+2Na(aq)
Hg2+(aq)+Na+2Cr+O-4(aq) →Hg2CrO4+2Na+(aq)

3. Based on your results, what are the chemical names of the precipitate formed?

● Silver Chloride → White caseous precipitate

● Mecury Chloride → White Crystal precipitate
● Lead Chloride → White amorphous precipitates
● Silver chromate → Red precipitate
● Mercury Chromate → Yellow Brown precipitates
● Lead Chromate → Yellow precipitate

4.  In order to identify Ag+, the solution must be acidified before a precipitate can form why?

It is needed to acidify so that metals ions will remain. A reaction will occur when HCI is
added to the metal ions. If a dilute solution of HCl is added to a solution containing all of
thecommon metal ions, a white precipitate will be formed. This precipitate will contain AgCl(s),
Hg2Cl2(s), and PbCl2(s). The solution is centrifuged to collect the solid material; the excess
liquid will be removed. The remaining solid can be washed with distilled water so that the only
metal ions that remain are Ag+, Hg22+, and Pb2+. The reactions that occur are:
Ag+(aq) + Cl-(aq) -> AgCl(s)

Hg22+(aq) + 2 Cl-(aq) -> Hg2Cl2(s)

Pb2+(aq) + 2 Cl-(aq) -> PbCl2(s)

When Silver ion is mixed with ammonia in basic solution, complex ions are formed (these
complexes are not formed in acidic solution in which the ammonia exists as ammonium ion):

Ag+(aq) + NH3(aq) = Ag(NH3)+(aq)

Ag(NH3)+(aq) + NH3(aq) = Ag(NH3)2+(aq)

The formation of these complex ions lowers the concentration of free silver ion, allowing
precipitated silver chloride to dissolve:

AgCl(s) + x NH3(aq) -> Ag(NH3)x+(aq) + Cl-(aq) ; x = 1 to 2 .

Thus, when the Group I cations are precipitated with HCl, ammonia may be added to the
precipitate until litmus indicate that the solution is basic. If the precipitate contains silver ion, it
will dissolve and may be removed from the others by centrifuging and decanting the supernatant
solution. Addition of HCl to this solution until litmus indicates that the solution is acidic will re-
precipitate silver ion, if present.

Mercurous chloride may be distinguished from the other two Group I chlorides by its
ability to resist re-dissolving by either heating or the addition of ammonia.

Once the Group I cations have been separated by heating and the addition of ammonia,
their presence(s) may be confirmed by their precipitates with chromate ion:

Ag+(aq) + CrO42-(aq) -> Ag2CrO4(s) Red precipitate

Hg22+(aq) + CrO42-(aq) -> Hg2CrO4(s) Yellow-brown precipitate

Pb2+(aq) + CrO42-(aq) -> PbCrO4(s) Yellow precipitate

V. Conclusion

In conclusion, adding reagent causes one ion to precipitate while leaving others in
solution. The chloride of Pb2+,Hg22+ and Ag+ are all insoluble in cold water. Group 1
cations will be separated when heated and precipitate will form when the metal ions
(Ag+, Hg22+ and Pb2+) are added with a dilute solution Hydrochloric Acid (HCL).
Furthermore, metal ions will also form a precipitate when it is added with chromate
ion.

References:
Bertrand, G.L. (2003). Qualitative Analyis: Cations- Group 1. Retrieved October 5, 2020, from
http://web.mst.edu/~gbert/qual/qual.html.
Bauer, R., Birk, J., & Marks, P. (2016). Introduction to Chemistry. 4 th edition. McGraw Hill
Education. New York.
https://chem.libretexts.org/Bookshelves/Ancillary_Materials/Laboratory_Experiments/Wet_Lab_
Experiments/General_Chemistry_Labs/Online_Chemistry_Lab_Manual/Chem_12_Experiments/
06%3A_Qualitative_Analysis_of_Group_I_Ions_(Experiment). Retrieved October 5, 2020.