CHEM 1412 Lab Qualitative Analysis 56

Qualitative Analysis of Cations

Short Overview
The most common cations have been placed into five groups based upon solubility in aqueous solutions
when different reagents are added. The reactions which occur are useful in identifying the presence of
these cations in unknown samples. The process of identifying the cations is called qualitative analysis.
The purpose of this experiment is to identify which cations are present in unknown solutions.
A data sheet was not prepared or this e!peri"ent# so you "ust re$ord your observations in the lab
noteboo% as you do the e!peri"ent& 'his e!peri"ent will last several laboratory periods&
A. Theory
Read Sections !.6 " !.! # pp. !56"!6$% and Table &. #p. '!% in your textbook #Chemistry:
The Central Science( $
th
)d.( *rown( +e,ay( *ursten( - *urdge%. .ou should also refer to
Qualitative Analysis and the Properties of Ions in Aqueous Solutions, '
nd
)d.( Slowinski -
,asterton( a book which has been placed on reserve at .eary +ibrary.
The separation scheme used to identify the cations is based on their reactions. The five groups into which
the cations are placed are as follows/
Group Property Ions
I Insoluble chlorides Ag
+
Pb
2+
Hg2
2+
II Acidinsoluble sulfides Cu
2+
!i
"+
Cd
2+
Pb
2+
Hg
2+

#b
"+
#n
2+
#n
$+

III !aseinsoluble sulfides and
hydro%ides
Al
"+
Cr
"+
Co
2+
&e
"+
'n
2+

(i
2+
)n
2+

I* Insoluble phosphates !a
2+
Ca
2+
'g
2+
#r
2+

* #oluble salts +i
+
(a
+
,
+
(H$
+
0 series of flowcharts are used to summari1e the steps involved in the procedure of separating and
identifying the ions. These flowcharts are given at the end of the procedure.
0lthough more ions are listed above( we will concentrate on the separation of ten cations. These cations
will provide you with an understanding of the process of qualitative analysis and allow you to perform the
experiment in the alloted time.
The cations you will learn to identify are/
Ag
+
Pb
2+
Cu
2+
&e
"+
'n
2+
)n
2+
!a
2+
(a
+
,
+
(H$
+
CHEM 1412 Lab Qualitative Analysis 5!
!. Che-icals and Apparatus
Chemicals/ 2ater
Solutions/ $.$ M solutions of nitrate salts of the cations
various reagents called for by the experiment
Apparatus/ test tubes( eyedroppers( test tube brushes( stirring rods( litmus paper( 0+30456
paper( centrifuges( hot plates( &$$"m+ beakers #for hot water baths%
Safety Equipment/ goggles( gloves( hood.
O!ectives: 5n this experiment you will learn to/
. observe the results of precipitation reactions and color changes during the
separation of a mixture of ions.
'. observe different color flames associated with the different metal ions.
7. identify ions present in an unknown sample mixture by comparing the results
with those of the known solutions.
C. Procedure
(O'E) *nless otherwise indi$ated# all rea$tions should be peror"ed usin+ the "ediu",si-ed
test tubes# 1. ! 1// ""&
. 8btain 5 m+ each of the 9:roup 5 - 55;( 9:roup 555 - 5<;( and 9:roup <; solutions containing
the ten ions in approximately $.$ M concentrations in three 6"inch test tubes. +abel the test tubes
according to the solutions.
'. =se the :roup < solution to identify the ammonium ion first.
Identification of a--oniu- ion. (H$
+
Salts of ammonium ions are extremely soluble in aqueous solutions. Therefore( whenever possible(
determination of the presence or absence of ammonium ion should be done at the beginning of a
qualitative analysis scheme. This will allow you to use ammonium salts as reagents whenever possible
without affecting your results.
7. To determine the presence of ammonium ion( take m+ of solution and place in a 5$"m+ beaker.
0dd 5 drops of M >a8? to the solution.
&. 2et a piece of red litmus paper with water. @lace the litmus paper on the bottom side of a watch
glass.
CHEM 1412 Lab Qualitative Analysis 5A
5. 4over the beaker with the watch glass( so that the litmus paper can react with the fumes generated
by heating the solution slowly. #68 >8T *85+ T?) S8+=T58>.% The ammonia gas generated
by the ammonium ion will cause the damp litmus paper to turn blue. This represents a positive
test for the ammonium ion.
The reactions which occur in solution are/
#% >?&
B
B 8?
"
>?7 "#$ B ?'8 "#$
#'% >?7 "#$ B ?'8 "l$ >?&
B
B 8?
"

#7% 8?
"
B red litmus

lue litmus
CHEM 1412 Lab Qualitative Analysis 5C
Identification of Group I Cations /Chart 01
6. 5n a $"cm test tube( place ' m+ of the 9:roup 5 - 55; solution which you obtained earlier. 0dd
$ drops of 6 M ?4l. Stir well and centrifuge. R),),*)R T8 =S) 0 T)ST T=*) 25T? 0>
)D=0+ <8+=,) 8E 20T)R T8 *0+0>4) T?) 4)>TR5E=:).
!. 0dd three additional drops of 6 M ?4l to the test tube. 5f additional solid forms( centrifuge
again. Repeat this step until no additional precipitation is observed.
A. 4entrifuge the test tube again. Then use an eyedropper to transfer the supernatant liquid above the
solid to another test tube. This solution contains the 4u
'B
ion. +abel this as 9:roup 55;( and set the
test tube aside.
C. The precipitate from step ! is a mixture of 0g4l and @b4l'. 0dd ' m+ of distilled water to the
precipitate. Stir and heat the test tube in a hot"water bath for 7 minutes. 4entrifuge and transfer
the liquid to a clean test tube.
$. 0dd ' drops of 6 M acetic acid and 5 drops of $.$ M 3'4r8& to the liquid. 'he presen$e o a
yellow pre$ipitate $onir"s the presen$e o lead# 0b
21
& 6iscard the contents of the test tube in
the chromate waste container. Rinse the test tube twice with small amounts of water and add the
rinses to the chromate waste.
. 2ash the precipitate from step C with 7 m+ of distilled water. 4entrifuge and test for @b
'B
.
4ontinue until no positive test for lead is observed.
'. 8nce the lead is absent( wash the solid #A+Cl% with ' m+ of water. 6iscard the washes. Then add
' m+ of 6 M >?7 to the solid. The 0g4l will dissolve and form the diamminesilver#5% complex
ion F0g#>?7%'
B
G.
7. 0dd ' m+ of 6 M ?>87 to the solution. A white to o,white solid $onir"s the presen$e o
silver ion# A+
1
&
6iscard the silver solid in the 90g4l waste; container.
Identification of Group II Cations /Chart 21
&. The solution in the test tube from step C contains the 4u
'B
ions. To this solution( add m+ of 7H
?'8'. *oil the solution down to a volume of about m+. >ow add 6 M ?4l until the p? reaches
CHEM 1412 Lab Qualitative Analysis 6$
$.5. 8nce the p? has been lowered to $.5( add m+ of M 4?74S>?' #thioacetamide% to the
test tube.
5. ?eat the test tube in a *2* under a u"e hood for at least 5 minutes. The reactants will generate
?'S ( a toxic gas( in small quantities( so you should avoid breathing the fumes as much as
possible. The reaction will produce a precipitate which will get darker as heating continues.
4ontinue heating for two minutes after the color has stopped changing. @ut a cork stopper on the
test tube and cool it under the water tapI then allow the test tube stand for a minute or so before
centrifuging.
(ote) 2e$ause you have +enerated H2S# you "ust $entriu+e these sa"ples under a u"e hood&
6. 6ecant the solution above the precipitate and transfer to a clean test tube. 0dd m+ of M
>?&4l and m+ water to the precipitate and set aside.
!. 4heck the p? of the solutionI if it is below $.5( add M 4?7488>?&( ammonium acetate( to
bring the p? up to $.5. 0 brown or yellow precipitate may form. 0dd m+ of M thioacet"
amide( and heat for three minutes in the *2*. 4entrifuge and decant the liquid into a clean test
tube for future use. #>8T)/ 5f you have a general unknown that contains :roup 555( 5<( or <
cations( they will be in the solution. 5f you are only working with :roup 55 cations( you may
discard the liquid.%
A. 0dd m+ of M >?&4l and m+ water to the precipitate and combine with the precipitate of
step 6. 0dd ' m+ of M >a8? and heat with stirring for two minutes. 4entrifuge and discard
the solution. 2ash the precipitate twice with ' m+ of water and m+ of M >a8?( stir(
centrifuge( and discard the washes.
C. 0dd ' m+ of 6 M ?>87( nitric acid( to the precipitate. This will dissolve the 4uS and *i'S7
precipitates. Then add 6 M >?7 until the solution is basic to litmus. 0dd an additional $ J 5
drops of 6 M >?7. 'he presen$e o $opper ion# Cu
21
# is $onir"ed by a deep royal blue
solution&
Identification of Group III Cations /Chart "1
The identification of :roup 555 cations is determined from the solution obtained from step ! of the
procedure #during separation of :roup 55 cations from other cations%. 5f you did not have a mixture( you
should start the procedure using ' m+ of a general stock solution containing :roup 555 - 5< cations.
'$. @our ' m+ of the :roup 555 - 5< cations in a test tube. *oil the solution down to a volume of
m+. Then add m+ of M >?&4l to the solution. Swirl to dissolve any crystalli1ed salts.
CHEM 1412 Lab Qualitative Analysis 6
'. ,ake the solution basic to litmus by adding 6 M >?7I then add an additional $.5 m+. 0dd m+
M thioacetamide( stir well( and heat in a *2* under a u"e hood for 5 minutes( or at least
two minutes after the color stops changing. .ou should have formed a black solid with a yellow
solution on top.
''. 4entrifuge and separate the solid from the solution. 0dd more thioacetamide to the solution and
repeat the heating and centrifugation steps. Save the solution for analysis of the :roup 5< cations(
*a
'B
.
(ote) 2e$ause you have +enerated H2S# you "ust $entriu+e these sa"ples under a u"e hood&
'7. 2ash the precipitate twice with m+ M >?&4l( ' m+ water( and 5 drops of 6 M >?7.
4entrifuge and discard the washes.
'&. 0dd m+ 6 M ?4l and m+ water to the precipitate. ,ix thoroughly and pour into a 7$"m+
beaker. *oil gently for about one minute. 0dd m+ water( stir( and pour the slurry into a test
tube. 4entifuge and decant the liquid into a clean test tube. .
The solid material may be discarded since Ee
7B
( ,n
'B
( and Kn
'B
dissolved when the ?4l was
added.
'5. To the solution from step '&( add 6 M >a8? until it is basic to litmus( then add an additional $
J 5 drops. @our the resulting slurry into a 7$"m+ beaker and boil gently for two minutes with
stirring. 4ool to room temperature and add m+ M >a84l( sodium hypochlorite #bleach%.
Swirl for about 7$ seconds( then boilthe liquid gently( reducing the volume to about ' m+( 5f
,n
'B
is present( the foam will have a purple color. 0dd $.5 m+ of 6 M >?7( swirl for 7$
seconds( and boil for minute. Transfer to a test tube and centrifuge the solid. 6ecant the liquid
into a clean test tube. The iron and manganese ions have precipitated from solutionI the Kn
'B
ion
is in solution as Kn#8?%&
'"
.
'6. ,ake the solution acidic to litmus with 6 M ?4l. 0dd three drops ?4l in excess. Then add 5
drops of $.' M 3&Ee#4>%6( potassium ferrocyanide. A li+ht +reen pre$ipitate o
324n.56e7C(89: $onir"s the presen$e o 4n
21
&
'!. 0dd m+ water and m+ 7 M ?'S8& to the solid precipitate from step '5. Stir and heat the test
tube in the *2* for 7 minutes. 4entrifuge and decant the liquid( which contains Ee
7B
I the ,n8'
will not dissolve.
'A. 0dd ' m+ water and 5 drops of M >?&S4> to the solution. A deep ;blood red< $olor# due to
the or"ation o 56e7SC(89
.,
:# is a positive test or the 6e
.1
.
'C. 0dd m+ water( m+ 7 M ?'S8&( and m+ 7H ?'8' to the precipitate of ,n8'. The
precipitate will dissolve. Then pour m+ of the solution into a clean test tube( and add m+ 6
M ?>87 to the test tube. Einally( add $.7 " $.& g of sodium bismuthate with your spatula to the
test tube. +et the mixture stand for two minutes before centrifuging. A purple solution is due to
the presen$e o MnO4
,
and $onir"s the presen$e o Mn
21
.
CHEM 1412 Lab Qualitative Analysis 6'
Identification of Group I* 2 Group * Cations /Chart $1
7$. =se the solution from step '' to identify the presence of the :roups 5< and < cations. Transfer
the liquid to a 5$ m+ beaker and boil down to ' m+. 4entrifuge and discard any solid matter. 0dd
m+ 6M ?4l to the liquid. @our the liquid to the beaker( and boil essentially to dryness.Transfer
the beaker to the hood( and carefully heat the dry solid to drive off any ammonium salts produced
in previous steps. Stop heating when no visible smoke is being evolved.
7. +et the beaker cool to room temperature( then add ' m+ water and m+ 6 M ?4l to the beaker.
2arm gently to dissolve any remaining salts. Transfer the liquid to a test tube and centrifuge.
6ecant the liquid into a clean test tube. 6iscard the insoluble material.
7'. To the solution add m+ M #>?&%'487 and m+ 6M >?7. Stir and let stand for $ minutes.
*arium carbonate or barium hydroxide will precipitate out of solution. 4entrifuge and separate
the solution from the precipitate.
5f you have a general unknown( the >a
B
( 3
B
( and >?&
B
will be left in solution. 5dentification of
these unknowns should be done after you complete step 7&.
77. 2ash the precipitate with a few drops of M #>?&%'487 and 6M >?7. 6iscard the washes. Then
add $.5 m+ 6 M ?4l. The solid will dissolve. 0dd m+ M >a'S8&. *arium will precipitate
out as a fine white solid. Then add ' m+ $.$ M 3'4r8& and $.5 m+ 6 M >a8? to the
precipitate( with stirring. The *aS8& will be converted to *a4r8&( a yellow solid. 4entrifuge and
discard the liquid. 2ash the solid several times with water until the solution is no longer yellow.
7&. To the solid remaining after washing( add m+ 6 M ?4l and stir. The *a4r8& will dissolve and
produce an orange solution. 0dd $.5 m+ 7 M ?'S8&. A white pre$ipitate o 2aSO4 $onir"s the
presen$e o 2a
21
&
&la-e Tests Analysis of #odiu- and Potassiu-
8ne of the most common methods of identifying cations is by using a flame test. The flame color is due
to excitation of valence"shell electrons upon heating( followed by relaxation of the electrons with the
emission of photons of light.
Sodium ion can be identified by a very intense yellow"orange flame. @otassium ion is identified by a
lavender"pink flame. ?owever( if both ions are present together( the intense flame of >a
B
hides the color
of the 3
B
flame. 5t is therefore necessary to use a blue cobalt glass plate to absorb the color of the sodium
ion( so that the flame of potassium ion can be seen.
The ammonium ion will not interfere with the flame tests.
CHEM 1412 Lab Qualitative Analysis 67
75. 8btain a flame test wire from the instructor. +ight a bunsen burner and place the wire in the flame
to clean the wire. The wire will be clean when the color of the flame above the wire is blue.
'o assist in $leanin+ the wire# you "ay dip the wire in 9 M HCl beore pla$in+ the wire in the la"e&
76. 6ip the wire into a test tube containing the 9:roup <; ions. .ou should obtain a small drop of
solution in the loop of the wire. @lace the wire in the flame. .ou should observe the yellow"
orange flame of >a
B
almost immediately.
7!. Repeat step 76( except this time you should place a blue cobalt glass plate in front of your eyes.
?ere you will observe a slight color change of the flame( which will appear almost pinkish"purple
behind the cobalt glass plate.
CHEM 1412 Lab Qualitative Analysis 6&
Chart 1 below shows the separation of the :roup 5 cations 0g
B
and @b
'B
from the other cations.
Chart 1
Group II, III, IV, V

Cu
2+
Fe
3+
Mn
2+
Zn
2+
Ba
2+
Na
+
K
+
NH
4
+
Ag
+
Pb
2+
Cu
2+
Fe
3+
Mn
2+
Zn
2+
Ba
2+
Na
+
K
+
NH
4
+
HCl

AgCl
(s)
PbCl
2

(s)
H
2
O (hot)
AgCl
(s)

Ag(NH
3
)
2
+

AgCl
(s)

Pb
2+
PbCrO
4

(s)
Group I
HOAc, K
2
CrO
4

HNO
3

NH
3

white ppt confirms presence of Ag
+

yellow ppt confirms presence of Pb
2+

Continue using Chart 2
CHEM 1412 Lab Qualitative Analysis 65
4hart ' shows the separation of the :roup 55 cation 4u
'B
from the remaining cations of :roup 555( 5<( and <.
Chart 2&
Royal blue color confirms presence
of Cu
2+

CuS
(s)

H
2
O
2
HCl
thioacetamide
NaOH,
HNO
3
Cu
2+

NH
3

Cu(NH
3
)
4
2+

Continue using Chart 3

Cu
2+
Fe
3+
Mn
2+
Zn
2+
Ba
2+
Na
+
K
+
NH
4
+

Fe
3+
Mn
2+
Zn
2+
Ba
2+
Na
+
K
+
NH
4
+
CHEM 1412 Lab Qualitative Analysis 66
4hart 7 shows the separation of the :roup 555 cations Ee
7B
( ,n
'B
( and Kn
'B
from the cations of :roup 5< and <.

Chart .&

Zn(OH)
4
2-
HCl
K
4
Fe(CN)
6


K
2
Zn[Fe(CN)
6
]
2

(s)

light green
NH
3
NH
4
Cl
thioacetamide

Fe
3+
Mn
2+
Zn
2+
Ba
2+
Na
+
K
+
NH
4
+

Ba
2+
Na
+
K
+
NH
4
+

FeS
(s)
MnS
(s)
ZnS
(s)

NaOCl
NaOH NH
3

Continue using Chart 4

Fe(OH)
3 (s)
MnO
2 (s)
H
2
SO
4

Fe
3+
KSCN

Fe(SCN)
6
3+
blood red

MnO
2

(s)
H
2
SO
4
H
2
O
2

Mn
2+
MnO
4
-

purple ion
HNO
3
NaBiO
3
CHEM 1412 Lab Qualitative Analysis 6!
4hart & shows the separation of the :roup 5< - < cations *a
'B
( >a
B
( 3
B
( and >?&
B
.
B

Chart 4&


NH4
+
NH
3
(g)
Blue litmus
NaOH
red litmus,
H
2
O

BaCO
3

(s)
HCl
K
2
CrO
4
NaOH

BaCrO
4 (s)
yellow
HCl, Boil

Ba
2+
Na
+
K
+
NH
4
+

Ba
2+
Na
+
K
+

(NH
4
)
2
CO
3
NH
3

Na
+
K
+


Na
+

yellow-orange
flame

K
+

lavender
flame