M.Sc.

Chemistry

Practical - 2 [Second Year]

Organic Analysis, Estimation and Preparation

[MCHEP - 02]

School of Science
TAMIL NADU OPEN UNIVERSITY
577, Anna Salai, Saidapet
Chennai – 600 015
Tamilnadu, India.
 Master of Science in Chemistry

Practical - 2 [Second Year]

Inorganic Analysis, Estimation & Preparation

[MCHEP - 02]

School of Science
TAMIL NADU OPEN UNIVERSITY
577, Anna Salai, Saidapet,
Chennai – 600 015
Tamil Nadu, India.
 Course Team
Chairperson : Dr. K. Parthasarathy
Vice-Chancellor
Tamil Nadu Open University

Coordination : Dr. M. Murugan

Professor and Head
School of Science
Tamil Nadu Open University

Course Design,
Writing & Editing : Dr. P. Shanmugavelan
Assistant Professor of Chemistry
School of Science
Tamil Nadu Open University

© Tamil Nadu Open University

All rights reserved. No part of this book must be used in any form without obtaining a prior written permission
from the University.
First Edition: July, 2019.
 Contents

Chapter Title Page No.

Inorganic Analysis, Estimation & Preparation 01-36

General Instructions 1

1 Semi-micro Qualitative Analysis 2

2 Reagents required for Inorgnic Qualitative Analysis 14

3 Procedure for preparation of reagents for Inorganic Qualitative 15

Analysis
4 Procedure for preparation of Special reagents for Spot tests 16
For inorganic analysis

5 Estimation of Copper 17

6 Estimation of Nickel 20

7 Estimation of Iron 23

8 Preparation of Potassium tris (oxalate) aluminate (III) 26

trihydrate
9 Preparation of Potassium tris (oxalato) chromate (III) 28
trihydrate

10 Preparation of Tris (thiourea) copper (I) sulphate 30

11 Preparation of Tris Sodium hexanitrocobaltate (III) 32

12 Preparation of Chloropentammine cobalt (III) chloride 33

13 Preparation of Bis (acetylacetonato) copper (II) 35

 Practical-II: Inorganic Chemistry Practicals (MCHEP-02)
General Instructions
Chemistry is a discipline based on observation. In theory papers you will learn principles and theories and in laboratory you have
opportunity to experience these principles and theories in practice. When move to Chemistry lab for performing the experiment -
various safety rules keep in mind.
Kindly follow the guidelines given below:
 Laboratory aprons must be donned at all times in the lab and put up hair properly.
 Sandals, open-toed shoes and high heels are not permitted in the laboratory.
 Shorts or skirts cut above the knee are not permitted in the lab.
 Never wear cloth that hangs.
Kindly follow the general behaviour listed:
 No food or beverages will be permitted inside the lab.
 Always read the upcoming experiments carefully and thoroughly, being used tounderstand all of the directions before entering
the lab.
 Be in and ready, promptly when the lab begins.
 Always read the labels of the reagents and never use a reagent from an unlabelledbottle.
 Never smell a chemical straight out of the container.
 Never pour a waste chemical into drain or put in the garbage.
 Never pick broken glassware with your bare hands, regardless of the size of the piece.Please place all broken glassware in the
appropriate broken glassware bucket.
 Should any injury occur regardless of how minor it is report it immediately to theLab tutors.
 Strictly avoid the use of regional languages in the lab.
 Wash your hand frequently during the lab and definitely wash your hand twice at theend of the lab.

1
 I. Semi-micro Qualitative Analysis:
Analysis of mixture two common cations (Pb, Bi, Ca, Cd, Fe, Cr, Al, Co, Ni, Mn, Zn, Ba, Sr, Ca, Mg,) and two less common cations (W, Tl, Se, Te,
Mo, Ce, Th, Zr, Ti, V, U, Li).

Ions to be identified:
a) Ammonium (NH4 ), Silver (Ag ), Mercurous (Hg ), Mercuric (Hg2+), Lead (Pb2+), Bismuth (Bi3+), Cupric (Cu2+), Cadmium(Cd2+), Arsenic
+ + +

(As3+), Antimony (Sb3+),2+), Stannic (Sn4+), Aluminum (Al3+), Chromic (Cr3+), Ferrous (Fe2+),Ferric (Fe3+), Manganous (Mn2+), Cobalt
(Co2+),Nickel (Ni2+), Zinc (Zn2+), CalciumStannous(Sn(Ca2+), Strontium (Sr2+), Barium (Ba2+),Magnesium (Mg2+).

b) Thallium (Tl+), Tungsten as tungstate (WO42-), Selenium as selenite (SeO32-) or selenate (SeO42-), Tellurium as tellurite (TeO32-)or tellurate
(TeO42-), Molybdenum as molybdate (MoO42-), Cerium (Ce4+), Thorium (Th4+), Titanium (Ti4+), Zirconium as zirconyl (ZrO2+), Vanadium as
metavanadate (VO32-), Uranium as uranyl (UO22+), Lithium (Li+).
Preparation of the Original solution: Take small quantity of the powdered solid and examine the solubility in the following solvents in the order given:

1. Water (Cold and hot)

2. Dil. HCl ( Cold and hot)
3. Conc. HCl (Cold and hot)
4. Dil. HNO3 (Cold and hot)
5. Conc. NHO3 (Cold and hot)
6. Aqua Regia ( 3 parts of Conc. HCl + 1 part of Conc. HNO3 , mix and use the solution immediately,
do not keep it at all)
The given aqueous solution shall contain four cations, two cations from (a) and two from (b).

2
 CATION GROUPS AND REAGENTS
Group Group Reagent Cations (some metals as more stable oxy anions)
+ + 2+ + 2-
Group I Dil. HCl (2M) Hg , Ag , Pb , Tl , WO4 .
2+ 2+ 3+ 2+ 2+
Group II Dil. HCl + H2S gas Hg , Pb , Bi , Cu , Cd .
3+ 3+ 2+ 4+ 2- 2- 2- 2- 2-
As , Sb , Sn , Sn , SeO3 , SeO4 , TeO3 , TeO4 , MoO4
3+ 3+ 2+ 3+ 4+ 4+ 4+ 2+ 2- 2+
Group III A NH4Cl + NH4OH solutions (2M) Al , Cr , Fe , Fe , Ce , Th , Ti , ZrO , VO3 , UO2 .
2+ 2+ 2+ 2+
Group III B NH4Cl + NH4OH+ H2S gas Co , Ni , Mn , Zn .
2+ 2+ 2+
Group IV NH4Cl + NH4OH + (NH4)2CO3 solutions (2M) Ca , Sr , Ba .
2+
Group V NH4OH + (NH4)2HPO4 or Na2HPO4 Mg
+ + + +
Other Radicals No common reagent NH4 , Na ,Li , K 2

+
Tests for ammonium, (NH4)
Note: Do the tests for ammonium using the original solution given.

Test Observation Inference

1. Add 0.5 cm3 of NaOH solution (2M) to 0.5 cm3 of Ammonium may be present. Strong alkalis liberate
the given solution in a test tube and heat gently to Characteristic smell of ammonia ammonia from ammonium salts.
boiling. Smell the mouth of the tube occasionally NH4++ OH- NH3 + H2O
while heating.

2. Add 0.5 cm3 of NaOH solution (2M) to 0.5 cm3 of Ammonium may be present. The liberated ammonia
the given solution in a test tube and heat gently to Copious white fumes from the glass rod. reacts with HCl producing fumes of NH4Cl.
boiling. Insert a glass rod dipped in conc. HCl into the
mouth of the test tube while heating.

3. To 0.5 cm3 of saturated sodium hydrogen tartrate solution

(or saturated tartaric acid solution) in a tube and add few drops
of test solution. A white crystalline precipitate is formed. Presence of NH4+ is confirmed. The precipitate is

3
 Presence of NH4+is confirmed. The precipitate is

4. To 0.5 cm3 of saturated sodium hexanitrito

cobaltate (III) solution, add a few drops of the test solution A yellow precipitate is formed. ammonium (III).
solution. 3 NH4+ + [Co(NO2)6]3- (NH4)3[Co(NO2)6]↓

Spot test: Mix a drop of the test solution with a drop of sodium
Presence of NH4+ is confirmed. The colour is due to the
hydroxide solution on a watch glass. Place a micro drop of this
mixture on a piece of filter paper and add a drop of Nessler’s
reagent on it.
An orange red stain or ring is produced. formation of ammonium mercuric iodide.

(Note: Various formulae have been reported for the

product by different authors).

4
 Separation of Cations into Groups.

Note: After centrifuging in each group, transfer centrifugate into a small beaker for evaporation. Carry out precipitation in the beaker itself and then transfer into
the centrifuge tube.
3
Add a few drops of dilute (2M) HCl to 5 cm of the cold test solution. If a precipitate forms, continue adding the acid in drops with shaking till no further precipitation takes place.
Centrifuge.

Residue: Centrifugate: Add a drop of H2O2 and dilute the solution to double its volume with water. Heat nearly to boiling and saturate with H2S gas. Shake well. If a
Chlorides of precipitate forms, continue passing H2S till no more precipitate is formed and smell of H2S persists. Centrifuge.
Group I metals 3
Residue: Centrifugate: Boil down to half its volume in a small beaker till no smell of H2S remains. Add 1 cm of concentrated HNO3 (to
Or H2WO4.H2O. 2+ 3+ 3
Sulphides of oxidize any Fe to Fe ). Evaporate till almost dry and dilute to 5 cm with water. Add 2 g of solid NH4Cl and heat to boiling. Add
Group II metals. dilute NH3 solution drop by drop with shaking till a strong smell of ammonia persists. Heat to boiling and centrifuge.
+ +
White - Hg , Ag ,
2+ + 2- Residue: Centrifugate: Evaporate to reduce volume. Add dilute NH3 solution drop by drop with shaking till a
Pb , Tl , or WO4 . 2+
Black – Hg ,Pb ,
2+
3+ 2+ Hydroxides or strong smell of ammonia persists. Saturate with H2S gas. Shake well. If a precipitate forms, continue
Bi or Cu . passing H2S till no more precipitate is formed and smell of H2S persists. Boil. Centrifuge.
Examine as given 2+
Yellow – Cd , Sn
4+ oxides of Group III A
in Table 1. 3+ metals. 3
Se or As . Orange Sulphides of Centrifugate: Evaporate till almost dry and dilute to 5 cm with water. Add dilute
3+ NH3 solution drop by drop with shaking till a strong smell of ammonia persists. Add
red - Sb . Brown - 3+ 2- Group III B
White - Al , VO3 ,
2+ metals. (NH4)2CO3 solution dropwise with stirring till precipitation is complete.
Te, Sn or 4+ 2+
Ti , ZrO or Th ;
4+
6+
Mo . Centrifugate: Boil and reduce to half volume of solution then
White, 2+ Residue:
Black - Co or make it alkaline with NH4OH ,+4-5 drops of 5 %
Slowly turning 2+ Carbonates of
Examine as given 4+
Ni ; (NH4)2HPO4 or Na2HPO4 ,boil and allow it to cool and
Brown -Ce 2+ Group IV metals.
in Table 2. Pink - Mn ; centrifuge.
3+ 2+.
Bluish green - Cr ; White - Zn
3+ 2+ Residue : Centrifugate :
Brown - Fe ; White - Ca ,
2+ 2+ 2+ :(Group V Alkaline) : ( Group Other Radical)
Yellow - UO2 . Examine as given Sr or Ba . +
White – MgNH4PO4 Use W.E for the test of K ,
in Table 4. 2+ + + +
Examine as given Examine as given May contain Mg Na ,Li and NH4
in Table 3. Examine as given Examine as given
in Table 5.
in Table 6. in Table 7.

5
 Table 1.

3 3 3
The Group I (Silver Group) residue is washed using 2 cm of dilute HCl (see instruction 9) and then with 2 cm of water. Discard the washings. Boil residue in the centrifuge tube with 2 cm
3
of water and centrifuge while hot. Decant the centrifugate into a test tube. Repeat extraction with 2 cm boiling water and combine the centrifugate.
2+ +
Residue: White – Hg2Cl2 or AgCl. Yellow - H2WO4. Centrifugate: May contain Pb or Tl , which may crystallize on cooling. Carefully
3 3
Boil the residue with 5 cm of dilute NH3 solution and centrifuge. add 1 cm of conc. H2SO4 and evaporate till fumes are seen. Cool and dilute
3
carefully to 5 cm with water. If a precipitate is formed, centrifuge.
+ +
Residue: Black precipitate, Centrifugate: May contain [Ag(NH3)2] or H2WO4. Add dilute HCl Residue: White – PbSO4. Centrifugate: May contain Tl . Add dilute NH3
consisting of a mixture of in drops with shaking till a faint precipitate forms, which is re- Dissolve in ammonium acetate solution and boil off excess NH3. Cool and do
Hg(NH2)Cl and Hg. dissolved by adding one drop of dilute NH3 solution. Add KI solution (or a mixture of NH3 the following tests:
solution drop wise with shaking till precipitation, if any, is complete. solution and acetic acid) and 3
Dissolve the residue by heating Centrifuge. the following tests are done: 1) To 1 cm of the solution, add acetic acid
3
with 2 cm of aqua regia, cool 3 and K2CrO4 solution. A yellow precipitate
and do the following tests: Residue: Pale yellow precipitate Centrifugate: Tungstic acid 1) To 1 cm of the solution, add of Tl2CrO4 is formed.
3
of AgI. (H2WO4) solution. acetic acid and K2CrO4 solution. 2) Flame test: Evaporate 2 cm of the solution
3
1) To 1 cm of the solution, add 1)To a portion of the above Reduce to half its volume by A yellow precipitate of PbCrO4 to dryness in a china dish, cool and mix
NaOH solution in drops with precipitate, add excess of sod. evaporation, cool and do the is formed. residue with a drop of conc.HCl using a
shaking till excess. A black thiosulphate solution. The following tests: glass rod. A speck of the mixture is taken at
3
precipitate of Hg2O is formed. precipitate dissolves. Presence 2) To 1 cm of the solution, add the tip of a nickel spatula and introduced
+ 3
of Ag confirmed. 1) To 0.5 cm of the solution, add KI solution. Boil and cool. A into a Bunsen flame. An intense green
ferrous sulphate solution. A yellow precipitate of PbI2 is colour appears
3
2) To 1 cm of the solution, add 2) Spot test: Place a drop of the brown precipitate of ferrous formed, which dissolves on 3) Spot test: Place a drop of the solution on a
3
K2CrO4 solution and heat. A test solution (original) on a tungstate is formed. Add 1 cm of heating and re-precipitates as drop reaction paper and add a drop sodium
brown precipitate changing to watch glass and add a drop of dilute HCl and boil. The golden spangles on cooling. thiosulphate solution. Add a drop of KI
red Hg 2CrO4 on heating. ammonium carbonate solution precipitate turns white and then solution over it. A yellow spot of Tl (I) is
and mix. Withdraw a drop of yellow due to formation of 3) Spot test: Place a drop of the produced.
3) Spot test: Place a drop of clear liquid from the mixture and tungstic acid. solution on a drop reaction
faintly acid test solution place it on a drop reaction paper paper and add a drop of
2) Spot test: Place a drop of the
(original) on a drop reaction and add a drop of K2CrO4 ammonium sulphide solution. A
test solution (original) on a drop Presence of Tl (I)
paper and add a drop of saturated solution. A red ring is obtained black spot of PbS is formed.
reaction paper and add a drop of is confirmed.
potassium nitrite (KNO2) due to formation of Ag2CrO4. conc. HCl. A drop of saturated
solution. A black spot of Hg is Presence of Pb (II)
SnCl2 solution is placed at the
produced. Presence of Ag(I) is confirmed.
centre of the spot. A blue colour is
is confirmed.
produced due to formation of
Presence of Hg(I)
is confirmed. tungsten blue, W2O5.
Presence of W(VI)
is confirmed.

6
 Table 2.

3
Wash the Group II residue with 2 cm of a solution of ammonium chloride saturated with H2S and centrifuge. Discard centrifugate. Transfer residue into a small
3
beaker and add 5 cm of yellow ammonium sulphide (amm. polysulphide) solution. Heat to about 50 to 600C and maintain at this temperature for 5 minutes with
stirring. If there is a precipitate, cool and centrifuge.

Residue: Black – HgS, PbS, Bi2S3 or CuS. Yellow – CdS. Centrifugate: Add conc. HCl dropwise till just acidic (do not add excess!) and warm
while stirring. A fine white or pale yellow precipitate is only sulfur. If a flocculant
precipitate is formed, centrifuge. If not, discard the solution.
Analyse as given in Table 2A.
Residue: Yellow – SnS2, Se or As2S3. Orange red – Sb2S3.
Brown -Te, SnS or MoS3.

Analyse as given in Table 2B.

7
 Table 2A

3 3
The Group IIA (Copper Group) residue is washed two times using 2 cm of distilled water and centrifuged. Discard washings. Transfer residue to a small beaker, add 10 cm of dilute nitric acid
and boil for 5 minutes. If some solid material remains, cool and centrifuge.

Residue: Black – HgS. Centrifugate: May contain nitrate of Pb, Bi, Cu or Cd. Add dilute H2SO4 till precipitation (if any) is complete. Centrifuge.

Dissolve by boiling with 2 cm

3 Residue: White – PbSO4. Centrifugate: May contain nitrate or sulphate of Bi, Cu or Cd. Add concentrated NH3 solution dropwise with shaking
of aqua regia. Do the following tests Dissolve in ammonium acetate till smell of ammonia persists. If a residue remains, centrifuge.
with this solution: solution (or a mixture of NH3
3+ 3+
solution and acetic acid) and the Residue: White – Bi(OH)2. Centrifugate: May contain [Cu(NH3)4] or [Cd(NH3)4] . If deep blue in
3 following tests are done: The residue is divided into two colour, Cu is present. Add dilute acetic acid with shaking till a clear solution is
1) To 0.5 cm of the solution, add parts. obtained. Divide into two parts.
3
NaOH solution dropwise with 1) To 1 cm of the solution, add
shaking till excess. A brownish red acetic acid and K2CrO4 solution. 1) To one part of the residue, add a Divide the first part into three equal Divide the second part into three
precipitate changing to yellow HgO. few drops of conc. H2O2 solution. portions and do the following tests: equal portions and do the following
A yellow precipitate of PbCrO4
is formed. A yellowish brown tests:
3 precipitate of bismuthate ions
2) To 0.5 cm of the solution, add 1) To one part, add pot. Ferrocyanide
3 -
Na2CO3 solution dropwise and 2) To 1 cm of the solution, add (BiO3 ) is produced. solution. A reddish brown precipitate of 1) To one part, add NaOH solution. A
shake till effervescence just stops. KI solution. Boil and cool. A copper ferrocyanide is formed. white precipitate of Cd(OH)2 is
Then add KI solution dropwise with yellow precipitate of PbI2 is 2) Dissolve the second part of the formed.
3
shaking till excess. A red precipitate formed, which dissolves on residue in 1 cm of dilute HNO3 2) To the second portion, add
of HgI2 is formed, which dissolves heating and re-precipitates as and divide into two parts. To one pot.thiocyanate solution. A black 2)Through the second portion, pass
in excess reagent. golden spangles on cooling. part, add KI solution dropwise precipitate turning slowly white is H2S. A yellow precipitate of CdS is
with shaking to excess. A black formed. obtained.
3) Spot test: Place a drop of the test 3) Spot test: Place a drop of the precipitate of BiI3 is first formed, 2 Cu(SCN)2 → 2 CuSCN + (SCN)2.
solution on a spot plate. Add a drop solution on a drop reaction paper which dissolves in excess KI to 3) Spot test: Place a drop Cadion - 2
-
of amm.thiocyanate solution and a and add a drop of amm. Sulphide give an orange solution of [BiI4 ]. 3) Spot test: Place a drop of the third B reagent on a drop reaction paper.
drop of cobalt acetate solution. A solution. A black spot of PbS is part on a spot plate and add a drop of Place a drop from the third part over
blue colour is produced. formed. 3) Spot test: Place a drop of the tartaric acid solution, followed by a it, followed by a drop of KOH
second part on a spot plate and add drop of NaOH solution. An intense solution. A bright pink spot
a drop of thiourea solution. An blue colour is produced. surrounded by a blue circle is
Presence of Hg(II) Presence of Pb(II) intense yellow colour is produced. produced.
is confirmed. is confirmed. Presence of Cu(II)
is confirmed Presence of Cd(II)
Presence of Bi(III) is confirmed.
is confirmed

8
 Table 2B
3 3
Transfer the Group IIB (Tin Group) residue into a small conical flask and place a funnel in its mouth. Add 5 cm of conc. HCl and boil gently for 5 minutes. Dilute with 3 cm of distilled water, cool and
centrifuge.
3
Residue: Yellow - Se or As2S3. Brown –Te or MoS3. Dissolve in 5 cm of conc. HCl containing a pinch of solid potassium chlorate
Centrifugate: May contain Sb or Sn as chloride. Boil to expel H2S.
(KClO3). Transfer solution to a small beaker and concentrate by evaporating on a water bath. Cool and add NH 3 solution with
3
stirring till smell of ammonia persists. Add 2 cm of Mg(NO3) 2 solution and stir for 5 minutes. When precipitation is complete, Cool and carry out the following tests
using small portions of the
centrifuge. solution.

3 3
Residue: White crystalline Centrifugate: May contain Se, Te or Mo as chlorides. Transfer to a small beaker and boil off To 2 cm of the solution in a To 1 cm of the solution in a test tube,
3 3
Mg(NH4)AsO4.6H2O Shake NH3. Add 2 cm of conc. HCl and evaporate to half volume on a water bath. Add 2 cm of a test tube, add a pinch of add just enoughNH3 solution to
3
the residue well with 3cm of saturated solution of sodium sulphite (Na2SO3) solution. If a precipitate is formed, centrifuge. iron filings and boil to neutralize. (A slight precipitation may
water and divide into three 3 reduce Sn(IV) to Sn(II). occur ). Add a pinch of solid oxalic
portions. Residue: Red – Se. Centrifugate: Dilute with equal volume of water. Add 1 cm of KI Cool and centrifuge. With acid and boil. Pass H2S through the
Dissolve the residue by solution and a drop of sodium sulphite (Na2SO3) solution. If a draw the clear supernatant solution. An orange precipitate of
3
1) To one portion, add heating with 1 cm of conc. precipitate is formed, centrifuge carry out the following Sb2S3 is obtained.
AgNO3 solution containing a HNO3. Neutralise by 3 tests.
few drops of acetic acid. A red adding amm. carbonate Residue: Black – Te Centrifugate: Add 1 cm of Spot test: Place a drop of the solution
3
3
precipitate of silver arsenate, solution dropwise till Dissolve in 2 cm of cold dilute conc. HCl and boil to remove 1) to 1 cm of the solution in on a spot plate and add a minute crystal
Ag3 AsO4, is formed. effervescence stops. HCl. Divide the solution into dissolved SO2.Divide the a test tube, add two drops of of sodium nitrite (NaNO2) . Then add a
three parts. solution into three parts.
Divide the solution into mercuric chloride (HgCl2) drop of rhodamine- B reagent. A blue
2) To the second portion, add three parts. solution. A silky white or colour is obtained.
3 1) Neutralise one portion by 1) To one part, add
0.5 cm of conc. HNO3 and adding amm. carbonate pot.ferrocyanide solution. A grey precipitate of Hg2Cl2 is
excess of amm. molybdate 1) To one part, add BaCl2 solution dropwise till reddish brown precipitate of Mo obtained. Presence of Sb
solution. A yellow precipitate solution. A white effervescence stops. Add ferrocyanide is formed. 3 is confirmed.
of amm. arsenomolybdate is precipitate of BaSeO3 is 2) To 0.5 cm of the solution
BaCl2 solution. A white
formed. formed. precipitate of BaTeO3 is 2) To the second part, add two in a test tube, add NaOH
formed. drops of ferroussulphate solution dropwise with
3) Spot test: To the third 2) To the second part, add shaking. A white precipitate
solution. A blue colour is
portion, add two drops of CuSO4 solution. A bluish 2) To the second part, add produced. of Sn(OH)2 soluble in excess
conc. H2O2 solution and green precipitate of excess of KI solution. A red NaOH is obtained.
warm. Acidify with a few CuSeO3 is formed. colour is produced due to 3) Spot test: Place a drop of the
drops of acetic acid. Place a 3) Spot test: Place a drop of
formation of [TeI 6] 2- . third portion on a drop reaction
drop of this mixture on a 3) Spot test: Place a drop the solution on a drop
paper and add a drop of pot.
drop reaction paper followed of the third portion on a 3) Spot test: Place a drop of Thiocyanate solution. Then add reaction paper and add a
by a drop of AgNO3 solution. spot plate and add a drop the third portion on a spot a drop of SnCl2 solution. A red drop of bismuth nitrate and
A red spot is obtained. of thiourea solution. A red plate and add a drop of 50% spot of [Mo(SCN) 6] 3- is seen. a drop of NaOH solution. A
precipitate of Se is formed. hypophosphorus acid. black spot due to Bi metal.
Presence of As Evaporate. A black stain due to Presence of Mo (VI)
is confirmed. Presence of Se (IV) Te is seen. is confirmed. Presence of Sn
is confirmed. is confirmed.
Presence of Te (IV)
is confirmed.

9
9
 Table 3
3
The Group-III A (Iron Group) residue is washed with 2% amm. nitrite (NH4NO2) solution and dissolved in the minimum quantity of dilute HCl. Prepare a mixture containing 2 cm of 30% H2O2 solution and a fresh pellet of
3
NaOH dissolved in 2 cm of water. Add the weakly acidic test solution into it and boil for 5 minutes. Centrifuge.
2- - - 2-
Residue: White – TiO2.xH2O or ZrO2.xH2O or ThO2.xH2O or MnO2.xH2O; Brown – Fe(OH)3; Yellow – CeO3.xH2O.Wash the residue with Centrifugate: May contain CrO 4 , [Al(OH) 4] , VO 3 or U 2O 7 . Transfer to a small
3 3 3
hot 2% amm. nitrite (NH4NO2) solution (see instruction 9). Dissolve by boiling with 5 cm of dilute HCl and do the following tests as beaker and acidify with 2 cm of conc. HNO3 and dilute with 5cm of water. Boil and
3
appropriate: concentrate to half volume. Add 2 cm of lead nitrate solution and a pinch of solid amm.
acetate. Boil and centrifuge.

1) To 0.5 cm3 of the 2) To 1 cm3 of the 3) To 1 cm3 of the solution, add a few drops of 4) To 1 cm3 of the Residue: Yellow -
3+
Centrifugate: May contain Al , or UO2 and excess of
2+
2+
solution, add a drop of solution, add a few drops saturated oxalic acid solution. White precipitate
solution, add a few drops PbCrO4 or Pb(VO3)2. Pb . Pass H2S through the solution to precipitate all the
3
pot. (or amm.) thiocyanate of H2O2 solution. Orange indicates Th or Ce. Centrifuge and discard of conc. H2SO4 and PbS. Centrifuge. Wash the precipitate with 2 cm of
3 3
(KCNS) solution. Red colour indicates Ti. White evaporate till fumes. Cool,
supernatant. Boil residue with 5 cm of saturated Dissolve in 5 cm of dilute water and combine the centrifugates. Boil to expel all the
colour of FeCNS precipitate indicates Zr. amm. oxalate solution. If there is a
dilute and add two drops HNO3 by heating and H2S and concentrate. Neutralise with NH 3 solution and
3
indicates Fe(III). residue,centrifuge. of conc. HNO3 and a transfer into a test tube. add 5 cm of amm. carbonate solution. Boil for 5minutes.
3
Spot test : Place a drop of pinch of PbO2. Boil and Cool well and add 5 cm Cool and centrifuge.
Spot test: Place a drop of solution on a drop reaction allow to stand. Purple -
of amyl alcohol and two
the solution on a drop paper. Add a drop of Residue: Centrifugate: 3 supernatant (MnO4 ) drops of conc. H2O2 Residue: White – Centrifugate: May 4-
reaction paper. Add a drop catechol solution. A yellow Ce(III)oxalate. Acidify 1 cm of the indicates Mn. solution. Close the mouth Al(OH)3. contain [UO2(CO3)3] .
solution with dilute
of pot. Ferrocyanide or orange spot indicates Ti. of the tube and mix well by
Boil residue with 2 HCl. Thoriumoxalate Dissolve the residue Evaporate to a small volume,
solution. A blue spot of cm
3
of NaOH is re-precipitated. If Mn is indicated, add inverting a few times. 3
in 1 cm of dilute acidify with acetic acid and
ferric ferrocyanide Presence of Ti (IV) excess of NH3 solution Allow the two layers to
solution. A yellow HCl. Add NaOH divide into two parts.
indicates Fe. is confirmed. into the remaining separate. A blue colour in
precipitate of Ce(OH)4 Spot test: Retrieve a solution dropwise
solution and pass H2S gas. the upper layer due to CrO5
is obtained. little of the above with shaking till 1) To one portion, add NaOH
Presence of Fe Spot test: Place a drop of A pink precipitate of indicates Cr. A brownish
precipitate and excess. A white solution. Yellow precipitate of
is confirmed. solution on a spot plate. MnS. Confirm as in red colour in the lower
Spot test 3+
Na2 U 2 O 7 indicates U.
Add a drop of Alizarin-S : Retrieve a dissolve it in two Table 4. layer due to VO2 precipitate dissolving
little of the above drops of conc. HNO3. in excess indicates
solution and a drop of precipitate and Place a drop of indicates V. Al. Do the
spot Spot test: Place a drop of the
conc.HCl. A red precipitate dissolve it in two solution on a spot ← testusing this solution on a spot plate and add
indicates Zr. Spot test: Place a drop of Spot test : Place a drop of
drops of conc.HNO 3. plate and add a drop of solution. pot. ferrocyanide solution and
the aqueous layer on a the amyl alcohol layer on a
Place a drop of pot. Ferrocyanide then NaOH solution. A brown
Presence of Zr(IV) spot plate and add a drop spot reaction paper and
solution on a spot solution. A white Spot test: Place precipitate of (UO2)2[Fe(CN)6]
is confirmed. of CuSO4 solution. A evaporate off the alcohol
plate and add a drop precipitate of thorium adrop of the solution changing to yellow in NaOH
green (metavanadate) or by warming .Place a drop
of a 5% alcoholic ferrocyanide is on a spot plate and indicates U.
yellow (pyrovanadate) of diphenyl carbazide
solution of anthranilic formed. add a drop of
precipitate. reagent on it. A blueviolet
acid. A blackish blue Alizarin-S reagent Presence of U(VI)
colour is seen.
precipitate rapidly Presence of Th (IV) .Add drops of acetic is confirmed.
changing to a brown is confirmed. Presence of V(IV) acid till violet
is confirmed. Presence of Cr(III)
solution. colourd is appears.
is confirmed.
A red precipitate.
Presence of Ce(IV)
is confirmed. Presence of Al(III)
is confirmed.

10

10
 Table 4

The Group III B (Zinc Group) residue may contain CoS (black), NiS (black), MnS (pink) or ZnS (grey). Wash the precipitate with 2 cm3 of water containing a little NH3, NH4Cl and
H2S (see instruction 9). Centrifuge and reject washings. Transfer the precipitate into a small beaker and add 5 cm3 of dilute HCl followed by 5 cm3 of water. Stir well and allow to stand
for 5 minutes. If there is a residue, centrifuge.

Residue: Black – CoS or NiS. Dissolve in 4 cm3 of aqua regia and transfer to a Centrifugate: May contain Mn2+ or Zn2+. Boil down to half volume to remove all H2S.
china dish. Evaporate carefully by heating over a wire gauze to dryness. Do the Add 2 cm3 of NaOH solution and two drops of conc. H2O2 solution. Boil for 2 minutes
following tests as appropriate: and if there is a residue, centrifuge.

Blue residue: Indicates Co2+. Yellow residue: Indicates Ni2+. Residue: Dark brown MnO2.xH2O. Centrifugate: May contain Na2ZnO2.
Dissolve residue in 2 cm3 of water. Dissolve residue in 2 cm3 of water. Dissolve by boiling with 2 cm3 of dilute 1) To 1 cm3 of the solution, add dilute
Pink solution indicates Co2+. Green solution indicates Ni2+. sulphuric acid. Pink solution indicates Mn2+. H2SO4 solution drop wise with shaking
till excess. A white precipitate of
Carry out the following tests using Carry out the following tests using Carry out the following tests using this Zn(OH)2 forms, which dissolves in
this solution. this solution. solution. excess as ZnSO4. (Use this solution for
the following spot test).
1) To 1 cm3 of the solution, add 1) To 1 cm3 of the solution, add 1) To 1 cm3 of the solution, add NaOH
NaOH solution dropwise with shaking NaOH solution dropwise with solution dropwise with shaking till excess 2) Spot test: Place a drop of the above
till excess and warm. A blue shaking till excess and warm. A green and warm. A white precipitate of Mn(OH)2 solution on a spot plate. Add one drop
precipitate of Co(OH)NO3 appears precipitate of Ni(OH)2 appears which appears which is insoluble in excess. The each of CuSO4 solution and amm.
first, which changes to is insoluble in excess. precipitate rapidly becomes brown when Mercurothiocyanate reagent. A violet
pink Co(OH)2. exposed to air due to formation of precipitate consisting of the mixed
MnO(OH)2. mercurothiocyanates of Cu and Zn is
2) Spot test: Place a drop of the 2) Spot test : Place a drop of the 2) Spot test : Place a drop of the solution on formed.
solution on a spot plate and two drops solution on a spot plate. Add one drop a spot plate. Add one drop of conc. HNO3
of amm. (or pot.) thiocyanate solution. each of dimethylglyoxime reagent and a small crystal of solid sodium Presence of Zn(II) is confirmed
A blue colour appears due to the and NH3 solution. A red colour or bismuthate. A purple colour is produced due
formation of [Co(SCN)4]2-. precipitate of nickeldimethyl to formation of permanganate ions.
glyoxime complex is formed.

Presence of Co2+ is confirmed. Presence of Ni(II) is confirmed. Presence of Mn(II) is confirmed.

11
11
 Table 5

3
Transfer the Group IV (Barium Group) residue into a small beaker and dissolve in 5 cm of dilute acetic acid by heating on a water bath. When completely dissolved,
add pot. chromate (K2CrO4) solution dropwise while stirring the hot solution, till a faint yellow colour persists in the supernatant indicating excess of the reagent. If a
precipitate forms, boil, allow to cool and centrifuge.
3 3
Residue: Yellow - BaCrO4. Centrifugate: Transfer into a small beaker. Add 2 cm of saturated amm. sulphate solution and 0.5 cm of sodium
3 thiosulphate solution. Boil and reduce to half its volume. If a precipitate forms, cool and centrifuge
Dissolve the residue by heating with 1 cm of
conc.HCl and transfer into a china dish. Evaporate
to dryness. Residue: White – SrSO4. Centrifugate: May contain Ca as complex.
3 Transfer to a small beaker and make alkaline by adding NH 3
Flame test: Take a speck of the dry residue at the Dissolve the residue by heating with 1 cm of 3
tip of a charred match stick and introduce into a conc. HCl and transfer into a china dish. solution dropwise with shaking till smell persists. Add 2 cm of
colourless Bunsen flame near the base.The flame is Evaporate to dryness. amm. Oxalate solution. A white precipitate of CaC 2O4 appears
coloured an apple green, indicating Ba. slowly.
3 Flame test: Take a speck of the dry residue at the Centrifuge and discard centrifugate. Dissolve the residue by
Extract the remaining residue with 1 cm of dilute
HCl and divide into two parts. To one part, add tip of a charred match stick and introduce into a heating with 1 cm3 of conc. HCl and transfer into a china dish.
dilute H2SO4 solution. A white heavy precipitate colourless Bunsen flame near the base. The flame Evaporate to dryness.
of BaSO4 is obtained. is coloured crimson, indicating Sr.

3
Spot test: Place a drop of the second part on a drop Extract the remaining residue with 1 cm of Flame test: Take a speck of the dry residue at the tip of a
reaction paper and add a drop of sodium dilute HCl and divide into two parts. To one part, charred match stick and introduce into a colourless Bunsen
rhodizonate reagent. A red stain is produced due to add saturated CaSO4 solution. A scanty white flame near the base. The flame is coloured brick red, indicating
the formation of barium rhodizonate. precipitate of SrSO4 is obtained. Ca.

3
Presence of Ba(II) is confirmed. Spot test: Place a drop of the second part on a Spot test: Extract the remaining residue with 1 cm of dilute
drop reaction paper and add a drop of sodium acetic acid. Place a drop of it on a spot plate and add two drops
rhodizonate reagent. A reddish brown stain is of picrolinic acid reagent. A white precipitate of calcium
produced due to the formation of strontium picrolinate is produced.
rhodizonate.
Presence of Ca(II) is confirmed.
Presence of Sr(II) is confirmed.

12

12
 Table 6 Table 7 (Other Radicals)
3
Dissolve the Ppt in 2 cm of dilute HCl. The Solution is used as follows The Cations of this group are generally water soluble, hence they are detected from the water extract.
3
Water is prepared by boiling 0.2g of the mixture with 1 cm of water. It is centrifuge after cooling and the
centrifugate is used as follows.

For magnesium For lithium

1) Two drops of the solution in a test tube + 4N NH 4 OH, and then NH 3 1) Flame test: To two drops of the test solution in a china dish, add a drop of conc. HCl and evaporate to
3
solution drop wise till smell persists. Add 1 cm 3% Oxine reagent dryness. Take a speck of the dry residue at the tip of a charred match stick and introduce into a
in CHCl3.Shake well and centrifuge – Yellowish Green layer colourless Bunsen flame near the base. The flame is coloured carmine red, indicating Li.
3 2) Spot test: Place a drop of the test solution on a spot plate. Add a drop of NaCl solution and a
2) Two drops of solution in a test tube + 0.5cm of 10% NaOH + 2-3
drops of 0.1% Titan Yellow Reagent ,Centrifuge it – Red Ppt or drop of ferric periodate reagent. A white precipitate of KLiFe[IO6] is formed.
Colour. Presence of Li(I) is confirmed.
3) Two drops of solution in a test tube + 2 drops of 1N NaOH Solution
+ 2 drops of 0.001 % p-nitrobenzene azo resorcinol (Magneson-I) For Potassium
3
reagent – A blue colour or precipitate is obtained (which is different 1. Take 5-6 drops of water extract and add 0.5 cm of 4N NaOH solution to it .Boil strongly to remove
+
from the violet colour of the reagent). This is due to adsorption of the NH4 as NH3 gas, cool the solution and used as follows
dye on the precipitated Mg(OH)2. Acidify 2-3 drops of solution with 4N CH3COOH and add 3-4 drops of 5% Na2Co(NO2)6 solution to it
4) 2 drops of solution + 3-4 drops of freshly prepared hypo iodide .shake well and allow it to stand for about 10-15 sec – A yellow Crystalline Ppt
+
reagent – reddish brown Ppt. , K Present
C.T.
Presence of Mg(II) is confirmed. a) 3 drops of the solution (free from NH3) are treated with 4-5 drops of saturated picric acid solution
.On shaking Well a - A yellow Crystalline Ppt
+
b) 2 drops of the solution (free from NH4 ) + 3-4 drops of 50% EtOH + 4-5 drops of saturated
tartaric acid solution – White Ppt
Spot Test : A drop of solution on a paper containing 1% Dipicryl amine reagent – orange red
spot developed
For Sodium
Flame Test : Perform flame test with the mixture- Golden Yellow Flame
+
Na Confirm

Report:
The cations in the given solution are: (1) ______ (2) ______ (3) ______ and (4) ______ 13

13
 Reagents required for Inorgnic Qualitative Analysis
General: (2 molar) HCl, NH3, (NH4)2CO3, NaOH, K2CrO4, Na2S2O3, KI, FeSO4, SnCl2, HOAc, Amm. polysulphide, Na2CO3, Amm. acetate, MgNO3,
AgNO3, amm. molybdate, CuSO4, BaCl2, pot. ferrocyanide, mercuric chloride, Pb(NO3)2, amm. fluoride,

Conc.: HCl, H2SO4, HNO3, NH3, H2O2, HOAc,

Saturated: NaHtartrate (or tartaric acid), Na hexanitritocobaltate, CaSO4solution, Na2HPO4solution, oxine reagent (Mg),

Solid: NH4Cl, KNO2, KClO3, sod.sulphite, iron filings, oxalic acid, amm. nitrite, PbO 2, amm. acetate, Amm. (or Pot.) thiocyanate, sodium bismuthate

Spot test
Nessler’s reagent (for ammonium) diphenylcarbazide (Cr)
Pot. Nitrite (Hg) dimethyl glyoxime (Ni)
K2CrO4 (Ag) sodium bismuthate (Mn)
SnCl2 (W, Mo) amm.mercurothiocyanate (Zn)
Amm.sulphide (Pb) sodium rhodizonate (Ba, Sr)
KI (Tl) picrolinic acid reagent (Ca)
Pot. Thiocyanate (Hg, Mo, Co) magneson reagent (Mg)
Thiourea (Bi, Se) ferric periodate reagent (Li)
Tartaric acid (Cu)
Cadion-2B (Cd)
AgNO3 (As)
Hypophosphorus acid (Te)
Bismuth nitrate (Sn)
Rhodamine B (Sb)
Catechol (Ti)
Alizarin-S (Zr, Al)
Anthranilic acid (Ce)
Pot. ferrocyanide (Th, U)
CuSO4 (V)
14

14
 Procedure for Preparation of Reagents for Inorganic Qualitative Analysis
[Cation solutions for analysis are generally 5% aqueous solutions of their nitrates. When nitrates are not easily available commercially, some other soluble salt is used; for
3
example ammonium molybdate for molybdenum, lithium carbonate dissolved in dil.HNO 3 for lithium etc. About 2.5cm of each of the four cations are mixed together and
given. Care should be taken to avoid precipitation of other ions in the mixture if other anions like chloride or sulphate or phosphate are used.]
3 3
General (1 cm = 1 mL, 1 dm = 1 L) Keep all reagent bottles stoppered!
3 3
1. Acetic acid (dilute) - Dilute 114 cm of glacial acetic acid to 1 dm with distilled water.
3
2. Ammonium carbonate solution – Dissolve 96 g ammonium carbonate in distilled water and dilute to1 dm .
3
3. Ammonium fluoride solution - dissolve 1 g NH4F in 250 cm of distilled water.
3 3
4. Ammonium molybdate solution – Dissolve 11 g crystalline ammonium molybdate in a mixture of 15 cm conc. NH3 and 10 cm water. Add 30 g ammonium
3
nitrate and after complete dissolution, dilute to 250 cm with distilled water.
5. Ammonium polysulphide (yellow ammonium sulphide) solution –
3 3
Dilute 140 cm of conc. NH3 solution with distilled water to 1 dm and divide into two equal portions. Saturate one portion with H2S gas (use fume cupboard!).
Then add the second portion and mix. Add 32 g sulphur and heat gently until dissolved to give a yellow solution.
3 3
6. Ammonia solution (dilute) - dilute 140 cm of concentrated NH3 solution to 1 dm with distilled water.
3
7. Barium chloride solution - dissolve 15 g BaCl2.2H2O in 250 cm of distilled water.
3
8. Copper sulphate solution - dissolve 15 g CuSO4.5H2O in 250 cm of distilled water.
3
9. Ferrous sulphate solution - Add 5 drops of conc. H2SO4 in 250 cm of distilled water and dissolve 35 g FeSO4.7H2O in it.
3 3
10. Hydrochloric acid (dilute) – dilute 175 cm of concentrated acid to 1 dm with distilled water.
3
11. Lead nitrate solution - dissolve 20 g PbNO3 in 250 cm of distilled water.
3
12. Mercuric chloride solution - dissolve 4 g HgCl2 in 250 cm of distilled water.
3
13. Potassium ferrocyanide solution - dissolve 2.5 g K4Fe(CN)6.3H2O in 250 cm of distilled water.
3
14. Potassium chromate solution - dissolve 20 g K2CrO4 in 1 dm of distilled water.
3
15. Potassium iodide solution - dissolve 8 g KI in 250 cm of distilled water.
3
16. Silver nitrate solution - dissolve 5 g AgNO3 in 250 cm of distilled water. (Dark bottle).
3
17. Sodium carbonate solution – dissolve 13 g anhydrous Na2CO3 in 250 cm of distilled water.
3
18. Sodium hydroxide solution – dissolve 20 g NaOH pellets in 250 cm of distilled water.
3
19. Sodium thiosulphate solution - dissolve 6 g Na2S2O3.5H2O in 250 cm of distilled water.
3 3 3
20. Stannous chloride solution – Add 25 cm of conc. HCl to 25 cm of distilled water, mix and cool. Dissolve 14 g SnCl2.2H2O and dilute to 250 cm . Place a
granule of tin metal at the bottom of the bottle to prevent oxidation.

15
 Procedure for Oreparation of Special reagents for Spot tests For inorganic analysis

3
1. Alizarin-S reagent - dissolve 100 mg of Alizarin-S in 100 cm distilled water.
3
2. Amm. (or Pot.) thiocyanate solution* – Dissolve 200 mg of the salt in 1 cm of acetone (*prepare only before use).
3
3. Amm.mercurothiocyanate* - Dissolve a crystal of amm. thiocyanate and a crystal of mercuric chloride in 1 cm water (*prepare only before use).
4. Amm.sulphide solution –
3 3
Dilute 14 cm of conc. NH3 solution with distilled water to 100 cm and divide into two equal portions. Saturate one portion with H2S gas. Then add the
second portion and mix. The solution should be colourless.
3
5. Anthranilic acid reagent – Dissolve 5 g anthranilic acid in 100 cm ethanol.
3 3 3
6. Bismuth nitrate solution – To 50 cm of distilled water, add 5 cm of conc. HNO3 cautiously. Dissolve 8 g Bi(NO3)3.5H2O and dilute to100 cm .
3
7. Cadion 2B reagent – dissolve 20 mg of Cadion 2B in 100 cm ethanol and add a drop of NaOH solution.
3
8. Catechol solution - dissolve 10 g of catechol in 100 cm distilled water.
3
9. Dimethyl glyoxime reagent – Dissolve 1 g dimethyl glyoxime in 100 cm ethanol.
3
10. Diphenylcarbazide* - Mix a small crystal of diphenylcarbazide with two drops of glacial acetic acid and add 1 cm ethanol (*prepare only before use).
3
11. Ferric periodate reagent - Dissolve 11 g KOH in 100 cm distilled water. Add 2 g pot. periodate and stir to dissolve well. Then add 250 mg FeCl3 and dissolve.
3 3
12. Hypophosphorus acid – Pour 20 cm of commercial HPO2 into 80 cm of distilled water and mix.
3
13. Magneson reagent – Dissolve 2 g NaOH in 100 cm distilled water. Dissolve 500 mg magneson in it.
14. Nessler’s reagent –
3 3
Dissolve 5 g of KI in 5 cm of ammonia-free distilled water (solution a). Dissolve 3 g mercuric chloride in 50 cm of ammonia-free distilled water (solution b). Add b
3
to a dropwise with shaking till a slight, permanent precipitate appears. To this, add another solution containing 20 g KOH in 50 cm of ammonia-free distilled water.
3
Dilute to 100 cm and keep overnight in a stoppered bottle. Decant the clear liquid into a reagent bottle and keep tightly stoppered, away from ammonia.
3
15. Picrolinic acid reagent* - Shake 200 mg of picrolinic acid with1 cm water and use the clear supernatant (*prepare only before use).
3
16. Pot. nitrite solution* – Dissolve 5 g KNO2 in 5 cm of distilled water (*prepare only before use).
3
17. Rhodamine B reagent - dissolve 10 mg of Rhodamine B in 100 cm distilled water.
3
18. Sodium rhodizonate* - Dissolve a crystal of sodium rhodizonate in 1 cm water (*prepare only before use).
3
19. Tartaric acid solution – Dissolve 15 g tartaric acid in 100 cm distilled water (fungus growth after a few weeks!).
3 3
20. Thiourea solution - To 50 cm3 distilled water, add 43 cm conc. HCl. Allow to cool and dissolve 5 g thiourea in it. Dilute to 100 cm with distilled water.

16
 II. Photo Colorimetric Estimation

1. Colorimetric Estimation of Copper:

Photoelectric colorimeter is used for the estimation of ions in colored solutions. Herein, Copper is estimated using Photoelectric
colorimetric method.

Objective:
To determine the amount copper present in the given sample by using colorimetric analysis.

Required Apparatus:
1. Standard flask (100ml)
2. Beaker
3. Photoelectric colorimeter

Required Chemicals:
1. CuSO4.5H2O
2. Ammonia
3. Water

17
Procedure:

 Prepare a stock solution of 0.005M of Cu2+ of CuSO4.5H2O. From this various concentration are prepared as given in the
tabular column.
 The colour is developed with 1:1 NH3 solution.
 The instrument is adjusted to zero using blank solution.
 The absorbance of the solutions are measured and recorded.
 The calibration graph is drawn by plotting absorbance vs concentration.
 The given test solution is made upto 100mL in a standard flask.
 The absorbance of the given test solution is measured and recorded.
 Determine the concentration of unknown Cu2+ from the calibration graph.

The amount of copper present in the whole of the given solution is calculated as,

x = (concentration of unknown Cu2+× 63.5) / 249.55

18
 Table 1: Colorimetric Estimation of Copper
S.No. Volume of Copper Volume of Volume of Total Concentration of Absorbance
sulphate 0.005M (mL) 1:1 NH3 water volume Copper sulphate
(mL) (mL) (mL) (M)
1 8 1 1 10
2 6 1 3 10
3 4 1 5 10
4 2 1 7 10
5 1 1 8 10
6 0 1 9 10
7 5 1 4 10
Calculations:
 Preparation of Standard Solution :
 Concentration of Copper sulphate solution :
 Amount of copper present in the test solution :
 Total amount of copper present in the whole of the given solution :

Report:
 Filter Wavelength :
 Weight of standard solution :
 Percentage of Cu2+ in the Standard solution :
 Molar absorptivity of test solution :
 Amount of copper present in the given solution :

19
2. Colorimetric Estimation of Nickel as Ni(DMG)2 complex:

Photoelectric colorimeter is used for the estimation of ions in colored solutions. Herein, Nickel is estimated using Photoelectric
colorimetric method.

Objective:
To determine the amount Nickel (II) present in the given sample by using colorimetric analysis.

Required Apparatus:
1. Standard flask (100 ml)
2. Pipette
3. Photoelectric colorimeter

Required Chemicals:
1. Nickel ammonium sulphate
2. DMG
3. Potassium persulphate
4. ethanol
5. Water

20
Procedure:

Colorimetric estimation of Ni3+ by Ni(DMG)2 complex.

 Weigh accurately 0.112g of Nickel ammonium sulphate.
 Transfer it carefully into a 100mL standard flask, dissolve it completely and make it up to the mark. This is stock-I.
 20 mL of stock-1 solution is pipetted out into a 250mL standard flask and made up to the mark. This is stock II.
 A series of Ni salt solution is prepared from stock II and colour is developed by adding 10mL of 5% K2S2O4 solution, 1mL of 1:1
NH3 and 1mL of dimethyl glyoxime in alcohol as given in the tabular column.
 Absorbance is measured at 510nm and calibration graph is drawn.
 The given test solution is transferred into a 100mL standard flask and made up to the mark.
 Burette out 30mL of this solution into a 50mL Nessler’s tube and colour is developed by adding required reagents as before.
 Measure Absorbance and interpolate in calibration graph. From this, determine the amount of Ni present in the given solution.
 Reference/Blank solution is prepared by adding 10mL of 5% K2S2O8 and 1mL of 1;1 NH3.
 The amount of Ni2+ present in the whole of the given solution is calculated as,

x = (concentration of unknown Nickel × 58.693) / 394.99

21
 Table 1: Colorimetric Estimation of Nickel as Ni(DMG)2 complex
S.No. Volume of Volume of Volume of Volume of Total volume [Nickel ammonium Absorbance
Stock II Persulphate 1:1 NH3 1% DMG of solution sulphate], M
(mL) (mL) (mL) (mL) (mL)

1 30 10 1 1 50
2 25 10 1 1 50
3 20 10 1 1 50
4 15 10 1 1 50
5 10 10 1 1 50
6 Unknown 10 1 1 50
Calculations:
 Preparation of Standard Solution :
 Concentration of Nickel salt solution :
 Amount of Nickel present in the given (test) solution :
 Total amount of Nickel present in the whole of the given solution :

Report:
 Filter Wavelength :
 Weight of standard solution :
 Molar absorptivity of test solution :
 Amount of Nickel present in the whole of the given solution :

22
3. Colorimetric Estimation of Iron by Fe-NH4SCN complex:

Photoelectric colorimeter is used for the estimation of ions in colored solutions. Herein, Iron is estimated using Photoelectric
colorimetric method.

Objective:
To determine the amount Fe3+ ion present in the given sample by using colorimetric technique

Required Apparatus:
1. Standard flask (100 ml)
2. Pipette
3. Photoelectric colorimeter

Required Chemicals:
1. Ferric ammonium sulphate
2. NH4SCN
3. Ethanol
4. Water

23
Procedure:

 Prepare a stock solution of 0.0002M of Fe3+ of ammonium ferric sulphate.

 From this various concentration are prepared as given in the tabular column.
 The colour is developed with 1:1 10% NH4SCN solution.
 The instrument is adjusted to zero using blank solution.
 The absorbance of the given solutions is measured and recorded.
 The calibration graph is drawn by plotting absorbance Vs concentration.
 The given test solution is made upto 100mL in a standard flask.
 The absorbance of the given test solution is measured and recorded.
 Determine the concentration of unknown from the calibration graph.

The amount of Fe3+ present in the whole of the given solution is calculated as,

x = (concentration of unknown Fe3+ × 55.845) / 482.19

24
 Table: Colorimetric estimation of Iron by Fe-NH4SCN complex
S.No. Volume of Ferric ammonium Volume of 1:1 Volume of Total volume of Concentration of Ferric Absorbance
sulphate 0.0002M(mL) NH4SCN water solution ammonium sulphate (M)
(mL) (mL) (mL)
1 8 1 1 10
2 6 1 3 10
3 4 1 5 10
4 2 1 7 10
5 1 1 8 10
6 0 1 9 10
7 5 1 4 10
Calculations:
 Preparation of Standard Solution :
 Concentration of Ferric Ammonium Sulphate solution :
 Amount of Iron ion present in the test solution :
 Total amount of Fe3+ ion present in the whole of the given solution :

Report:
 Filter Wavelength :
 Weight of standard solution :
 Concentration of the Standard solution :
 Molar absorptivity of test solution :
 Amount of iron present in the given solution :

25
 III. Preparation
1. Preparation of Potassium tris (oxalate) aluminate (III) trihydrate:

Aluminium is a chemical element in the boron group with symbol Al and atomic number 13. It is a silvery-white, soft,
nonmagnetic, ductile metal. Aluminium is the third most abundant element (after oxygen and silicon) in the Earth's crust, and the most
abundant metal there. It makes up about 8% by mass of the crust, though it is less common in the mantle below. Aluminium metal is so
chemically reactive that native specimens are rare and limited to extreme reducing environments. Instead, it is found combined in over
270 different minerals. The chief ore of aluminium is bauxite.
Aluminium is remarkable for the metal's low density and for its ability to resist corrosiondue to the phenomenon of passivation.
Structural components made from aluminium and its alloys are vital to the aerospace industry and are important in other areas of
transportation and structural materials, such as building facades and window frames. The most useful compounds of aluminium,
at least on a weight basis, are the oxides and sulfates.
Oxalate ethanedioate is the dianion with the formula C2O42−, also written (COO)22−. Either name is often used for derivatives,
such as salts of oxalic acid, for example sodium oxalateNa 2C2O4, or dimethyl oxalate ((CH3)2C2O4). Oxalate also forms coordination
compounds where it is sometimes abbreviated as ox.

26
The Equation of the Experiment:
2Al + 2OH- + 6H2O 2[Al(OH)4]- + 3H2
2H2O

2C2O4= + [Al(OH)4(H2O)2]-

3K+ [Al(C2O4)3]3-.3H2O

K3[Al(C2O4)3].3H2O
Required Apparatus:
1. Beaker
2. Measuring cylinder
2. Conical flask
3. Filter paper
4. Glass rod
5. Watch glass
6. Spatula
7. Buchner funnel

Required Chemicals:
1. Aluminum shavings
2. Potassium hydroxide

27
 3. Oxalic acid dehydrates
4. Ethanol
5. Distilled water

Procedure:
Dissolve 1.75 g of potassium hydroxide in 4 ml of distilled water. Then, put aluminum shavings 0.05 g to the solution when the
evolution of the hydrogen gas is stopped; heat the solution to boiling to dissolve aluminum. Filter the solution and then add to the filtrate
(0.75 g of oxalic acid dissolve in 2.5 ml of distilled water) drop wise. Then cool the solution to room temperature by ice-bath, and then
add 10 drops of ethanol. Scratch the beaker well and stir well to help crystallization. Filter the crystals, wash them with ethanol and dry at
room temperature. Weigh and report the synthesized Potassium tris (oxalate) aluminate (III) trihydrate crystals.

2. Preparation of Potassium tris (oxalato) chromate (III) trihydrate:

The experiment is based on the following equation:

H2 O
K2Cr2O7 + 7H2C2O4 + K2C2O4 K3[Cr(C2O4)3] + 6CO2 + H2O

Required Apparatus:
1. Beaker
2. Conical flask
3. Buchner funnel
4. Filter paper

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 5. Glass rod
6. Watch glass
7. Spatula

Required Chemicals:
1. Potassium dichromate
2. Potassium oxalate monohydrate
3. Oxalic acid dehydrate
4. Potassium iodide
5. Sodium hydroxide
6. Potassium permanganate
7. Oxalic acid
8. Starch solution
9. Sulphuric acid
10. Silver nitrate
11. Ammonoium persulphate
12. Sodium thiosulphate
13. Distilled water

Procedure:
Make a solution of potassium oxalate monohydrate (2.3 g) and oxalic acid dihydrate (5.5 g) in water (110-120 ml). To this
solution add solid potassium dichromate (1.9 g) in small portions with constant stirring. Concentrate the solution nearly to dryness. On

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cooling deep green shiny crystals of Potassium tris-oxalate chromium (III) trihydrate will be formed. Filter the solid and dry by pressing
between filter paper. Weigh and report the synthesized Potassium tris-oxalate chromium (III) trihydrate crystals.

3. Preparation of Tris (thiourea) copper (I) sulphate:

The experiment is based on the following equation:

16Cu2+(aq) + 8(H2N)2CS(aq) + 16H2O(l) 16Cu+(aq) + S8(s) + 16NH4+ (aq) + 8CO2(g)
Cu+(aq) + 3(H2N)2CS(aq) [Cu{(H2N)2CS}3]+(aq)

Required Apparatus:
1. Burette
2. Measuring cylinder
3. Buchner funnel
4. Filter paper
5. Conical flask
6. Beaker
7. Evaporating disc
8. Conical flask

Required Chemicals:
1. Sodium thiosulphate
2. Thiourea solution

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 3. Copper sulphate solution
4. Copper(II)pentahydrate
5. Distilled water
6. Starch indicator

Procedure:
Initially, thiourea solution was prepared by dissolving thiourea (2.5g) in water (15ml), Copper sulphate solution was
prepared by dissolving Copper (II) pentahydrate (2.5g) in water (15ml), thiourea solution was prepared by dissolving thiourea (1.0g)
in water (30 ml).
To the cold solution of thiourea was added a cold solution of copper (II) sulphate with constant stirring. The solution was
then left to stand for about ten minutes. When oil drops on the sides of the beaker appeared, to this was added a cold solution of
thiourea (1.0g) in water (10ml) and stirred vigorously to effect complete crystallization.
The reaction mixture was allowed to stand for five minutes and the white crystals ware filtered off. They were then
recrystallized from a thiourea solution [thiourea (0.150g) in water (30 ml) plus sulphuring acid (5 drops)] heated first to 75ºC and
then cooled to form pure crystals. The crystals were filtered and then washed with several portions of water (5 ml) and ethanol (5
ml). Weigh and report the synthesized Tris (thiourea) copper (I) sulphate crystals.

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4. Preparation of Tris Sodium hexanitrocobaltate (III):

Required Apparatus:
1. Test tube
2. Measuring cylinder
3. Conical flask
4. Beaker
5. Filter flask with filter paper
6. Glass rod

Require Chemicals:
1. Sodium nitrite
2. Cobalt nitrate hexahydrate
3. Acetic acid
4. Ethanol
5. Distilled water

Procedure:
Dissolve pure potassium‐free sodium nitrite (6g) in hot water (8mL) (in a 50ml test tube). After cooling the solution to 50C,
dissolve cobalt nitrate hexahydrate (2g) into the liquid. With continuous stirring using a glass rod, 50% acetic acid (2mL) is added
drop wise from a separating funnel and the dark brown solution is transferred (in the test tube) to a filter flask fitted with a stopper

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and an inlet tube leading almost to the bottom of the vessel. A steady stream of air is drawn through the solution for twenty minutes
to remove excess oxides of nitrogen; some product may crystallize out during the aeration.
The liquid and any solid that has formed (the more vigorous the air current the more material tends to Settle out) are
now placed in a beaker and surrounded by an ice bath. From a dropping funnel 95% alcohol (15 mL) is added slowly with agitation,
and the mixture is then allowed to crystallize in the cold for twenty minutes. The orange‐brown product is filtered by suction and the
mother liquor is set aside. The material is washed three times with alcohol (5 mL); the final washing should be almost colourless.
The crystals are dried in air. Weigh and report the synthesized Tris Sodium hexanitrocobaltate (III) crystals.

5. Preparation of Chloropentammine cobalt (III) chloride:

The product forms according to this equation:

2 CoCl2 • 6H2O + 4 NH4Cl + 8 NH3 + H2O2 2 [Co(NH3)5Cl)]Cl2 + 14 H2O

Required Apparatus:
1. Erlenmeyer flask
2. Measuring cylinder
3. Conical flask
4. Beaker
5. Filter flask with filter paper
6. Glass rod
7. Dropper
8. Test tube

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Require Chemicals:
1. Ammonium chloride
2. Ammonium hydroxide
3. Cobalt chloride hexahydrate
4. Hydrogen peroxide
5. Ethanol
6. Hydrochloric acid
7. Distilled water

Procedure:
In a 125-mL Erlenmeyer flask, dissolve 15 mmol ammoniumchloride in 12ml of concentrated ammonium hydroxide.
To this solution add 7 mmol cobalt (II) chloride hexahydrate solid. Stir with a magnetic stirbar until all of the salt dissolves and
a brown slurry is formed.
Take 1.5 ml of 30% hydrogen peroxide solution into a small test tube. While continuing to stir, add the hydrogen
peroxide with a dropper, adding 1-2 drops every 15-30 seconds. Wait for the bubbling to subside after all of the peroxide is
added. Obtain 7ml of conc. hydrochloric acid. Using a disposable dropper, add ~1 ml portions while maintaining continuous
stirring; wait until the bumping subsides before adding subsequent portions.
Continue to stir and set the hotplate on a low setting. Using the hotplate, maintain a temperature of 80-85°C for 30
minutes. Next, allow the mixture to cool to room temperature. While waiting, cool 15 ml water and 10mL of 95% ethanol in an
ice water bath. Once cooled, filter the product by vacuum filtration. Wash the product on the filter two times with about 5 ml of

34
ice cold water, then two times with ice cold ethanol, then three times with acetone. Set aside to dry and obtain mass of product
and filtered. Weigh and report the synthesized Chloropentammine cobalt (III) chloride crystals.

6. Preparation of Bis (acetylacetonato) copper (II):

Required Apparatus:
1. Glass rod
2. Dropper
3. Measuring cylinder
4. Buchner funnel
5. filter paper
6. Beaker
7. Spatula

Required Chemicals:
1. Copper (II) nitrate
2. Water
3. Ammonia
4. Acetyl acetone
5. Distilled water

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Procedure:

6g of copper (II) nitrate (Cu (NO₃)₂∙3H₂O) was dissolved in 60 ml of water. The solution of 1:1 ammonia was slowly
added with stirring until the precipitate first formed had just redissolved. The solution was continuing to stir then 6 ml of acetyl
acetone was added drop wise. The crude product was filtered off by using suction filtration. Then it was washed well with
water, drained thoroughly and filtered. Weigh and report the synthesized Bis (acetylacetonato) copper (II) crystals.

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