M.Sc.

CHEMISTRY LAB MANUAL

1st Semester

Prepared By
Pure & Applied Science Dept.
Chemistrty

MIDNAPORE CITY COLLEGE

Chemistry Lab Manual Dept. of Pure & Applied Science

PREFACE TO THE FIRST EDITION

This is the first edition of Lab Manual for PG Chemistry first semester. Hope this edition will help
in practical. This edition mainly tries to cover the whole syllabus. Some hard core instrument
based topic are not present here that will be guided by responsive teachers at the time of practical.

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ACKNOWLEDGEMENT

We are really thankful to our students, teachers , and non-teaching staffs to make this effort little
bit complete.
Mainly thanks to Director and Principal Sir to motivate for making this lab manual.

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Chemistry Lab Manual Dept. of Pure & Applied Science

Laboratory Practice Safety Rules

1. Use safety glass when dealing with fire and chemical.

2. Should use front cover clothes during biochemistry practical.
3. Always use hand wash after dissection and any type of chemical use.
4. Carefully handle needles , forceps, microscope and any other dissecting instrument.
5. Use dustbin always.

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INDEX

Sl. No. CONTENT PAGE No.

CEM-195, Inorganic Practical Paper
1. Synthesis and Characterization of inorganic compounds 5
2. Synthesis and Characterization of inorganic compounds 8
3. Synthesis and characterization of [Cu(NH3)4(SO4)(H2O)] 11
4. Synthesis and Characterization of inorganic compounds 14

5. Synthesis and characterization of Potassium Trisoxalatoferrate(III) 17

Trihydrate, K3[Fe(C O ) ].3H O

6. Synthesis and characterization of potassium tris oxalato chromate (III) 20

trihydrate

7. Synthesis and characterization [K SO ,Cr (SO ) ,24H O] 22

8. Equilibrium studies on inorganic reaction 24
9. Spectrophotometric Estimation 27
10. Gravimetric estimation of Ni(II) as Ni(DMGH) 29

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CEM-195 Inorganic Practical Paper

1. Synthesis and Characterization of inorganic compounds:

1A. REINECKE SALT

Experimental:
A. Chemicals: Apparatus:
1. Alcohol 1. Thermometer
2. Ammonia 2. Magnetic stirrer and heater
3. Ammonium chloride 3. Suction
4. Ammonium thiocyanate 4. Large beaker
5. Hydrogen cyanide
6. Acetone
7. Potassium dichromate
8. Ammonium dichromate

Synthesis of Reinecke Salt:

B. Procedure:
Eight hundred grams (10.5 moles) of ammonium thiocyanate is gently heated, by means of
three small flames (Note 1), in a white enameled cooking pot of about 4-l. capacity. The mass
is stirred with a thermometer enclosed in a glass tube until the solid has partially melted and
the temperature has reached 145–150°. At this point an intimate mixture of 170 g. (0.675
mile) of finely powdered ammonium dichromate and 200 g. (2.6 moles) of ammonium
thiocyanate is added in portions of 10–12 g. with constant stirring. After about ten such
portions have been added a fairly vigorous reaction takes place with evolution of ammonia
and the temperature rises to 160°. The flames are extinguished, and the remainder of the
mixture is added at such a rate that the heat of reaction maintains the temperature at
160° (Note 2). Stirring is continued while the mass cools, and any lumps of solid which form
around the sides of the vessel are broken loose (Note 3). The product, while still warm (Note
4), is finely powdered and stirred with 750 cc. of ice water in a large beaker. After fifteen
minutes the insoluble portion is filtered by suction, freed as completely as possible from
mother liquor without washing (Note 5), and stirred into 2.5 l. of water previously warmed to
65°. The temperature is then rapidly raised to 60° (Note 6), the solution is filtered at once
through a hot-water funnel, and the filtrate is placed in a refrigerator overnight.

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The resulting crystals are collected and the mother liquor employed for a second similar
extraction of the residue at 60°. This yields a further crop of crystalline Reinecke salt. The
mother liquor is finally concentrated to 250–300 cc. by evaporation at 40–50° under reduced
pressure, when a small third crop (12–13 g.) is obtained. The total yield of air-dried crystals
is 250–275 g. (52–57 per cent of the theoretical amount) (Note 7). The undissolved residue
from the second extraction consists chiefly of Morland salt (the guanidine
salt of the Reinecke acid) and amounts to 130–135 g. (33–34 per cent of the theoretical
amount) (Note 8).

C. NOTES
1. Heat must be applied as uniformly as possible.
2. The addition of the mixture requires five to seven minutes.
3. The product is detached from the walls during cooling as it is difficult to remove
when cold.
4. The material should be pulverized while warm before it has had an opportunity to
attract moisture from the air.
5. The filtrate, which consists largely of unchanged ammonium thiocyanate and its
decomposition products, contains too little Reinecke salt to repay further
treatment.
6. Reinecke salt decomposes in aqueous solution with formation of a blue color and
free hydrogen cyanide. At room temperature this decomposition occurs in about
two weeks, and above 65° it takes place quite rapidly. A similar decomposition
takes place in boiling alcohol.
7. Reinecke salt is of value as a precipitant for primary and secondary amines,
proline and
hydroxyproline, and certain amino acids.1
8. The Morland salt, which is soluble in acetone, contains a small proportion of a
colorless sulfur compound insoluble in hot water. It can be partially converted into
Reinecke salt by treatment in dilute ammonia solution with a large excess of
ammonium chloride, but the amounts so obtainable are unprofitably small.

D. Yield: ………………………
E. Melting Point: …………….
F. Chemical Formula and structure of Reinecke's salt:
It is a chemical compound with the formula NH4[Cr(NCS)4(NH3)2]·H2O. The dark-
red crystalline compound is soluble in boiling water, acetone, and ethanol. The chromium
atom is surrounded by six nitrogen atoms in an octahedral geometry. The NH3 ligands are
mutually trans and the Cr–NCS groups are linear. The salt crystallizes with one molecule of
water. NH4[Cr(NCS)4(NH3)2] is prepared by treatment of molten NH4SCN (melting point
around 145–150 °C) with (NH4)2Cr2O7.

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G. Discussion:

Reinecke salt has been prepared by adding either potassium dichromate or ammonium
dichromate to fused ammonium thiocyanate.

H. References and Notes:

1. Kapfhammer and Eck, Z. physiol. Chem. 170, 310 (1927); Grassmann and Lang,
Biochem. Z.269, 223 (1934).
2. Reinecke, Ann. 126, 113 (1863); Christensen, J. prakt. Chem. (2) 45, 213 (1892);
Zeleny and Gortner, J. Biol. Chem. 90, 430 (1931).
3. Werner, Z. anorg. Chem. 15, 260 (1897); Ann. 406, 276 (1914).

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1. Synthesis and Characterization of inorganic compounds:

1B. [Co(NH3)6]Cl3 :
Since CoCl3 is not available (the Co3+ would oxidise chloride to chlorine gas), [Co(NH3)6]Cl3
is prepared from cobalt(II) chloride using a redox synthesis. The latter is treated with
ammonia and ammonium chloride followed by oxidation. Oxidants include hydrogen
peroxide or oxygen in the presence of charcoal catalyst.

2CoCl2 + 10NH3 + 2NH4Cl + H2O2 → 2[Co(NH3)6]Cl3 + 2H2O ………………..…….. (1)

4CoCl2 + 4NH4Cl + 20NH3 + O2 → 4[Co(NH3)6]Cl3 + 2H2O …………………….…. (2)
4Co(C2H3O2)2.4H2O + 4NH4C2H3O2 + 20NH3 + O2 + 12HCl → 4[Co(NH3)6]Cl3 + 18H2O +
12CH3COOH ………………………..(3)

Experimental:
A. Chemicals: Apparatus:
1. Alcohol 1. Thermometer
2. Ammonia 2. Magnetic stirrer and heater
3. Ammonium chloride 3. Suction
4. Hydrogen Peroxide 4. Large beaker
5. Cobalt Chloride
6. Charcoal catalyst
7. Cobalt acetate
8. Ammonium acetate

Synthesis of Reinecke Salt:

B. Procedure:
Eight hundred grams (10.5 moles) of ammonium thiocyanate is gently heated, by means of
three small flames (Note 1), in a white enameled cooking pot of about 4-l. capacity. The mass
is stirred with a thermometer enclosed in a glass tube until the solid has partially melted and
the temperature has reached 145–150°. At this point an intimate mixture of 170 g. (0.675
mole) of finely powdered ammonium dichromate and 200 g. (2.6 moles) of ammonium
thiocyanate is added in portions of 10–12 g. with constant stirring. After about ten such
portions have been added a fairly vigorous reaction takes place with evolution of ammonia
and the temperature rises to 160°. The flames are extinguished, and the remainder of the
mixture is added at such a rate that the heat of reaction maintains the temperature at
160° (Note 2). Stirring is continued while the mass cools, and any lumps of solid which form
around the sides of the vessel are broken loose (Note 3). The product, while still warm (Note
4), is finely powdered and stirred with 750 cc. of ice water in a large beaker. After fifteen
minutes the insoluble portion is filtered by suction, freed as completely as possible from
mother liquor without washing (Note 5), and stirred into 2.5 l. of water previously warmed to
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Chemistry Lab Manual Dept. of Pure & Applied Science

65°. The temperature is then rapidly raised to 60° (Note 6), the solution is filtered at once
through a hot-water funnel, and the filtrate is placed in a refrigerator overnight.

The resulting crystals are collected and the mother liquor employed for a second similar
extraction of the residue at 60°. This yields a further crop of crystalline Reinecke salt. The
mother liquor is finally concentrated to 250–300 cc. by evaporation at 40–50° under reduced
pressure, when a small third crop (12–13 g.) is obtained. The total yield of air-dried crystals
is 250–275 g. (52–57 per cent of the theoretical amount) (Note 7). The undissolved residue
from the second extraction consists chiefly of Morland salt (the guanidine
salt of the Reinecke acid) and amounts to 130–135 g. (33–34 per cent of the theoretical
amount) (Note 8).

C. NOTES
1. Heat must be applied as uniformly as possible.
2. The addition of the mixture requires five to seven minutes.
3. The product is detached from the walls during cooling as it is difficult to remove
when cold.
4. The material should be pulverized while warm before it has had an opportunity to
attract moisture from the air.
5. The filtrate, which consists largely of unchanged ammonium thiocyanate and its
decomposition products, contains too little Reinecke salt to repay further
treatment.
6. Reinecke salt decomposes in aqueous solution with formation of a blue color and
free hydrogen cyanide. At room temperature this decomposition occurs in about
two weeks, and above 65° it takes place quite rapidly. A similar decomposition
takes place in boiling alcohol.
7. Reinecke salt is of value as a precipitant for primary and secondary amines,
proline and
hydroxyproline, and certain amino acids.1
8. The Morland salt, which is soluble in acetone, contains a small proportion of a
colorless sulfur compound insoluble in hot water. It can be partially converted into
Reinecke salt by treatment in dilute ammonia solution with a large excess of
ammonium chloride, but the amounts so obtainable are unprofitably small.

D. Yield: …………………..
E. Melting Point: …………

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F. Chemical formula and structure of Reinecke's salt:

Hexaamminecobalt(III) chloride is the chemical compound with the formula [Co(NH3)6]Cl3.
This salt consists of [Co(NH3)6]3+ cations, each accompanied by three Cl− anions. The cation
itself is a metal ammine complex with six ammonia molecules as ligands on the cobalt atom.
[Co(NH3)6]3+ is diamagnetic, with a low-spin 3d6 octahedral Co(III) center. The cation obeys
the 18-electron rule and is considered to be a classic example of an exchange inert metal
complex. As a manifestation of its inertness, [Co(NH3)6]Cl3 can be recrystallized unchanged
from concentrated hydrochloric acid: the NH3 is so tightly bound to the Co(III) centers that it
does not dissociate to allow its protonation. In contrast, labile metal ammine complexes, such
as [Ni(NH3)6]Cl2, react rapidly with acids, reflecting the lability of the Ni(II)–NH3 bonds.
Upon heating, hexamminecobalt(III) begins to lose some of its ammine ligands, eventually
producing a stronger oxidant.

G. Discussion:

Reinecke salt has been prepared by adding either potassium dichromate or ammonium
dichromate to fused ammonium thiocyanate.

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H. References:

1. Huheey, James E. (1983). Inorganic Chemistry (3rd ed.). p. 360.

2. Bjerrum, J.; McReynolds, J. P. (1946). "Hexamminecobalt(III) Salts". Inorg.
Synth. 2: 216–221. doi:10.1002/9780470132333.ch69.
3. Fremy, M. E. (1852). "Recherches sur le cobalt". Ann. Chim. Phys. 35: 257–312.
4. Lindholm, R. D.; Bause, Daniel E. (1978). "Complexes of Cobalt Containing
Ammonia or Ethylene Diamine: Hexaamminecobalt(III) Salts". Inorg. Synth. 18:
67–69. doi:10.1002/9780470132494.ch14.
5. Ramakrishnan, B.; Sekharudu, C.; Pan, B.; Sundaralingam, M. (2003). "Near-
atomic resolution crystal structure of an A-DNA decamer d(CCCGATCGGG):
cobalt hexammine interaction with A-DNA". Acta Crystallogr. D59: 67–
72. doi:10.1107/s0907444902018917. PMID 12499541.
6. Rudisser, S.; Tinoco, I., Jr. (2000). "Solution structure of Cobalt(III)hexammine
complexed to the GAAA tetraloop, and metal-ion binding to G.A mismatches". J.
Mol. Biol. 295: 1211–1232. doi:10.1006/jmbi.1999.3421. PMID 10653698.
7. McPherson,, Alexander (2002). Introduction to Macromolecular Crystallography.
John Wiley & Sons. ISBN 0-471-25122-4.

1. Synthesis and characterization of [Cu(NH3)4(SO4)(H2O)]:

1C. Preparation of [Cu(NH3)4(SO4)(H2O)] complex:
From a solution containing copper(II) ions insoluble basic salts can be precipitated by the
action of ammoniumhydroxide. The light blue precipi tate dissolves in the excess of NH4OH,
forming dark blue [Cu(NH3)4]2+ complex ions. Reacting copper(II)sulfate with excess
ammoniumhydroxide results in a dark blue sol ution, from which [Cu(NH3)4]SO4∙ H2O can
be crystallized.

2 CuSO4(aq) + 2 NH4OH(aq) = Cu2(OH)2SO4(s) + (NH4)2SO4(aq)

Cu2(OH)2SO4(s) + (NH4)2SO4(aq) + 6 NH4OH(aq) = 2 [Cu(NH3)4]SO4(aq) + 8 H2O(l)

EXPERIMENTAL:
A. Chemicals: Apparatus:
1. Copper sulphate 1. Mortar
2. Ammonium hydroxide 2. Magnetic stirrer and heater
3. Methanol 3. glass filter

Synthesis of [Cu(NH3)4(SO4)(H2O)] complex:

B. procedure:
Grind 6.2g CuSO4 ∙5H2O in a mortar and add it to the solution of 15 cm3 concentrated
ammoniumhydroxide and 10 cm3water. In order to decrease the solubility add 15 cm3

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methanol to the solution slowly while stirring. The solution is stored for three hours in a
cool place. The formed dark blue crystals are separated on a glass filter and washed with
25 cm3of 1:1 mixture of methanol and NH4OH. Finally the crystals are rinsed with
methanol and dried in air stream. Since methanol is flammable, avoid working close to a
flame.

C. NOTES
1. Heat must be applied as uniformly as possible.
2. The addition of the mixture requires five to seven minutes.
3. Separation should be done by glass filter and washed with 25 cm3of 1:1 mixture of
methanol and NH4OH solution.
D. Yield: …………………..
E. Melting Point: …………

F. Chemical Formula and structure of Tetraamminecopper(II) sulphate complex:

The solid state salt of tetraamminecopper(II) sulfate contains the [Cu(NH3)4H2O]SO4, which
has a square pyramidal molecular geometry. The bond length between the atoms in the
crystal are measured using X-ray crystallography; the Cu-N and Cu-O distances are about
210 and 233 pm. Cu(NH3)The correct concentrations of ammonia and copper sulfate solution
can be determined by colorimetry. The combination of the correct concentrations will
produce the highest absorbance read out on the colorimeter and as a result the formula of the
complex can be verified.

Structure of Tetraamminecopper(II) sulphate complex

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G. Discussion:

The deep blue crystalline solid tends to hydrolyse and evolve (release) ammonia upon
standing in air. It is fairly soluble in water. The brilliant dark blue-violet color of
tetraamminecopper(II) sulfate solution is due to presence of [Cu(NH3)4]2+. Often, the dark
blue-violet color is used as a positive test to verify the presence of Cu2+ in a solution.

Tetraamminecopper(II) sulphate complex

H. References and Notes:

1. O. Glemser, H. Sauer "Tetraamminecopper (II) Sulfate" Handbook of Preparative

Inorganic Chemistry, 2nd Ed., Academic Press, 1963, NY. Vol. 1. p. 1021.
2. Jump up to: American Elements – The material science company; tetraammine
copper(II) sulfate monohydrate; CAS 10380-29-7
3. Morosin "The Crystal Structures of Copper Tetraammine Complexes. A. and "
Acta Crystallogr. 1969, vol. B25, pp. 19-30. doi:10.1107/S0567740869001725
4. Li, Yudan; Wang, Wenjie; He, Chuan.; Chemical reduction method for preparing
copper nanopowder with high purity using sodium hypophosphite as reductant,
Faming Zhuanli Shenqing, Dec 4, 2013, CN 103418801

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1. Synthesis and Characterization of inorganic compounds:

1D. Synthesis of [Co(NH3)5Cl]Cl2 compound:

The complex is prepared with a two-step process starting with oxidizing a solution of cobalt
chloride and ammonia.
2 CoCl2·6H2O + 10 NH3 + 2 HCl + H2O2 → 2 [Co(NH3)5(OH2)]Cl3 + 12 H2O
This intermediate is then heated to induce coordination of one of the outer sphere chloride
ligands:
[Co(NH3)5(OH2)]Cl3 → [Co(NH3)5Cl]Cl2 + H2O

Experimental:
A. Chemicals: Apparatus:
1. Alcohol 1. Buchner funnel
2. Ammonia 2. Magnetic stirrer and heater
3. 30% H2O2 3. Suction
4. Cobalt(II) chloride-hexahydrate 4. ice bath
5. Concentrated HCl

Preparation of [Co(NH3)5Cl]Cl2:

B. Procedure:
In the fume hood, completely dissolve 6 g of NH4Cl in ~40 mls of concentrated ammonia in a
400 ml beaker. With continuous stirring, add 12 g of cobalt(II) chloride-hexahydrate in small
portions. With continued stirring of the resulting brown slurry, slowly add 10 mls of 30%
H2O2. After the effervescence has stopped, slowly add ~30 mls of concentrated HCl. With
continued stirring, heat on a hot plate and maintain 85 o C for 20 minutes. Cool mixture to
room temperature in an ice bath and filter (using a Buchner funnel) the crystals of
[Co(NH3)5Cl]Cl2.

C. NOTES
1. Heat must be applied as uniformly as possible.
2. The addition of the mixture requires five to seven minutes.
3. The product is detached from the walls during cooling as it is difficult to remove when
cold.
4. The material should be pulverized while warm before it has had an opportunity to
attract moisture from the air.

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D. Yield: …………………..
E. Melting Point: …………

F. Chemical Formula and structure of [Co(NH3)5Cl]Cl2 compound:

It is a chemical compound with the formula [Co(NH3)5Cl]Cl2. It is a red-violet, diamagnetic,
water-soluble salt. In [Co(NH3)5Cl]Cl2, two chloride ions are outer sphere (counter ions) and
one is bound to the Co(III) center: reaction with excess silver nitrate would immediately
precipitate the two chloride counter ions, but the bound chloride ion would not be
precipitated.

Structure of [Co(NH3)5Cl]Cl2 complex

G. Record IR spectra and interpret:

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H. Discussion:

[Co(NH3)5Cl]Cl2 complex has been prepared by adding Cobalt(II) chloride-hexahydrate with

ammonia.

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I. References and Notes:

1. Gert G. Schlessinger (1967). "Chloropentaamminecobalt(III)

Chloride". Inorganic Syntheses. 9: 160. doi:10.1002/9780470132401.ch43.
2. Williams, Gregory M; Olmsted, John, III; Preksa, Andrew P., III (1989).
"Coordination complexes of cobalt: inorganic synthesis in the general chemistry
laboratory". Journal of Chemical Education. 66: 1043–5. doi:
10.1021/ed066p1043.
3. G. G. Messmer; E. L. Amma (1968). "Redetermination of the crystal structure of
chloropentaamminecobalt(III) dichloride". Acta Crystallogr. B. 24: 417–422. doi:
10.1107/S0567740868002475.
4. Hambley, Trevor W.; Lay, Peter A. (1986). "Comparisons of π-bonding and
hydrogen bonding in isomorphous compounds: [M(NH3)5Cl]Cl2 (M = Cr, Co, Rh,
Ir, Ru, Os)". Inorganic Chemistry. 25: 4553–8. doi: 10.1021/ic00245a020.
5. Schwab, E. (8 September 2003). "Cobalt". Chemical & Engineering
News. 81 (36): 80. doi: 10.1021/cen-v081n036.p080.

1. Synthesis and characterization of Potassium Trisoxalatoferrate(III)

Trihydrate, K3[Fe(C2O4)3].3H2O:

1E. Synthesis of K3[Fe(C2O4)3].3H2O:

To prepare the complex trisoxalatoferrate(III), Fe(C2O4)3-3 anion and isolate it as its hydrated
potassium salt, K3[Fe(C2O4)3].3H2O. Also, to study the photochemical reduction of the
sample.

THEORY:
Potassium trisoxalatoferrate(III) trihydrate, K3[Fe(C2O4)3].H2O is a green crystalline salt,
soluble in hot water but rather insoluble when cold. It can be prepared by the reaction of
K2C2O4.H2O with FeCl3.6H2O.
3K2C2O4.H2O(aq) + FeCl3.6H2O(aq) → K3Fe(C2O4)3].3H2O(aq) + 3KCl(aq)
Experimental:
A. Chemicals: Apparatus:
1. K2C2O4.H2O 1.Filterpaper
2. FeCl3.6H2O 2.funnel
3. K3Fe(CN)6 solution 3. opaque objects
4. H2SO4 solution 4. Largebeaker
5.distilled water 5.test tubes

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Synthesis of of Potassium Trisoxalatoferrate(III) Trihydrate, K3[Fe(C2O4)3].3H2O:

B. Procedure:
1. Weigh approximately 9.0 g of hydrated potassium oxalate, K2C2O4.H2O into a 250
mL beaker.
2. Add 30 mL of distilled water and heat to dissolve (do not boil).
3. In a second small beaker dissolve 4.4 g of FeCl3.6H2O in a minimum amount of
cold water (10-15 mL). Add the FeCl3.6H2O solution to the warm oxalate solution
and stir with a glass rod. Allow the product to crystallize (away from strong
sunlight) by cooling the solution in an ice-water mixture.
4. Collect the crystalline product by filtration. The product is K3Fe(C2O4)3].3H2O.

C. NOTES
1. Heat must be applied as uniformly as possible.
2. The addition of the mixture requires five to ten minutes.
3. The product is detached from the walls during cooling as it is difficult to remove
when cold.
D. Yield: …….… xxxxx g.
E. Melting Point: ………yyyy……………

F. Chemical Formula and structure of K3[Fe(ox)3]:

It is a chemical compound with the K3[Fe(ox)3]. K3[Fe(C2O4)3].H2O is a green crystalline

salt, soluble in hot water but rather insoluble when cold. The configuration of the two stereo
isomeric complex ions K3[Fe(ox)3] is described. The three oxalato groups in a complex ion
are planar, their inner oxygen atoms form a slightly distorted octahedron round the central Fe
atom. It is shown that both ionic and hydrogen bonds link the complex ions in the structure.

Structure of K3[Fe(ox)3]
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G. Record IR spectra and interpret:

H. Discussion:

K3[Fe(C2O4)3].H2O is a green crystalline salt, soluble in hot water but rather insoluble when
cold. The complex K3[Fe(C2O4)3]. H2O was synthesize. The actual mass obtained was xxx g
while the theoretical yield obtained was xxx g.

I. References and Notes:

1. https://pubchem.ncbi.nlm.nih.gov/compound/71310365
2. https://www.researchgate.net/.../263032238_The_crystal_structures_of_potassium_T is
oxalato complex.

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1. Synthesis and characterization of potassium tris oxalato chromate (III)

trihydrate:

1F. Synthesis of K3[Cr(ox)3]

The experiment is based on the following equation:

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

Experimental:
A. Chemicals: Apparatus:
1. Potassium dichromate 1. Filter paper
2. Potassium oxalate monohydrate 2. Magnetic stirrer and heater
3 Oxalic acid dihydrate 3. Suction
4. Potassium permanganate 4. Large beaker
5. Oxalic acid
6. Sulphuric acid
7. Sodium hydroxide
8. Silver nitrate

Synthesis of of potassium tris oxalato chromate (III) trihydrate:

B. Procedure:
Make a solution of potassium oxalate monohydrate (2.3 g, 12.5 mmol) and oxalic acid
dihydrate (5.5 g, 43.6 mmol) in water (110-120 ml). To this solution add solid potassium
dichromate (1.9 g, 6.45 mmol) in small portions with constant stirring. Concentrate the
solution nearly to dryness. On 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.

C. NOTES
1. Heat must be applied as uniformly as possible.
2. The addition of the mixture requires five to ten minutes.
3. The product is detached from the walls during cooling as it is difficult to remove
when cold.
D. Yield: …… 6.20438 g.
E. Melting Point: ……………………

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F. Chemical Formula and structure of K3[Cr(ox)3]:

It is a chemical compound with the formula K3[Cr(ox)3]. The configuration of the two stereo
isomeric complex ions [Cr(C2O4)3] is described. The three oxalato groups in a complex ion
are planar, their inner oxygen atoms form a slightly distorted octahedron round the central
chromium atom. It is shown that both ionic and hydrogen bonds link the complex ions in the
structure.

Structure of K3[Cr(ox)3]

G. Record IR spectra and interpret:

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H. Discussion:

Conclusion Potassium tri(oxalato) chromium (III) trihydrate, K3[Cr(C2O4)3].3H2O was

synthesize. The actual mass obtained was 3.6887 g while the theoretical yield obtained was
6.20438 g.

I. References and Notes:

1. https://pubchem.ncbi.nlm.nih.gov/compound/71310365
2. https://www.researchgate.net/.../263032238_The_crystal_structures_of_potassium_Tris
oxalato complex.

1. Synthesis and characterization [K2SO4,Cr2(SO4)3,24H2O]:

1G. Crome alum [K2SO4,Cr2(SO4)3,24H2O]
Potassium and chromium sulfates are directly obtained by reducing potassium dichromate
with ethanol in acid medium.

Experimental:
A. Chemicals: Apparatus:
1. Potassium dichromate 1. Filter paper
2. Ethanol 2. Magnetic stirrer and heater
3 Conc. Sulphuric acid 3. Suction
4. Large beaker
Synthesis of of Crome alum [K2SO4,Cr2(SO4)3,24H2O]:

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B. Procedure:
98 grams of potassium dichromate are placed in a porcelain dish containing 400 ml of water.
76 ml of concentrated sulfuric acid are slowly added and stirred until all the salt is dissolved.
If potassium dichromate has not completely dissolved the mixture is warmed gently. After all
the salt has dissolved, the solution is filtered if it is not absolutely clear. Then 63 ml of ethyl
alcohol are cautiously added, by stirring the reaction mixture after each addition and by
allowing the heat of the reaction to raise the temperature of the solution to the boiling point.
When all ethanol has been added the flask is covered and the hot solution is left to stand for a
week or longer. The obtained crystals of chrome alum are filtered and if the filtrate is
evaporated the additional amount of chrome alum is obtained. The crystals are dried and
stored in a bottle since they are efflorescent. Chrome alum obtained by described method
contains twelve molecules of crystalized water (dodecahydrate) – KCr(SO4)2· 12H2O.

C. NOTES
1. Heat must be applied as uniformly as possible.
2. The addition of the mixture requires five to ten minutes.
3. The crystals are dried and stored in a bottle since they are efflorescent.

D. Yield: …… xxxx %.
E. Melting Point: ………yyyy……………

F. Chemical Formula and structure of [K2SO4,Cr2(SO4)3,24H2O]:

It is a chemical compound with the formula [K2SO4,Cr2(SO4)3,24H2O].

Structure of [K2SO4,Cr2(SO4)3,24H2O]:

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G. Discussion:

Potassium and chromium sulfates are directly obtained by reducing potassium dichromate
with ethanol in acid medium. The chemical formula of chrome alum is
[K2SO4,Cr2(SO4)3,24H2O]. The actual mass obtained was xxx g while the theoretical yield
obtained was yyy g.

H. References and Notes:

1. Austin, George T. (1984). Shreve's Chemical process industries (5th ed.). New
York: McGraw-Hill. p. 357. ISBN 9780070571471.
2. "Alhydrogel | Alum vaccine adjuvant for research | InvivoGen".
www.invivogen.com. Retrieved 2018-06-08.
3. Picon, M.; et al. (2005). "L'alun des oasis occidentales d'Egypte: researches sur
terrain et recherches en laboratoire". In Borgard P.; et al. L'alun de Mediterranée.
4. Archontidou, A. (2005). "Un atelier de preparation de l'alun a partir de l'alunite
dans l'isle de Lesbos". In Borgard P.; et al. L'alun de Mediterranée.
5. Hall, A. J.; Photos-Jones, E. (2005). "The nature of Melian alumen and its
potential for exploitation in Antiquity". In Borgard P.; et al. L'alun de
Mediterranée.

2. Equilibrium studies on inorganic reaction:

2A. Determination of composition of Fe(II)-1,10-phenanthroline complex in solution
by Mole-Ratio method.
THEORY:
Complexation reactions of the form

xM + yL ↔ MxLy …………………………..(1)

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are based on the reaction of a metal cation (M) and a ligand (L). These reactions are widely
used in analytical chemistry. Absorption spectroscopy is a powerful tool for exploring these
complexation reactions. In this experiment, two general approaches to studying the
composition of complexes are used to demonstrate the necessity of carefully evaluating the
properties of a particular chemical system in order to select the best method for determining
the composition (metal to ligand ratio) of a complex by absorption measurements.
Mole-Ratio Method:
In this method, a series of solutions is prepared in which the concentration of one reactant is
held constant while that of the other is varied. The absorbance of each solution is measured
and plotted vs. the mole ratio of the reactants. Assuming the complex absorbs more than the
reactants, this plot will produce an increasing absorbance up to the combining ratio. At this
point, further addition of reactant will produce less increase in absorbance. Thus a break in
the slope of the curve occurs at the mole ratio corresponding to the combining ratio of the
complex.
REAGENTS
(i) Ferrous ammonium sulfate ((NH4)2Fe(SO4)2⋅6H2O, FW = 392.13), 7.0 x 10-4 M
(250mL)
(ii) 1,10-phenanthroline (FW = 198.23), 7.0 x 10-4 (250 mL) M
(iii) Acetic acid (17.45 M) / sodium acetate buffer, pH 4.0, total acetate = 0.01 M
(iv) Hydroxylamine hydrochloride (FW = 69.49), 5 % (w/v = g/mL) (50 mL)

PROCEDURE:
A. Solution Preparation:
Prepare the solutions listed above in the specified amounts. Make the phenanthroline
solutions first. To prepare the buffer, make 250 mL of 0.01 M sodium acetate and titrate to
pH 4.0 by addition of acetic acid (monitor addition with pH meter). Prepare a spectroscopic
blank by adding 5 mL of the acetate buffer and 1 mL of the hydroxylamine hydrochloride
solution to a 25 mL volumetric flask and diluting to the mark with distilled water.
B. Absorbance Spectra of Stock Solutions.
Record the absorbance spectrum of each of your stock solutions vs. a distilled water
reference.
D. Mole-Ratio Method.
Transfer exactly 2 mL of the standard Fe2+ solution to eight separate 25 mL volumetric
flasks. Add 5 mL of the acetate buffer solution followed by 1 mL of the hydroxylamine
hydrochloride solution. Add 2, 3, 4, 5, 6, 8, 10, and 12 mL of the 7.0 x 10-4 M 1,10-
phenanthroline solution to the various flasks. Dilute to the mark with distilled water, and mix.
After ten minutes measure the absorbance of each solution vs. the spectroscopic blank. Make
three replicate absorbance measurements.
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CALCULATIONS
Sections 1 below produce plots with linear portions that intersect. For each plot,
associate each point with either the left or right linear portions and perform two least-squares
calculations to estimate the linear equations (y = mx + b) that represent the left and right
linear portions of the plot. Slopes, intercepts, and values of r2 should be tabulated for each of
these least-squares calculations. The intersections of the lines can be found mathematically
by finding the point on the x- axis where the lines have the same y-value (i.e., setting the
equations equal to each other and solving for x). If replicate absorbance measurements have
been made, all plots should have error bars based on the 95% confidence intervals of the
absorbance measurements.
1. For the mole-ratio method, plot absorbance vs. moles of reagent/mole of iron. Extrapolate
the linear portions of the graph and locate the intersection by use of the mathematical
procedure described above. 2. Postulate the formula for the complex and draw its structure. In
the discussion section of your report, comment on any discrepancies between the combining
ratios suggested by the two measurement approaches.

Figure 1. Mole-ratio plots for 1:3 complexe.

REFERENCES
1. W. C. Vosburgh and G. R. Cooper, J. Amer. Chem. Soc. 1941, 63, 437.
2. D. A. Skoog, D. M. West, F. J. Holler, Fundamentals of Analytical Chemistry, 5th Ed.;
Saunders: New York, 1988; pp. 525-528.

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3. Spectrophotometric Estimation:
3A. Colourimetric estimation of Fe(III) (as thiocyanate complex)
Aim: To determine the mass of ferric iron present in the whole of the given solution
colourimetrically as the thiocyanate complex.
Principle:
When treated with excess of thiocyanate ions, ferric salt solutions produce red colour
proportional to the amount of iron present.
Fe3+ + 6CNS- → [Fe(CNS)6]3-
A calibration curve can be obtained by plotting the absorbance against concentration for a set
of standard solutions after developing the colour using thiocyanate. The concentration of an
unknown solution can then be obtained by developing its colour under similar conditions and
measuring its absorbance. The colour fades with time due to reduction of ferric iron by
thiocyanate ions. Therefore readings have to be taken immediately after developing the
colour.
Chemicals required:
(1) Ferric alum [NH4Fe(SO4)2 12H2O; molar mass =482.2] – 1 g.
(2) approx. 5 N HCl (iron-free) - 100 cm3.
(3) 20% amm. thiocyanate solution - 100 cm3.
Apparatus required:
(1) Ten 100 cm3 volumetric flasks.
(2) 10 cm3 graduated pipette.
(3) Funnel, beaker.
(4) Photoelectric colourimeter / spectrophotometer.
Procedure:
(Note: Colours are developed in the solutions for calibration and estimation simultaneously.
Switch on the colourimeter at least 30 minutes before use. Set zero using the blank solution.
Do not switch off or change settings till all readings are taken)
A standard iron solution containing 0.1 mg iron per milliliter is prepared as follows: 0.8634 g
ferric alum is weighed into a 100 cm3 volumetric flask. 10cm 3 of conc. HCl (iron-free) is
added to prevent hydrolysis. It is then made up to 100 cm3. 10 cm3 of this solution is pipetted
into another volumetric flask and made up to 100 cm3. This solution now contains 0.1 mg
iron per milliliter. Transfer the given solution quantitatively into a 100 cm3 volumetric flask
and make up to the mark using distilled water. 2, 4, 6, 8 and 10 cm3 of standard iron solution
are taken in 5 different 100 cm3 volumetric flasks. 10 cm3 of distilled water is taken in
another volumetric flask to be used as blank to set the spectrophotometer. Two suitable
volumes (say 4 cm3 and 6 cm3) of the given solution are also taken in two other volumetric
flasks. 5 cm3 of 5 N HCl and 5 cm3 of 20% amm. thiocyanate solution are added to each and
made up to 100 cm3. The absorbances are measured at 480 nm. Plot the absorbance against
volume of standard iron solution to obtain the calibration curve. Using the absorbance values
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for the given solution, find the corresponding volume equivalent to the standard iron solution
from the calibration curve. Mass of iron in this volume and hence mass of iron in the whole
of the given solution is then computed.

Result:
Mass of iron in the whole of the given solution = (1) _______________ g.
(2) _______________ g.
Calculation:
Calibration:
Mass of ferric alum weighed = w g.
Therefore, mass of iron per cm3 of standard solution, (m) = (0.1 / 0.864) × w mg.
Estimation:
Volume of made up solution used for colour development = v cm3.
Volume corresponding to standard solution from graph = V cm3.
Mass of iron corresponding to V cm3.standard = V.m = x mg.
Mass of iron corresponding to v cm3 = x mg.
Therefore, Mass of iron in the whole of the given solution = (x / v) ×100 mg.
(Note to instructor: Solution remaining from the first 100 cm 3 of standard solution can be
used for giving unknown to students. Give a volume between 8 cm3 and 12 cm3 from this for
estimation to each student.)

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4C. Gravimetric estimation of Ni(II) as Ni(DMGH)2

Objectives:
· To precipitate nickel from the solution by adding dimethyl glyoxime.
· Filtration of precipitate using sintered glass crucible.
· Mass of nickel calculated from the mass of precipitate.

Theory:
Gravimetric analysis is one of the most accurate analytical methods available. It is concerned
with the determination of a substance by the process of weighing. The element or radical to
be determined is converted into a stable compound of definite composition and the mass of
the compound is determined accurately. From this, the mass of element or radical is
calculated. The gravimetric analysis involves a) precipitation b) filtration c) washing of the
precipitate and d) drying, ignition and weighing of the precipitate. Nickel ion can be estimate
quantitatively by precipretating nickel as the nickel dimethyl glyoximate complex.
The nickel is precipitated as nickel dimethyl glyoxime by adding alcoholic solution of
dimethyl glyoxime C4H6(NOH)2 and then adding a slight excess of aqueous ammonia
solution.

nickel bis(dimethylglyoximate) complex

Chemicals required:
(1) Nickel sulphate (3gm)
(2) Dimethylglyoxime
(3) Hydro chloric acid

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Apparatus required:
(1) Ten 100 cm3 volumetric flasks.
(2) 10 cm3 graduated pipette.
(3) Funnel, beaker.
(4) Goch crucible
(5) glass rod

Procedure:
The steps commonly followed in gravimetric analysis are;
(1) Preparation of a solution containing a known weight of the sample.
(2) Separation of the desired constituent.
(3) Weighing the isolated constituent.
(4) Computation of the amount of the particular constituent in the sample from the
observed weight of the isolated substance.
When the pH is buffered in the range of 5 to 9, the formation of the red chelate occurs
quantitatively in a solution. The chelation reaction occurs due to donation of the electron
pairs on the four nitrogen atoms, not by electrons on the oxygen atoms. The reaction is
performed in a solution buffered by either an ammonia or citrate buffer to prevent the pH of
the solution from falling below 5. If the pH does become too low the equilibrium of the above
reaction favors the formation of the nickel (II) ion, causing the dissolution of Ni (DMG)2
back into the mother liquor.
A slight excess of the reagent has no action on the precipitate, but a large excess should be
avoided because of the possible precipitation of the reagent itself. The precipitate is soluble in
the free mineral acids. It is therefore crucial to avoid the addition of too large and excess of
the reagent because it may crystallize out with the chelate. It is also important to know that
the complex itself is slightly soluble to some extent in alcoholic solutions. By adding small
amount of chelating agents will minimize the errors from these sources. The amount of the
reagent added is also governed by the presence of other metals such as cobalt, which form
soluble complexes with the reagent. If a high quantity of these ions is present, a greater
amount of DMG must be added. The nickel dimethylglyoximate is a very bulky precipitate.
Therefore, the sample weight used in the analysis must be carefully controlled to allow more
convenient handling of the precipitate during the transfer to the filtering crucible. The
compactness of the precipitate is improved by adjusting the pH to 3 or 4, followed by the
addition of ammonia solution.
A slow increase in the concentration of ammonia in the solution causes a slight increase in
the pH gradually and results in the precipitation of the complex. The result is the formation of
a denser precipitate. Once the filtrate has been collected and dried, the nickel content of the
solution is calculated stoichiometrically from the weight of the precipitate.

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Ni-DMG Complex

Result:
Weight of Goch crusible constant(w 1) Weight after drying(w2)

Calculation:
Weight of Goch crusible constant(W1) = xxx gm
Weight of Goch crusible constant + Nickel dimethyl glyoximate complex =W2= yyy gm.
Therefore, Weight of Nickel dimethyl glyoximate complex = (W2 - W1) gm

Ni(C4H7O2N2)2 ≡ Ni
288.69 59.69
288.91 g nickeldimethylglyoximate contains = 58.69 g of nickel
So, X g of nickeldimethylglyoximate contains = 58.69/288.91 x X
Or, 25 ml of the solution contains = 58.69/288.91 x X g of nickel
1000 ml of the given solution contains = 58.69 / 288.91 x X x 1000/25 g

Therefore, weight of Ni in 1000 ml of the given solution contains

([ 6 ? [ 5) ek 5444
≡ : 59.69 : = ??
6<<.<= 69
…………………………………………………………………………………………………………
References
1. Semon, W. L.; Damerell, V. R. (1930). "Dimethylglyoxime". Organic Syntheses. 10:
22. doi:10.15227/orgsyn.010.0022.
2. Lev Tschugaeff (1905). "Über ein neues, empfindliches Reagens auf Nickel". Berichte
der deutschen chemischen Gesellschaft. 38 (3): 2520–2522.
doi:10.1002/cber.19050380317.
3. Girolami, G.. S.; Rauchfuss, T.B.; Angelici, R. J. (1999). Synthesis and Technique in
Inorganic Chemistry: A Laboratory Manual (3rd ed.). pp. 213–215.

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