Cations Separation Exp

1
Academic Year

A14

2

Contents Page
Preface 3
General instruction to the students 4
Basic tools 5
Before coming to laboratory 6
Experimental procedure 7
Preparation of the salt solution 9
Classification of cations 10
Group I 11
Report sheet 14
Group IIA 17
Report sheet 20
Group IIB 23
Report sheet 24
Group III 27
Report sheet 29
Group IV 32
Report sheet 34
Group V 37
Report sheet 39
Group VI 42
Report sheet 44
Test of ammonium 46
Report sheet 47
Scheme for identification of basic radical in mixture 48
General questions 50

Contents

3

Preface

etals are a very important part of our society and the majority of
these are not found in the metallic form in nature. The more
useful metals (including copper, nickel, zinc, etc.) occur as
positively charged ions (cations) incorporated into minerals. The
cations of the more useful metals are often mixed with an array of less valuable
cations. Separation of the cations of the desired metal from the others is a
critical step in metal production. This experiment will explore some of the
strategies used to separate (and identify) metal cations. The term analysis
means the identification of the components in a substance. When the term
qualitative is used, it means that only visual observation are required. Not
include information about the quantity of the component in question is obtained.

Qualitative analysis is possible because experience has shown that
certain chemical reactions of ions in solution are limited to at most a few kinds
of ions. Some reactions are unique to a specific ion. If we conduct an experiment
in such a way that a positive reaction is possible for only one kind of ion, we can
get a yes or no answer to the presence of the ion in question. The separation
and qualitative analysis of a large number of the common cations is based on the
selective solubilities of the compounds of the cations. Qualitative analysis is a
method used for identification of ions or compounds in a sample. In many cases,
qualitative analysis will also involve the separation of ions or compounds in a
mixture. Examples of qualitative tests would include ion precipitation reactions
(solubility tests) or chemical reactivity tests. The separation of ions is easily
achieved by taking advantage of their solubility properties. 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.

M
4

Keep your work-table clean and neat which helps one to achieve the work
quickly in the laboratory.
Record your observations, write down the readings when you make them.
Wash all glass apparatus using dilute solution of detergent.
Wash immediately the apparatus after use.
Do not turn the test tube while heating towards your neighbors.
Turn off gas both tap and water tap whenever they are not in use.
Do not attempt to perform unprescribed experiments unless specific
permission is granted by the teacher in the laboratory.
In the case of any accident like swallowing of chemicals, solutions or
splashing of acids and other chemicals in the eyes or on the body, report
to the teacher immediately.
Wash your hands thoroughly with soap before leaving the lab. If the
soap is not set out in the lab, ask your instructor for it. This hand washing
should be a normal routine at the end of each laboratory period.

General Instructions to the Students
5

Tools
Funnel
Test tube
Beaker
Filter papers
Folding filter paper
Rack of test tubes
Conical flask and
beaker
6

To prepare for the experiments, you should:
Read the experiment you will be doing.
Covering the specific analytical group you will be working with.
Make marginal notes or high-light directions which you are required to
follow. Note any specific solution preparation directions.
Study the direction for centrifuging, connected with the separation.
Study the flow chart for the analysis and understand the logic in the
chart.

BEFORE COMING TO LABORATORY
7

I. Techniques
Addition of reagents
Always use a dropper or capillary pipette when adding a small quantity of a liquid to a test
tube or other vessel. One ml is about 20 drops. If a reagent bottle has a dropper, replace it
promptly after use. Do not allow the dropper to touch the container or solution to which you
are adding the droppers contents. Do not set the dropper down on the bench top or another
surface, and be sure to return it to the right bottle. Always mix thoroughly after adding
reagent.

Precipitation
To detect the formation of a precipitate on mixing two solutions, it is essential that
both solutions be initially clear; if necessary, centrifuge to clarify. A clear solution
is transparent but not necessarily colorless.After adding a reagent to bring about
precipitation, always test for complete precipitation if the purpose is to separate one
substance from another. Suppose, for example, that a solution contains 0.10 millimole of
Ba
+2
. We add to this solution a few drops of dilute H
2
SO
4
, and the amount happens
to contain 0.08 millimole of SO
4
-2
. We have thus produced 0.08 millimole of solid BaSO
4
,
but 0.02 millimole of Ba
+2
remains in the supernatant liquid, because we did not add
enough H
2
SO
4
to precipitate all the Ba
+2
as BaSO
4
. This fact can be discovered by centrifuging
and adding another drop of reagent (dilute H
2
SO
4
in this case) to the clear supernatant. If
precipitation is complete, no additional precipitate will form. However, if insufficient reagent
was added the first time, the additional drop will cause formation of more precipitate. If more
precipitate is observed, add several more drops of reagent, centrifuge, and again test for
completeness of precipitation. Repeat until no precipitate is formed on adding reagent. After
the precipitate and supernatant are separated, the precipitate is washed by adding a few drops
of the washing reagent (usually water), mixing thoroughly with a stirring rod, centrifuging,
and removing the washings with a capillary pipette. Two or more washings are generally
necessary to prevent contamination of the precipitate. Failure to wash precipitates is one
of the most common sources of error in qualitative analysis.

EXPERIMENTAL PROCEDURE
8

Transfer of Precipitates
The easiest way to transfer a residue from one container to another is to mix the residue
with small amounts of washing liquid and pour the suspension quickly into the new
container. Repeat this two or three times to get complete transfer. For small volumes,
draw the suspension into a pipette for transfer.

Heating of solutions
To avoid excessive evaporation use a water bath. Always stir when heating test tubes. A
water bath with an aluminum test tube holder will be set up for you in your fume hood. Place
your test tubes into the pre-labeled positions and heat the water to a gentle boil.

Adjusting acidity
Always stir well when adding acid or base. To test the pH of the solution, apply a drop onto
litmus paper. Never dip the paper into the solution.

II. Available Equipment
Centrifuge
The centrifuge is used to speed up the separation of a precipitate from a liquid. When a
mixture of solid and liquid is placed in a tube and rotated at high speed in a centrifuge, the
more dense precipitate is forced to the bottom of the tube by a centrifugal force that is many
times greater than the force of gravity. After centrifuging, the supernatant, or clear liquid
above the precipitate, can easily be poured off or withdrawn with a capillary (Pasteur)
pipette. The centrifuge may be damaged if allowed to run unbalanced. Insert your test tubes
in opposite positions in the centrifuge, noting their locations by number. Set the
machine in motion for one minute, which should be sufficient to achieve effective separation
of the solid from the liquid. Allow the centrifuge to stop spinning before trying to remove
your test tubes.
Vortex Mixer
This motorized mixer can be used to ensure complete homogeneity after reagent addition.
Simply place your test tube in the cup at the top and gently but firmly press down to achieve
mixing.
9

To prepare the salt solution firstly dissolve the solid mixture in the proper
solvent by trying the following solvents in the cited order.

1 Distilled water (Cold and then hot).
2 Dilute hydrochloric acid (HCl) (Cold and then hot).
3 Dilute nitric acid (HNO
3
) (Cold and then hot).
4 Conc. hydrochloric acid (HCl) (Cold and then hot).
5 Conc. nitric acid (HNO
3
) (Cold and then hot).
6 Aqua regia [Conc. HCl + Conc. HNO
3
3 : 1 ( v/v)]

Notes:
If the solid mixture is soluble in a certain solvent on hot and reprecipitate
on cooling in this case dissolve in the next solvent.

It is better to prepare the solution as concentrated as possible. The obtained
solution must be clear regardless of its colour.
Preparation of the salt solution
10

Classification of cations
Group Group reagent Cations Distinguishing features
I
(Silver group)

Dilute HCl

Ag
+
, Pb
++
, Hg
2
++

Precipitate as
Chlorides
II
(Acid sulphide group)

HCl + H
2
S
Hg
++
, Pb
++
, Bi
+++
, Cu
++
, Cd
++
,
Sn
++
, As
+++
, Sb
+++
, Sn
++++

Precipitate as
Sulphides in acid medium
III
(Iron group)

NH
4
OH + NH
4
Cl
Al
+++
, Cr
+++
, Fe
+++
Precipitate as
Hydroxides
IV
(Alkaline sulphide
group)
NH
4
OH + NH
4
Cl
+H
2
S
Ni
++
, CO
++
, Mn
++
, Zn
++
Precipitate as
Sulphides in alkaline medium
V
(Alkaline earth
group)
NH
4
OH + NH
4
Cl +
(NH
4
)
2
CO
3

Ba
++
, Sr
++
, Ca
++
Precipitate as
Carbonates.
VI
(Alkali metal group)
No
group reagent
Mg
++
, Na
+
, K
+
, NH
4
+
Ions not Precipitate in previous
groups.

Note: The ions indicated with a Roman numeral probably do not exist as simple ions in solution and the Roman numeral given is the oxidation
state.
11

Silver (Ag
+
), Lead (Pb
++
), and Mercurous (Hg
2
++
)

This group is insoluble in water,
Group reagent is cold dilute hydrochloric acid (HCl).
Group (I) is precipitate as chloride.

Chemistry of Group (I)
The more commonly encountered cations can be separated and analyzed
according to the solubilites of their various compounds in water, acid, etc. The cations
in analytical group (I) are silver ion, mercury or mercurous ion, and lead ion. The
chlorides of these cations are practically insoluble in cold dilute hydrochloric acid,
and these are the only common chlorides which are insoluble. This insolubility may
be used to effect the separation of this group of cations from other cations which
might be present but which do not form insoluble chloride salts.

In the first step,
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),
Hg
2
Cl
2
(s), and PbCl
2
(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
+
, Hg
2
2+
, and Pb
2+
. The reactions that occur are
Ag
+
(aq)
+ Cl
-
(aq)
-> AgCl
(s)

Hg
2
2+
(aq)
+ 2 Cl
-
(aq)
-> Hg
2
Cl
2 (s)

Pb
2+
(aq)
+ 2 Cl
-
(aq)
-> PbCl
2 (s)

12

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) + NH
3
(aq) = Ag(NH
3
)
+
(aq)
Ag(NH
3
)
+
(aq) + NH
3
(aq) = Ag(NH
3
)
2
+
(aq)
The formation of these complex ions lowers the concentration of free silver ion,
allowing precipitated silver chloride to dissolve:
AgCl(s) + x NH
3
(aq) -> Ag(NH
3
)
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 ontains
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.

13

Silver (Ag
+
), Lead (Pb
++
), and Mercurous (Hg
2
++
)

1- Take 1ml of the mixture + 1ml of cold dilute HCl if white precipitate (ppt.) is
formed that means group (I) is present. The filtrate contains other groups.
2- Then transfer the ppt. into a clean beaker; add water, boil, and then filter.
Filtrate
Contains PbCl
2

Precipitate
Contains AgCl and Hg
2
Cl
2
Pour hot ammonium hydroxide solution on the ppt. and collect
the filtrate.
Filtrate Precipitate
Confirmation of
lead(Pb
2+
)

Take portion of filtrate +
acetic acid (CH
3
COOH) +
potassium dichromate

Yellow ppt. (PbCrO
4
)
Confirmation of silver
(Ag
+
)

Take portion of filtrate + dilute
nitric acid (HNO
3
)

White ppt. (AgCl)

Confirmation of
mercuros (Hg
2
2+
)

The ppt. (Hg
0
+ Hg (NH
2
) Cl)
is dissolve in aqua regia, then
heat to evaporate excess aqua
regia., add SnCl
2
.

White ppt.
Turns to gray

potassium iodide solution.

Yellow ppt. (PbI
2
)
Soluble by boiling
solution of potassium iodide

Pale yellow ppt. (Agl)
dilute sulphuric acid.

White ppt. (PbSO
4
)
Soluble by boiling in amm.
acetate solution.
L e a d

is present
S i l v e r

is present

M e r c u r o u s

is present

Group (I)
14

EXPERIMENT 1: Qualitative analysis results of group (I)

Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties
Experiment Observation Results

15


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

16


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

Conclusion

17

Group (IIA): Lead (Pb
2+
), Mercuric (Hg
2+
), Bismuth (Bi
3+
), Copper (Cu
2+
),
and Cadmium (Cd
2+
)

Group (IIB): Arsenic (As
3+,5+
), Antimony (Sb
3+,5+
) and Stannate (Sn
2+,4+
)

It is called the Acid Sulphide group
Group reagent : dil HCl + H
2
S
Both group II and group IV have their sulphides insoluble in water. But
group IV has higher Ksp (needs high S
-2
to precipitate).
So to precipitate the group II only we use dilute HCl with H
2
S

Chemistry of Group (II)
The next two steps in the flow chart separate group II ions and group III ions from the
remaining solution by their ability to form insoluble sulfides upon reaction with H
2
S.
M
2+
+ H
2
S MS(s) + 2H
+

This equilibrium is really a combination of three standard equilibria:
H
2
S HS
-
+ H
+
K
a1
= 8.910
-8

HS S
2-
+ H
+
K
a2
= 1.210
-13

M
2+
+ S
2-
MS
(s)
1/Ksp
When these are combined (added together), the resulting equilibrium constant is strongly
dependent on the K
sp
of the particular sulfide (MS). According to the common ion effect rule,
addition of strong acids will shift equilibrium to the left, leading to a sharp decrease in [S
-2
] in
the solution. On the other hand, alkaline medium enhances ionizations of H2S producing higher
concentration of sulphide ion in solution. Group (IV) sulphides having higher solubility products
than those of group (II) may precipitate if the acidity of the solution is lower than 0.2N. If the
acidity is higher than 0.3N sulphides of lead, candmium and tin are not completely precipitated.
18

1. To the filtrate from group (I), add dilute HCl + H
2
S gas. If precipitate is formed.
2. Group II is present
3. Filter, and then dilute the filtrate with HCl, add excess H
2
S till no ppt.
Filtrate
Contains groups 3, 4, 5 and 6
Precipitate
Contains sulphides of group 2A and 2B

Step 1
Separation of group (IIA) from group (IIB)
1- Transfer ppt. of group IIA and IIB into a clean beaker, add ammonium sulphide, heat with
stirring and then filter.
Filtrate
Contains group (IIB)
Precipitate
Contains group (IIA)
AS
2
S
5
Ammoium thio-
arsenate
Yellow
ppt.
HgS Mercuric sulphide Black
ppt.
Sb
2
S
5
Ammonium thio-
antimonate
Orange
ppt.
CuS Copper sulphide Black
ppt.
SnS
2
Ammonium thio-
stannate
Yellow
ppt.
Bi
2
S
3
Bismuth sulphide Dark
brown
CdS Cadmium sulphide Cannary
yellow

Step 2
2- Transfer the precipitate of group IIA into a clean beaker, add dilute nitric acid (HNO
3
), boil,
and then filter.
Precipitate Filtrate
Contains mercuric sulphide
(HgS)

Note
May be yellowish is formed
due to sulphur.
Dissolve in aqua regia, heat
till the excess of sulphur,
dilute with water, and add
solution of SnCl
2
white ppt.
changes to grey.
Contains nitrate of Bi, Cu, Cd, and Pb

Take portion of filtrate + H
2
SO
4
if white ppt. is formed
that means lead is present.

Here, precipitate all of Pb in the filtrate using conc.
H
2
SO
4
and boil, cool, dilute with water, filter and
neglect the ppt.
Add to the filtrate excess NH
4
OH.
If whit ppt. is formed bismuth also is present.

Group IIA
19

Mercuric is present Hg
2+

Contains Bi(OH)
3

Confirmation of Bismuth
(Bi
+3
):-

Dissolve in least amount of
dilute HCl then add sodium
stannite solution.

if black ppt. is formed

Bismuth Bi
3+

Note:
Preparation of sodium
stannite solution:

SnCl
2
solution + NaOH
white ppt. and then add
excess NaOH.
Contains copper (Cu
2+
) and
cadmium (Cd
2+
)

Detect in presence of each
other

Detection of copper:
1- Blue colour indicate
copper
2- Portion + acetic acid +
potassium ferrocyanide
k
4
[Fe(CN)
6
].

If brown ppt. is formed

Copper Cu
2+
is present

Detection of copper in
presence of copper:
1- Take portion + KCN till
the solution became
colourless add H
2
S.

If yellow ppt. is formed

Cadmium Cd
2+
is present

2- If copper absent, add H
2
S
directly

20

EXPERIMENT 2: Qualitative analysis results of group (IIA)

Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

21


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

22


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

Conclusion

23

Aresnate (As
3+,5
)
+
, Antimonate (Sb
3+,5
)
+
,

and Stannate: (Sn
2+,4+
)
1- Transfer the precipitate of group IIB into a beaker.
2- Add solid ammonium carbonate + some water, boil, and then filter.

Filtrate contains:
Aresnate (AS
3+
) as Ammonium
thioarsenate

Take portion of filtrate + conc.
HCl

Yellow ppt.

Arsenic is present

Precipitate contains:
Ammonium thio-antimonate Sb
2
S
3
(orange)
Ammonium thio-stannate: SnS (yellow)

Iokc portion o ppt. oJJ conc. ECl, boiling

Then divided the solution into two portions:

Test for Tin:
Take portion of solution add iron powder, heat, filter and
then add HgCl
2

White ppt. (turns to grey or black)

Test for Antimony in presence of Tin:
Take portion of solution add NH
4
OH + solid oxalic acid,
heat, and then add H
2
S.

If orange precipitate is formed
Antimony is present

Test for Antimony in absence of Tin:
Take portion of solution+ H
2
S if orange precipitate is
formed.

Antimony is present

Group (II)B
24

EXPERIMENT 3: Qualitative analysis results of group IIB

Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

25


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

26


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

Conclusion

27

Ferric (Fe
3
)
+
, Aluminum (Al
3+
), and Chromium (Cr
3+)

It is called Ammonium hydroxide
Group (III) is precipitate as hydroxide
Group reagent: NH
4
Cl + NH
4
OH

28

Ferric (Fe
3
)
+
, Aluminum (Al
3+
), and Chromium (Cr
3+)

1- To the filtrate from group II add conc. HNO
3
, boil for 3 minutes, add excess NH
4
CL,
boil again and then add NH
4
OH. If precipitate is formed.
2- Group (III) is present.
Contains: Contains:

Groups 4, 5, and 6
Aluminum
hydroxide
Al(OH)
3
Whit gelatinous ppt.
Chromium
hydroxide
Cr(OH)
3
Green ppt.
Ferric hydroxide Fe(OH)
3
Reddish brown ppt.
3- Transfer the precipitate into a clean beaker, add excess NaOH, boil, and then filter.

Contains:
Sodium aluminate

Confirmatory test:

Take portion of filtrate + solid
NH
4
Cl boil till no odour of
ammonia

If white precipitate is formed

Aluminum
is present

Contains: Cr(OH)
3
and Fe(OH)
3

ppt. + (Na
2
O
2
+H
2
O), strong boil, and then filter
If yellow in colour
K
2
CrO
4
present

Confirmatory test:
acetic acid + lead acetate

Yellow ppt.

Chromium is present
If brown ppt. in colour
Fe(OH)
3
present

Confirmatory test:
Take portion of ppt. +
K
4
[Fe(CN)
6
]

Prussian blue
Take portion of ppt. + NH
4
CNS

Blood red

Iron is present

Group (III)
29

EXPERIMENT 4: Qualitative analysis results of group III

Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

30


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

31


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

Conclusion

32

Manganese (Mn
2+
), Zinc (Zn
2+
), Cobalt (Co
2+
), and Nickel (Ni
2+
)

This group is called Ammonium sulphide group

Group reagent: NH
4
Cl + NH
4
OH + H
2
S
Group IV is precipitate as sulphide in alkaline medium

33

Manganese (Mn
2+
), Zinc (Zn
2+
), Cobalt (Co
2+
), and Nickel (Ni
2+
)

1- To the filtrate of group III, add NH
4
Cl (solid) + NH
4
OH solution, and add H
2
S till complete
precipitation. If precipitate is formed.
2- Group IV is present.
Contains:
Group V & VI

Contains:
CoS
NiS
MnS
ZnS

Cobalt sulphides
Nickel sulphides
Manganese
sulphides
Zinc sulphides

Black ppt.
Black ppt.
Buff ppt.
White ppt.

3- Transfer the ppt. into a clean beaker add dilute HCl , stir , wait for 3 minutes , and then
filter the solution.

Contains : CoS + NiS Black
Dissolve the precipitate in aqua regia ,
evaporate till nearly dryness, dilute with
water , divide into 3 portions.

Test for Ni:
Take a portion of precipitate + NH
4
OH +
Dimethylglyoxime
Red PPt.
Ni
2+
is present

Test of Cobalt:
Take a portion of precipitate + NH
4
CNS
Blue colour

Pot. Cobaltnitrite test :

Take a portion of precipitate + KNO
2
+
acetic acid Yellow PPt

Co
2+
is present
Contains: MnCl
2
+ ZnCl
2
Boil the filtrate to expel H
2
S , add Excess NaOH ,
Boil , Filter

Contains: Mn(OH)
2

Dissolve the ppt. in
conc.HNO
3
, add
lead oxide
(PbO),boil for 3
minutes, and wait,

violet color

Mn
2+
is present

Contains: NaZnO
2

Take a portion of filtrate
+ H
2
S gas

White ppt.
ZnS.

Take a portion of filtrate +
Acetic acid + K
4
[Fe(CN)
6
]

white ppt. of Zn
2
[Fe(CN)
6
],
may be yellowish white

Zn
2+
is present
Group (IV)
34

EXPERIMENT 5: Qualitative analysis results of group IV

Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

35


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

36


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

Conclusion

37

Barium (Ba
2
)
+
, Strontium (Sr
2+
) , and Calcium (Ca
2+
)

It is called Alkaline earth group or Ammonium carbonate group

Group reagent : NH
4
Cl + NH
4
OH + (NH
4
)
2
CO
3

The cations precipitate as carbonate in alkaline medium

38

Barium (Ba
2
)
+
, Strontium (Sr
2
)
+
, and Calcium (Ca
2+
)

1. To the filtrate of Group IV add NH
4
Cl till alkaline, heat, and then add ammonium
carbonate (NH
4
)
2
CO
3
white ppt. then Group V is present.

Contains :
Group VI

Contains:
CaCO
3

BaCO
3

SrCO
3

Calcium carbonate
Barium carbonate
Strontium carbonate

White ppt.
White ppt.
White ppt.

2. Transfer the precipitate into the beaker, add acetic acid till dissolve, and boil.
3. To a portion of this solution add K
2
CrO
4
(potassium chromate) if yellow ppt.
then add K
2
CrO
4
to the whole solution, and filter.

Contains : BaCrO
4

Dissolve in conc. HCl, evaporate till
dryness,
Use the residue in flame test Apple
green.

Ba
2+
is present
Contains: SrO
4
& CaCrO
4

Take portion of the ppt.

+ conc soln. of CaSO
4
White
ppt.
Sr
2+
is present

In this case add CaSO
4
to all the solution, boil , and then
filter

Contains : SrSO
4

Dissolve in conc.HCl
,evaporate till dryness, use
the residue in flame test

Crimson red

Sr
2+
is present.
Contains: complex of
calcium ammonium
sulphate.
Portion + amm. oxalate

White PPt.
Evaporate portion till
dryness and use the residue
in
Flame test Brick red

Ca
2+
is present.

Group (V )
39

EXPERIMENT 6: Qualitative analysis results of group (V)

Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

40


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

41


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

Conclusion

42

Magnesium (Mg
2+
), Sodium (Na
+
), Potassium (K
+
), and (NH4
+
)

This group is known as
Alkali metal group

43

Magnesium (Mg
2+
), Sodium (Na
+
), Potassium (K
+
), and (NH4
+
)

Test of magnesium Mg
2+
Test of potassium K
+
& Sodium Na
+

Portion of filtrate of group V + NH
4
Cl
(solid) + NH
4
OH + excess of sodium
phosphate shake strong White PPt.

Mg
2+
is present.

MgSO
4
+ Na
2
CO
3
Na
2
SO
4
+ MgCO
3

(White)

MgSO
4
+ 2 NaOH Na
2
SO
4
+ Mg(OH)
2

(White)

Evaporate large portion of filtrate till no white
fumes of ammonium salts then add conc. HNO
3
,
add water to dissolve any formed precipitate. And
then divide the solution into two portions:

1- Test for potassium K
+

Cobalt nitrate solution + amount of NaNO
2

+ drops of acetic acid then add this
solution to a portion of the solution if
yellow ppt.

Potassium K
+
is present

2- Test for sodium Na
+

Flame test Golden
yellow colour

Sodium Na
+
is present.

Group (VI )
44

EXPERIMENT 7: Qualitative analysis results of group (VI)

Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

45

Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

46


Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

Conclusion

47

Test for Ammonium

To test for ammonium ions (NH
4
+
), sodium hydroxide solution is added to the test
solution and gently heated. If ammonium ions are present, ammonia gas will be
given off. This can be shown in the following equation:
Ammonium ions + hydroxide ions ammonia + water
NH
4
+
(aq)
+ OH
-
(aq)
==> NH
3(g)
+ H
2
O
(l)

The hydroxide ion removes a proton from the ammonium ion to release the
ammonia

Observation
Smelly ammonia released and red litmus turns blue, gentle warming helps BUT
the ammonia should be released at room temperature.
Ammonia gas is evolved because alkali frees ammonia from its salts.

48

EXPERIMENT 8:
Report sheet
Physical properties
Colour :
..
Shape : .
Solubility : ..

Chemical properties

Conclusion

49

Scheme For Identification of Basic Radical in Mixture
Solution Containing one or more of the members of each group
Cold dil. HCl
ppt.
Filtrate
[dil HCl +H
2
S]
Filtrate ppt.
Chlorides of group I Follow analysis as
represented by the scheme of group I
Containing soluble Cations of
group II.III, IV, V and VI
Sulphides of group II Follow
analysis as represented by the
scheme of group II
Containing soluble Cations
of group III, IV, V and VI
To filtrate of group II add concentrated HNO
3
. Boil for 3 minutes to make
1-Oxidation of ferrous to ferric 2- Oxidation of H
2
S gas to S.
50

To Filtrate of group II add
NH
4
Cl +NH
4
OH
ppt.. Filtrate
Filtrate
ppt.
Hydroxides of group III Follow analysis
as represented by the scheme of group
III
group IV, V and VI
Carbonates of group V Follow
scheme of group V
Containing soluble Cations
of group V and VI
NH
4
Cl +NH
4
OH +H
2
S
Sulphides of group IV Follow
scheme of group IV
group VI. Follow analysis From
scheme VI
NH
4
Cl +NH
4
OH till alkaline b0il + (NH
4
)
2
CO
3
ppt..
Filtrate
51

General questions
Why slight excess of hydrochloric acid is added to group (I)?.
We add slight excess HCl to ensure complete precipitate of group (I), by the common ion
effect.

Why dil. HCl is added to group (I)?.
Because PbCl
2
tends to form soluble complex and escape to group II in conc. HCl (i.e
PbCl
2
is soluble in excess Cl
-
)
Pb
+2
+ Cl
-
PbCl
2

PbCl
2
+ Cl
-
[PbCl
3
]
-
+ Cl
-
[PbCl
4
]
2-

Soluble complex
Why not use conc. HCl to ensure that group IV will not interfere?
Because if we use conc HCl the concentration of S
2-
ion will decrease dramatically that it
becomes insufficient to ppt. some cations of group II which has slightly high Ksp eg: Cd,
Pb, Sn..
Therefore we have to adjust acidity. The suitable acidity was found to be 0.2 - 0.3 N HCl
(0.25N). We use crystal violet (external indicator) to adjust acidity.

Why do we oxidize Fe
2+
to Fe
3+
?
Because H
2
S used in pptn of group II is a reducing agent which reduces Fe
+3
(if present)
to Fe
+2
and Fe(OH)
2
has high Ksp so not ppt. in conditions such that of group III but
Fe(OH)
3
has a lower Ksp which can ppt with group III and iron does not escape

Why do we boil after NH
4
Cl ?
1- To coagulate the ppt.
2- To break Cr Amine complex
[Cr(NH
3
)
6
] (OH)
3
Cr(OH)
3
+ 6NH
3

soluble Cr amine complex
52

3- To expel O
2
and prevent oxidation of manganus (Mn
2+
) which has higher Ksp i.e. [not
ppt. as OH
-
] to (Mn
3+
) which has low Ksp and can be ppt. as Mn(OH)
3
so it escapes
from group IV to group III

Why do we add NH
4
Cl ?
By common ion effect it decreases OH
-
conc. so prevent pptn of group IV as hydroxide

Before we test for K
+
we must remove NH
4+
.
Because NH
4+
gives all tests for K
+

Write the color of the precipitate formed
PbCl
2
+ K
2
CrO
4
PbCrO
4
+ 2 KCl ..ppt
[Ag(NH
3
)
2
]Cl + 2 HNO
3
AgCl + NH
4
NO
3
..ppt
Hg
2
Cl
2
+ excess SnCl
2
2 Hg
0
+ SnCl
4
..ppt
Cu
2+
+ [Fe(CN)
6
]
4
Cu
2
[Fe(CN)
6
] ..ppt
(Cu(NH
3
)
4
]
2+
+ 2 CN Cu(CN)
2

..ppt
[Cd(CN)
4
]
2-
+ H
2
S CdS + HCN + CN ..ppt
Fe
3+
+ K
4
[Fe(CN)
6
] K Fe [Fe(CN)
6
] ..ppt
CrO
2-
+ H
2
O
2
CrO
4
2-
+ 4 H
2
O ..ppt
Pb(CH
3
COO)
2
+ (CrO
4
)
2-
PbCrO
4
..ppt
Al(OH)
3
+ OH
-
AlO
2-
+ H
2
O ..ppt
Zn
2+
+ [Fe(CN)
6
]
4-
Zn
2
[Fe(CN)
6
] ..ppt
MgSO
4
+ 2NaOH Na
2
SO
4
+ Mg(OH)
2
..ppt

K+ ion give .. color in Flame test

53

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