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Abstract

In this experiment, a semi-micro qualitative analysis scheme based on selective precipitation,


coordination, acid-base, and redox chemistry, was used to separate and identify metal ions in an
unknown aqueous mixture. With simultaneous tests conducted on a control sample containing
Ag+ Hg22+, Mn2+, Fe3+, Ni2+, Cr3+, Zn2+, positive results confirmed the presence of Ag+, Mn2+, Fe3+,
Ni2+, Zn2+ in unknown #5.

Introduction
Different from quantitative analysis, which determines the amount of certain
components
in a sample, qualitative analysis allows for the separation
and identification of chemical species in a sample. It is based on selective
precipitation, PH control, complex ion formation, and redox reactions to
isolate and confirm the presence of ions in solution. Qualitative analysis has
a wide range of application on a variety of things including drinking water
(2). For example, qualitative analysis was used to test the Calcium hardness,
concentration of choloride, and Alkalinity of drinking water in Pakistan.
In this experiment, qualitative analysis was used to identify the presence of
Ag+ Hg22+, Mn2+, Fe3+, Ni2+, Cr3+, Zn2+ in an unknown solution.
Ag+ can be precipitated by Cl- and form a white precipitate.
Ag(NH3)2+ (aq) + 2H+ + Cl- (aq) AgCl (s) + 2NH4+
Hg22+ can also be precipitated by Cl- and form a white precipitate. The precipitate Hg2Cl2 can react
with NH3 and form a gray precipitate HgNH2Cl.
Hg22+ (aq) + 2 Cl- (aq) Hg2Cl2 (s)
Hg2Cl2 (s) + 2 NH3 Hg + HgNH2Cl + NH4+ + ClMn2+ is confirmed by the addition of NaBiO3 into MnO2. The product MnO4 is purple.
Mn2++ 2 OH- Mn(OH)2
Mn(OH)2 + H2O2 MnO2 + 2H 2 O
2 MnO 2 (s) + 3 BiO3-(aq) + 10 H+(aq) 2 MnO4 (aq) + 3 Bi3+(aq) + 5 H 2 O (l)
Fe3+ can be precipitated with the addition of NH4SCN.
Fe3+(aq) + 6 NH4SCN (aq) Fe(SCN)63- (aq) + 6 NH4+(aq)
Ni2+ can be precipitated with the addition of ammonium and dimethylglyoxime solution.
Ni2+ + 6 NH3 Ni(NH3)62+

2 (CH3)2C2(NOH)2 + Ni(NH3)62+ 2 NH4+ +4 NH3 + Ni(C4H7N2O2)2

Cr3+ can be precipitated with the addition of BaCl2.


Cr(OH)4- + 3 H2O2 CrO42- + 8H 2 O
CrO42- + BaCl2 BaCrO4 + 2 ClZn2+ ion can be precipitated with K4Fe(CN)6.
Zn2+ + 4 OH- Zn(OH)42Zn(OH)42- (aq) + 4 HCl(aq) Zn2+(aq) + 4 Cl- (aq) + 4 H2O(l)
3 Zn2+ (aq) + 2 K4Fe(CN)6 (aq) Zn3K2[Fe(CN)6]2(s) + 6 K+(aq)

Experimental
As described in the CHEM 7L Laboratory Manual (1), all tests were run on
both unknown sample and a control sample (sometimes colloquially called a
known). The control sample contains all ions that need to be analyzed. All
samples were precipitated and separated from supernatant by
centrifugation. The color of the precipitate was observed to determine if a
particular ion exists. In procedure 1, 6 drops of water and 4 drops of 3M HCl
were added to 10 drops of group A control sample that contains Ag+ and Hg22+
and 10 drops of the unknown respectively. Then, the samples were
centrifuged. Precipitates in both samples were separated from supernatants
and the supernatant in the unknown was transferred to a test tube for further
analysis. In procedure 2, the precipitates were washed with 1 drop of 3 M
HCl and 5 drops of water, centrifuged, and then separated from supernatant.
About 15 drops of 15 M NH4OH was added to both samples. Then gray
precipitates of Hg22+ were again separated from supernatant after
centrifuging. In procedure 3, 6 M HNO3 was added to the supernatant to
confirm Ag+. Subsequently, in procedure 4,10 drops of 6 M NaOH was
added to a solution containing a mixture of some or all of the following ions Mn2+, Fe3+, Ni2+, Cr3+, Zn2+, which was the supernatant separated in procedure 1.
Group B control sample was used as well. In procedure 5, 7 drops of 6%
H2O2 were added to the solutions while heating and stirring. The
supernatants and precipitates were separated. In procedure 6, 5 drops of 6
M H2SO4 were added to a precipitate containing a mixture of some or all of
the following ions - Mn2+, Fe3+, Ni2+, and the supernatant that may contain Fe3+, Ni2+
and precipitate that should be MnO2 separated. In procedure 7, 20 drops of
6M HNO3 were added to MnO2 precipitates. Following, solid NaBiO3 was
added. After centrifuging, purple solutions indicate the presence of Mn2+. In
procedure 8, 3 drops of NH4SCN was added to the supernatant from

procedure 6 to confirm the existence of Fe3+. In procedure 9, 5 M NH4OH was added to


the supernatant from procedure 6 until basic, and then ((CH 3)2C2(NOH)2) solution was dropped to indicate
the presence of Ni2+. In procedure 10, to confirm Cr3+ 0.2 M BaCl2 was added to a solution from
procedure 5, and the supernatant and precipitate separated. In procedure 11, 6 HCl was added to the
supernatant from the last step which may contain Zn2+, and then 0.2M K4Fe(CN)6 added. After the
formation of a light bluish precipitate, the precipitates were separated and dissolved with the addition of
6M NaOH. 0.5ml water and 6M HCl were added dropwise and an off-white precipitate reforms.

Results
In this section, reagents added, reactions in different procedures, possible
ions including Ag+ Hg22+, Mn2+, Fe3+, Ni2+, Cr3+, Zn2+ present in supernatant and
precipitates in the end of each step, and all observations are shown below.
All aforementioned data are present in the two tables below. Table 1 is for
group A known that contains Ag+ and Hg22+. Table 2 is for group B Known that contains
Mn2+, Fe3+, Ni2+, Cr3+, Zn2+. Potential ions are bracketed. Ions confirmed are bold. Reactions are
possible reactions that may happen.
Table 1. Reagents, reactions, potential ions present and confirmed, and
observations for Group A known
Proce
dure

#1

#2

#3

Reagents
added

4 drops of
3M HCL
and 6
drops of
water
15 M
NH4OH
6 M HNO3

Reaction

ions in the known


Sup
erna
tant

Hg22+ (aq) + 2 Cl- (aq)


Hg2Cl2 (s)
Ag+ (aq) + Cl- (aq)
AgCl (s)
AgCl (s) + 2 NH3
Ag(NH3)2++ Cl- (aq)
Hg2Cl2 (s) + 2 NH3 Hg
+ HgNH2Cl + NH4+ + ClAg(NH3)2+ (aq) + 2H+ +
Cl- (aq) AgCl (s) +
2NH4+

Observatio
n

Precipi
tate
White
AgCl
Hg2Cl2 precipitate

ions in the unknown


Supern Preci
atant pitat
e
(AgCl
Hg2Cl2
)

Ag(N
H3)2+

Hg
HgNH2
Cl

Gray
precipitate

AgCl

White
precipitate

(Ag(NH
+
3)2 )

Observa
tion
White
precipit
ate

Gray
Hg
HgNH precipit
ate
2Cl

Table 2. Reagents, reactions, ions present, and observations for Group B


known
Proc
edur
e

Reagents
added

#4

10 drops of
6M NaOH
(excess)

Reaction

Fe3++ 3 OH-
Fe(OH)3
Mn2++ 2 OH-
Mn(OH)2

ions in the
known
Supe Precipit
rnata ate
nt
Zn(O
Mn(OH)2
H)42Fe(OH)3
Ni(OH)2
Cr(OH

ions in the unknown

Observ
ation

Supernat
ant

Precipit
ate

Observ
ation

Tan
precipi
tate,
Colorle
ss
solutio
n

Cannot
determin
e

Cannot
determ
ine

red
precipit
ate,
Colorle
ss
solutio
n

MnO2
Fe(OH)3
Ni(OH)2

black
precipi
tate
yellow
solutio
n

(Zn(OH)42)

(MnO 2
Fe(OH)3
Ni(OH)2)

MnO2

black
precipi
tate

Fe3+
Ni2+

MnO 2

Brown
precipit
ate
Colorle
ss
solutio
n
Brown
precipit
ate

)4-

Ni2++ 2 OH-
Ni(OH)2
Cr3+ + 4 OH-
Cr(OH)4Zn2+ + 4 OH-
Zn(OH)42#5

#6

7 drops of
6% H2O2

Mn(OH)2 + H2O2
MnO2 + 2H 2 O
Cr(OH)4- + 3 H2O2
CrO42- + 8H 2 O

5 drops of 6
M H2SO4

2 Fe(OH)3+ 3H2SO4 Fe3+


Ni2+
2 Fe3+ + 3
SO42- + 6 H2 O

Zn(O
2-

H)4
CrO42-

#7

#8

#9

#10

#11

Ni(OH)2 + H2SO4
Ni2++ SO42- +
2 H2O
20 drops of
2 MnO2 (s) + 3
6M HNO3 and BiO3-(aq) + 10
NaBiO3
H+(aq) 2
MnO4-(aq) + 3
Bi3+(aq) + 5
H2O (l)
3 drops of
Fe3+(aq) + 6
NH4SCN
NH4SCN (aq)
Fe(SCN)63- (aq)
+ 6 NH4+(aq)
5 M NH4OH to
Ni2+ + 6 NH3
basic
5 drops of
(CH3)2C2(NOH)2

Ni(NH3)6
2 (CH3)2C2(NOH)2 +
Ni(NH3)62+ 2

8 drops of 0.2 M
BaCl2

NH4+ +4 NH3 +
Ni(C4H7N2O2)2
CrO42- + BaCl2
BaCrO4 + 2 Cl-

6 HCl to acidic
6 drops of 0.2M
K4Fe(CN)6
5 drops of 6M
NaOH
8 drops of 6M
HCl

MnO2

Ni2+
Fe(S
CN)63

green
solutio
n
Purple
solutio
n

MnO 2

Red
solutio
n

Ni2+
Fe(SCN)63

green
solutio
n
Purple
solutio
n

Fe3+

Ni(C4H7
N2O2)2

Pink
precipi
tae

Fe3+

Zn(O

BaCrO4

Yellow
precipi
tate
white
precipi
tate
yellow
solutio
n
Blue
precipi
tate

(Zn(OH)42)

2+

2-

H)4

Zn(OH)42- (aq) + 4
HCl(aq) Zn2+(aq)
+ 4 Cl- (aq) + 4
H2O(l)
3 Zn2+ (aq) + 2
K4Fe(CN)6 (aq)
Zn3K2[Fe(CN)6]2(s)
+ 6 K+(aq)

Zn3K2[Fe(
CN)6]2(s)

Ni(C4H7
N2O2)2

White
precipit
ate
clear
solutio
n

Zn3K2[Fe(
CN)6]2(s)

Discussion
The presence of Ag+, Mn2+, Fe3+, Ni2+, Zn2+ are confirmed. Although the presence of Zn2+ is
confirmed, the color of Zn3K2[Fe(CN)6]2(s) precipitate is not exactly off-white to green probably due to
contamination caused by inaccurate operation.

Pink
precipit
ae

Blue
precipit
ate

Conclusion
The application of Qualitative Analysis performed in this experiment is
limited on solutions that may contain a narrow set of well-studied ions. It can
be hardly used to determine the composition of a totally unknown solution.

Reference
(1) Berniolles, S. Gravimetric Analysis. CHEM 7L Laboratory Manual, 3 rd Edition:
Hayden-McNeil: Plymouth, MI. 2014; pp 85-96
(2) Anwar Khalid, Amir Haider Malik, Amir Waseem, Shazmeen Zahra, Ghulam Murtaza Qualitative
and quantitative analysis of drinking water samples of different localities in Abbottabad district,
Pakistan, International Journal of the Physical Sciences Vol. 6(33), 9 December, 2011; pp. 7480 7489

Reflection
In this experiment, I learned that even in qualitative analysis which does not
have much requirement for precise operation, it is important to avoid
contamination. Otherwise the color of precipitate may not be exactly as
expected. Also it is important to clearly label different samples to avoid
confusion, especially when there are a lot of them.
Moreover, in qualitative analysis, it is very important to know the possible
reactions between chemicals, colors of solutions and precipitates. Therefore
when I want to determine the composition of an unknown solution, it might
not be a good idea to use qualitative analysis. However, in situations such
that the solution is possibly a mixture of several well-studied chemicals, it is
an easy way to use qualitative analysis.