Cation 3,4 lab report

Introduction
Analysis of metallic elements in compounds or samples is an integral part of chemical research. The
purpose of this experiment is to learn the techniques to separate and identify some common cations
and to understand the principles for the equilibria of precipitation and complex formation. The
systematic analysis of cations is an integral part of the  qualitative analysis.
Qualitative analysis is the systematic approach that involves precipitation reaction to remove cations
sequentially from a mixture. The behavior of the cations toward a set of common test reagents
differs from one cation to another and furnishes the basis for their separation.
The qualitative analysis of an inorganic mixture is started by first carrying out some preliminary tests.
The Preliminary tests for cations are Physical examination, Charcoal cavity test, Borax bead test and
Flame test. These tests do not give conclusive evidence yet they provide some information about the
ions present in the mixture.Qualitative analysis of cations usually consists of three
stages.First based on different solubility properties the cations are separated into 5 groups through
the successive addition of selective precipitating reagents.Second, within each group precipitated
cations are separated through selective dissolution processes.Third, the presence of each cation is
verified through different identification tests.The cations are classified into the following 5 groups. In
this case only cation group III and IV are considered. Group III (Al3+, Cr3+, Fe3+, , Mn2+)
precipitated as hydroxide or hydrated oxides.Group IV Cations (zn2+,Mn2+ ,Co+2 and Ni2+ 
precipitated as sulfates

Object

 To follow a classic qualitative analysis scheme to separate and identify the ions
in a known mixture of Group III cations
 To apply this scheme to identify the Group III cations present in an unknown
sample

Introduction
In this case analyze solutions of the Group III cations, which
include Cr3+, Al3+, Fe3+, and Mn2+. All the Group III cations form insoluble
hydroxides or hydrates in a basic solution. in qualitative analysis the ions in a given
group are first separated from each other, and then a characteristic test is performed
for each ion in order to confirm the presence of that ion.

Ammonia or NaOH is now added to the solution until it is basic, and

then (NH4)2S(NH4)2S is added. This treatment removes any remaining cations that

form insoluble hydroxides or sulfides. The divalent metal ions Co2+, , Mn2+, Ni2+

and Zn2+precipitate as their sulfides, and the trivalent metal ions  contains Fe3+Fe3+,

sulfide reduces the cation to Fe2+Fe2+, which precipitates as FeS.

The next metal ions to be removed from solution are those that form insoluble
carbonates and phosphates. When Na2CO3Na2CO3 is added to the basic solution that
remains after the precipitated metal ions are removed, insoluble carbonates precipitate
and are collected. Alternatively, adding (NH4)2HPO4(NH4)2HPO4 causes the same
metal ions to precipitate as insoluble phosphates.

Discussion

An aqueous mixture of Cr3+Cr3+, Al3+Al3+, Fe3+Fe3+, and Ni2+Ni2+ is first

treated with a mixture of NaOH and NaOCl solutions. This causes the iron and nickel
cations to precipitate out as hydroxide salts, while the chromium and aluminum cations
remain in solution.

Fe3+(aq)+3OH−(aq)⟶Fe(OH)3(s)
Ni2+(aq)+2OH−(aq)⟶Ni(OH)2(s)
2Cr3+(aq)+3OCl−(aq)+10OH−(aq)⟶2CrO2−4(aq)+3Cl−(aq)+5H2O(l)
Al3+(aq)+4OH−(aq)⟶Al(OH)−4(aq)

Note in the last two equations above that Cr3+Cr3+ is oxidized to the

soluble CrO2−4CrO42− ion while Al3+Al3+ forms a soluble complex ion

with OH−OH−. Neither iron nor nickel form hydroxo-complex ions and therefore
precipitate out as solids. The resulting mixture is centrifuged and then decanted,
separating the solids (Fe(OH)3Fe(OH)3 and Ni(OH)2Ni(OH)2) from the supernatant

solution (containing CrO2−4CrO42− and Al(OH)−4Al(OH)4−).

In order to separate the chromium ions from the aluminum ions in the aqueous
supernatant solution, the solution is first acidified in order to destroy the aluminum
hydroxo-complex ion:

Al(OH)−4(aq)+4H+(aq)⟶Al3+(aq)+4H2O(l) Al(OH)4−(aq)+4H+(aq)⟶Al3+(aq)
+4H2O(l)

Next the solution is made just basic enough to precipitate out the aluminum as its
hydroxide salt, but not so basic that it would remain in solution as the hydroxo-complex
ion. This is accomplished by slowly adding aqueous ammonia:

Al3+(aq)+3NH3(aq)+3H2O(l)⟶Al(OH)3(s)+3NH+4(aq) Al3+(aq)+3NH3(aq)
+3H2O(l)⟶Al(OH)3(s)+3NH4+(aq)

The supernatant solution containing CrO2−4 CrO42− can then be decanted from the

white gelatinous precipitate which is the solid Al(OH)3Al(OH)3. A positive
confirmation for Al3+Al3+ is accomplished by dissolving the solid precipitate in acetic
acid and adding the reagent catechol violet, which reacts with Al3+Al3+ to produce a
blue solution.

In order to confirm the presence of chromium in the supernatant solution, aqueous

BaCl2 is added to it. This results in the formation of a finely divided, pale yellow
precipitate of barium chromate:

Ba2+(aq)+CrO2−4(aq)⟶BaCrO4(s)

Recall that a mixture of solid precipitates of Fe(OH)3 and Ni(OH)2 is collected at the

beginning of this analysis scheme. The next step is to separate them. First the
hydroxide precipitates are dissolved in nitric acid:

Ni(OH)2(s)+2H+(aq)⟶Ni2+(aq)+2H2O(l)
Ni(OH)2(s)+2H+(aq)⟶Ni2+(aq)+2H2O(l)
Fe(OH)3(s)+3H+(aq)⟶Fe3+(aq)+3H2O(l)
Fe(OH)3(s)+3H+(aq)⟶Fe3+(aq)+3H2O(l)
The acidified solution is then made basic by adding aqueous ammonia. Once the
solution has become basic, the excess ammonia will react with Ni2+Ni2+ to form an
aqueous complex ion while the Fe3+Fe3+ will precipitate out once more as
red Fe(OH)3Fe(OH)3 since Fe3+Fe3+ does not typically form complex ions
with NH3NH3:

Ni2+(aq)+6NH3(aq)⟶Ni(NH3)2+6(aq)
Ni2+(aq)+6NH3(aq)⟶Ni(NH3)62+(aq)
Fe3+(aq)+3NH3(aq)+3H2O(l)⟶Fe(OH)3(s)+3NH+4(aq)
Fe3+(aq)+3NH3(aq)+3H2O(l)⟶Fe(OH)3(s)+3NH4+(aq)

The presence of Ni2+Ni2+ in the aqueous solution is confirmed by adding

dimethylglyoxime (C4H8N2O2C4H8N2O2) resulting in the formation of a rose red
precipitate:

Ni2+(aq)+2C4H8N2O2(aq)⟶Ni(C4H7N2O2)2(s)+2H+(aq)
Ni2+(aq)+2C4H8N2O2(aq)⟶Ni(C4H7N2O2)2(s)+2H+(aq)

In order to confirm the presence of Fe3+Fe3+, the red Fe(OH)3Fe(OH)3 precipitate

is dissolved in HClHCl (aq), and then KSCNKSCN (aq) is added to the solution. A
positive result is the formation of a dark red solution indicating the presence
of FeSCN2+FeSCN2+ (aq):

Fe3+(aq)+SCN−(aq)⟶FeSCN2+(aq)

1. Prepare a mixture of Group III cations by adding 1.0 mL of each of the following
0.1 M aqueous solutions to a small test
tube: Cr(NO3)3Cr(NO3)3, Al(NO3)3Al(NO3)3, Fe(NO3)3Fe(NO3)3,
and Ni(NO3)2Ni(NO3)2. Transfer 2.0 mL of this mixture to a 30-mL beaker and
use it for your positive control experiment.
2. Add 2 mL of 6 M NaOHNaOH to the 30-mL beaker containing your positive
control solution. Boil the solution very gently (use a pair of beaker tongs to hold
the beaker) over an open Bunsen burner flame for about one minute. Note that
the time to boil is variable and depends on the volume of solution you have. Do
not boil the solution to dryness. If you boil the solution to dryness, then you
must repeat this step again.
 3. Remove the beaker from the flame and slowly add 2 mL of 1 M NaClONaClO.
Swirl the beaker for 30 seconds using your beaker tongs, then gently boil the
mixture for about one minute.
4. Again, remove the beaker from the flame and add sixteen drops of 6M NH3NH3.
Swirl the mixture, then gently boil for another minute.
5. Transfer the mixture from the beaker into a small test tube and centrifuge in
order to separate the solid from the solution. Decant the supernatant solution
(containing the chromium and the aluminum) into another test tube and save the
solid (containing the nickel and the iron). Save this supernatant solution for
further analysis. It contains the aluminum and chromium cations.
6. Wash the solid by adding 4 mL of water and twenty drops of 6 M NaOHNaOH.
Stir vigorously then centrifuge the mixture. Decant the supernatant solution into
your “waste” beaker and discard this solution.
7. Add 2 mL of 6 M HNO3HNO3 to the washed solid. Save the contents of this
test tube for further analysis. It contains the iron and nickel cations.

Separation of  Al3+Al3+ from  Cr3+Cr3+

8. Slowly add 6 M acetic acid to the supernatant solution saved from Step 5 until it
is acidic (test with blue litmus paper).
9. Add 6 M NH3NH3 one drop at a time until the solution just becomes basic again
(test with red litmus paper). Now add twenty additional drops of
excess NH3NH3. At this point a translucent, gelatinous precipitate
of Al(OH)3Al(OH)3 should appear in the clear (or pale yellow) solution.
10.Stir the mixture for about a minute to allow the system to reach equilibrium.
Centrifuge the mixture, then decant the supernatant solution into another small
test tube. This solution must be saved for further tests.
11.To wash the collected solid, first add 6 mL of deionized water to it. Then place
the test tube with the solid (and water) in a hot water bath for about two
minutes while occasionally stirring the mixture. Check with your instructor if you
are unsure about how to set up a hot water bath. Finally, centrifuge this mixture
and decant the supernatant solution into your “waste” beaker. Discard the
solution and save the solid.

Confirmation of  Al3+Al3+

12.To the solid from Step 11 add four drops of 6 M acetic acid and 6 mL of water.
Stir in order to dissolve the solid. Finally, add four drops of catechol violet to the
resulting solution. The appearance of a blue solution confirms the presence
of Al3+Al3+ in the original solution.

Confirmation of  Cr3+Cr3+

 13.To the decanted solution from Step 10, add twelve drops of 1 M BaCl2BaCl2.
The formation of a very fine, pale yellow precipitate (BaCrO4BaCrO4) confirms
the presence of Cr3+Cr3+ in the original solution.

Separation of  Fe3+Fe3+  from  Ni2+Ni2+

14.If the precipitate from Step 7 is not completely dissolved, stir it until it is
completely dissolved. If necessary, place the test tube in a hot water bath in
order to completely dissolve the precipitate.
15.Slowly add 6 M NH3NH3 to the solution until it is basic (test with red litmus
paper). You should see a red-brown precipitate of Fe(OH)3Fe(OH)3 appear
when the solution turns basic.
16.Add an additional 20 drops of 6 M NH3NH3 and stir to mix well. At this point the
nickel should be dissolved in the solution as Ni(NH3)6Ni(NH3)6.
17.Centrifuge the mixture and decant the supernatant solution into another test
tube. Save both the solid and solution.

Confirmation of  Ni2+Ni2+

18.Add eight drops of dimethylglyoxime to the solution saved in Step 17. The
appearance of a rose-red precipitate confirms the presence of Ni2+Ni2+ in the
original solution.

Confirmation of  Fe3+Fe3+

19.To the precipitate saved in Step 17 add twelve drops of 6 M HClHCl. Next, add
4 mL of deionized water and stir well until the precipitate is completely dissolved.
Finally, add four drops of 0.5 M KSCNKSCN. The formation of a dark red
solution confirms the presence of Fe3+Fe3+ in the original solution.

Lab report 2
The four group III cations in this lab are Cr+3, Al+3, Fe+3, and Ni+2. The first step in analysis involves
separating the ions into two subgroups by treating the solution with NaOH and NaOCl. The hypochlorite
ion oxidizes Cr(III) to a higher, more stable oxidation state (namely Cr(VI)) which is soluble:

2 Cr+3(aq) + 3 OCl-1(aq) + 10 OH-1(aq) → 2 CrO4-2(aq) + 3 Cl-1(aq) + 5 H2O(l)

In addition, Al+3 forms a soluble hydroxo-complex ion in the presence of excess hydroxide:
Al+3(aq) + 4 OH-1(aq) → Al(OH)4-1(aq)
In contrast, Ni+2 and Fe+3 do not readily form hydroxo-complexes and are not oxidized by hypochlorite.
They form insoluble hydroxides under these conditions:

Ni+2(aq) + 2 OH-1(aq) → Ni(OH)2(green solid) Fe+3(aq) + 3 OH-1(aq) → Fe(OH)3(red solid)

To separate aluminum from chromium, the solution containing

CrO4-2 and Al(OH)4- is acidified to destroy the hydroxo-complex:

Al(OH)4-1(aq) + 4 H+(aq) → Al+3(aq) + 4 H2O(l)

Treatment with aqueous ammonia gives a gelatinous white precipitate of aluminum hydroxide. The
concentration of hydroxide in ammonia is too low to form the hydroxo-complex:

Al+3(aq) + 3 NH3(aq) + 3 H2O(l) → 3 NH4+(aq) + Al(OH)3(white solid)

The chromate ion remains in solution. It can be tested and confirmed by precipitation as yellow BaCrO4:

Ba+2(aq) + CrO4-2(aq) → BaCrO4(yellow solid)

The BaCrO4 precipitate dissolves in acid. The solution is then treated with H2O2 to produce a deep blue
color due to the presence of a peroxo-compound, probably CrO5:

2 BaCrO4(s) + 4 H+(aq) + 4 H2O2(aq) → 2 Ba+2(aq) + 6 H2O(l) + 2 CrO5(blue, aq)

The mixed precipitate of Ni(OH)2 and Fe(OH)3 can be dissolved by adding a strong acid. The Ni+2 and
Fe+3 ions can be separated by adding ammonia. Ni+2 is converted to the deep-blue complex
Ni(NH3)6+2 which stays in solution. The Fe+3 ion does not readily form a complex and re-precipitates as
Fe(OH)3:

Ni+2(aq) + 6 NH3(aq) → Ni(NH3)6+2(blue, aq)

Fe+3(aq) + 3 NH3(aq) + 3 H2O(l) → 3 NH4+(aq) + Fe(OH)3(red solid)

Confirm the presence of Ni+2 by adding dimethylglyoxime (DMG), C4H8N2O2, to give a deep rose
precipitate:

Ni+2(aq) + 2 C4H8N2O2(aq) → 2 H+(aq) + Ni(C4H7N2O2)2(red solid)

Confirm the presence of Fe+3 by dissolving Fe(OH)3 in a strong acid and adding KSCN to form a blood-
red FeSCN+2 complex ion:

Fe+3(aq) + SCN-(aq) → FeSCN+2(red, aq)

Discussion

Group 3 cations is also called the hydroxides group, because it is made up of cations

which precipitate as hydroxides in ammonia alkaline solution. More specifically they
precipitate around pH 9, the pH made with ammonia and ammonium chloride (NH3 /
NH4Cl), a very common buffer solution.

NH3 + H2O   NH4+ + OH-

NH4Cl   NH4+ + Cl-

As you can see two equilibria are involved. NH4Cl has a threefold function:

1) By acting as a common ion in the equilibrium of NH3, it reduces the concentration

of OH- ions, thus preventing the precipitation of undesirable hydroxides, such
as Mg(OH)2 . 

2) Still by acting as a common ion, it ensures a great availability of NH3, which forms

soluble amino complexes with species such as Zn2+, Co2+ and Ni2+ in which this cations
coordinate 4 or 6 molecules of ammonia.

3) As electrolyte reduces the likelihood of colloidal precipitates formation.

Manganese is actually analyzed as a group 4 cation and precipitates only partially as

an hydroxide.

Some theory: hydroxides precipitation mechanism

 We can easily predict when our hydroxides will start to precipitate and even when they
will be quantitatively precipitated. We take 10 -2 M as start of precipitation and 10-5 M as
quantitative precipitation (we're obviously referring to the free cations in solution).

…………………………………………………………………………………………………………………….
Group IV
https://amrita.olabs.edu.in/?sub=73&brch=7&sim=180&cnt=1

……………………………………………………………………………………………………………………

Group V

  cations are calcium (II) Ca2+, strontium (II) Sr2+ and barium (II) Ba2+. Its group reagent is 1M solution
of ammonium carbonate (NH4)2CO3  in neutral or alkaline medium. The medium needs to be neutral
or alkaline because it is readily decomposed even by weak acids like acetic acid.

CO32- + CH3COOH ⇌ CO2 ↑ + H2O + CH3COO-

This reagent is easily hydrolyzed but in alkaline medium, the equilibrium shifts backwards and

reagent remains un-hydrolysed.

CO32- + H2O ⇌ HCO3- + OH-

Cations of group IV precipitate in the form of carbonate. For the test of IV group cations, take
the filtrate ofIII(B) group and follow these steps:
1.  Transfer the filtrate of III(B) to a porcelain dish and acidify it with dilute acetic acid. Evaporate it to
a pasty mass, and allow to cool.
2. Add 3-4ml concentrated nitric acid HNO3, and heat until the mixture is dry. Then heat more strongly
until all ammonium salts are volatilised and allow it to cool.
3. Add 3ml 2M hydrochloric acid HCl and 10ml water, heat till warm while stirring to dissolve the salt.
4. Add 0.25g solid ammonium chloride NH4Cl and add concentrated ammonia NH3 solution to make it
alkaline and add group reagent 1M ammonium carbonate (NH4)2CO3 in slight excess. Place it in
water bath at 50-60°C for 5 minutes and keep stirring. Boiling the reagent is necessary for the
removal of ammonium hydrogen carbonate (NH4)HCO3 and ammonium carbamate NH4O(NH2)CO3.
These salts are present as impurities in commercial (NH4)2CO3 and they can interfere in analysis, as
they are soluble in water.
5. Filter and wash with little hot water. Precipitate may contain Barium carbonate BaCO3, Strontium
carbonate SrCO3 and Calcium carbonate CaCO3.

          Ba2+ + CO32- ⟶ BaCO3↓
          Ca2+ + CO32- ⟶ CaCO3↓
          Sr2+ + CO32- ⟶ SrCO3↓

Separation of Ba2+ from Sr2+ and Ca2+

Carbonates of all the three cations are insoluble in water but soluble in acetic acid and in dilute
mineral acid. So, we can dissolve the precipitate of IV group cations in dilute acetic acid.

BaCO3↓ + H+ ⟶ Ba2+ + H2O + CO2

CaCO3↓ + H+ ⟶ Ca2+ + H2O + CO2
SrCO3↓ + H+ ⟶ Sr2+ + H2O + CO2

This way we get the solution of cations of IV group, let's call it solution (A). These cations form
chromate salt on reacting with potassium chromate solution. These chromate salts have different
solubilities; barium chromate is insoluble in dilute acetic acid while the other two are soluble. By
using this difference in solubility, we can separate Ba2+ from others. 

Test a small amount of solution with potassium chromate K2CrO4 solution, a yellow precipitate
indicates Ba2+. Solubility product of SrCrO4 and CaCrO4 is much higher than BaCrO4, so they
need much higher concentration of CrO42- ion to precipitate them. That’s why they can’t get
precipitated from dilute solution.

Ba2+ + CrO42-  ⟶ BaCrO4 ↓

If Barium is absent then proceed without adding potassium chromate to the whole
solution. If barium is present then heat the rest of the solution (A) till boiling and add slight excess of
0.1M potassium chromate K2CrO4 solution until the solution becomes yellow coloured and
precipitation is complete. Filter and wash the precipitate with little hot water. The precipitate
contains BaCrO4. Keep the filtrate (B) and washings for the test of Sr2+ and Ca2+.

Confirmatory Test for Ba2+

Wash the precipitate with hot water. Dissolve it in concentrated hydrochloric HCl acid. HCl coverts
barium chromate into soluble dichromate. Divide the solution in two parts.

BaCrO4 ↓ + H+  ⟶ BaCr2O7 + H2O

Part 1: Dilute it with water and add dilute sulphuric H2SO4 acid. A white precipitate of barium
sulphate is formed which is insoluble in dilute acids but soluble in concentrated sulphuric
H2SO4 acid. This confirms Ba2+.

BaCr2O7 + H2SO4 ⟶ Ba SO4 + H2Cr2O7

Part 2: Evaporate the solution to dryness and apply flame test. Green or yellowish green flame
confirms Ba2+.

Test for Sr2+ and Ca2+

If Ba2+ is absent: Boil the solution (a) for 1 min to expel excess CO2  and test for Sr2+ and Ca2+.
If Ba2+ is present: Take the filtrate (b), which we saved after removal of Ba2+ as chromate, and
neutralised it with 2M ammonia NH3 solution and add excess of ammonium carbonate
(NH4)CO3 solution or you can add a little solid sodium carbonate Na2CO3. A white precipitate
indicates SrCO3 or CaCO3 or both. Wash the precipitate with hot water and dissolve it in 4ml acetic
acid and boil to remove excess CO2.

Add 2ml saturated solution of ammonium sulphate (NH4)2SO4 , followed by 0.2g sodium
thiosulphate Na2S2O3 and heat in a water bath for 5min and allow to stand for few minutes then filter.
Sulphates of Sr2+ and Ca2+ are formed. Strontium sulphate is insoluble in ammonium sulphate
solution, so the  white precipitate we get  here is strontium sulphate and calcium sulphate goes in the
filtrate.

Ca2+ + SO42- ⟶ CaSO4

Sr2+ + SO42-  ⟶ SrSO4↓

Confirmatory Test for Sr2+

Transfer the white precipitate along with filter paper to a small crucible, heat until precipitate has
charred. Moisten the ash with concentrated HCl and apply flame test. Crimson flame confirms Sr2+.

Confirmatory Test for Ca2+

Take the filtrate and add a little 0.1M ammonium oxalate (NH4)2C2O4 solution and 2ml of 2M acetic
acid CH3COOH, warm the solution on a water bath. White precipitate of calcium oxalate is formed
which is insoluble in water as well as in acetic acid. This white precipitate of calcium oxalate
CaC2O4 confirms Ca2+.

Ca2+ + (COO)22- ⟶ Ca(COO)2 ↓
We have successfully separated the cations of group IV. In the next post of analytical chemistry we
will analyse the group V cations in the filtrate of group IV.

Summery
In qualitative analysis, the identity, not the amount, of metal ions present in a
mixture is determined. The technique consists of selectively precipitating only a
few kinds of metal ions at a time under given sets of conditions. Consecutive
precipitation steps become progressively less selective until almost all the metal
ions are precipitated. Other additional steps are needed to separate metal ions
that precipitate together.
3. Group III Cations (Al3+. Fe3+, Co2+, Ni2+, Cr3+, Zn2+ and Mn2+ – insoluble sulphides
or hydroxides in alkaline medium):
After isolating the insoluble sulphides in acidic medium, the solution is made basic and the metallic
sulphides having larger Ksp values such as ZnS, NiS, CoS and MnS precipitate. Moreover, since the
solution is basic Al3+, Fe3+ and Cr3+ form insoluble hydroxides and are also separated from the
solution.

4. Group IV Cations (Ca2+, Sr2+ and Ba2+ – carbonate precipitates):

These three metallic cations all belong to Group IIA in the periodic table of elements and therefore
their chemical properties are very similar. They form soluble chlorides and sulphides and hence are
separable from groups 1, 2 and 3 cations. However, their carbonates precipitate in a mixture of
ammonium carbonate, ammonium chloride or ammonia solution.

5. Group V Cations (Mg2+, Na+, K+ and NH4+):

None of the cations in this group form precipitates in the separation processes of group 1-4 cations
and thus remain in the final solution.
The flowchart for separating the five groups of cations is given below.