A Project Report Submitted to the Department of Chemistry
Manipur University in partial fulfilment of M.Sc. Final in Chemistry
BY:
GONGCHAMPOU KAMEI
4th Semester | Roll No. 2315017 | Regd.No. 20410294/20
UNDER THE SUPERVISION OF
PROF. R. K. HEMAKUMAR SINGH
Department of Chemistry, Manipur University
JULY 2025
This is to certify that Gongchampou Kamei, M.Sc. 4th semester has satisfactorily completed the required courses for the M.Sc. Program in Chemistry.
(Prof Nongmaithem Rajen Singh)
HOD, Chemistry Department
This is to certify that the project entitled "Synthesis and Structural Characterization of Tris-ethylenediamine Nickel(II) Sulphate" being submitted by Gongchampou Kamei, bearing Roll No. 2315017 and Regn. No. 20410294/20 to Chemistry Department for the award of the degree of Master of Science in Chemistry is a bonafide Project work carried out by him.
The results contained in this project have not been submitted, in part or full, to any other University or Institute for the award of any degree.
Date:
Place:
_______________________
(Prof. R.K. Hemakumar Singh)
I would like to express my sincere and deep sense of gratitude to Prof. R. K. Hemakumar Singh, Chemistry Department, Manipur University, for his constant guidance and supervision of this work. His kind interest, valuable suggestion and the encouragement have resulted in the completion of this project work.
I am grateful to Prof. N. Rajen Singh, Head, Department of Chemistry, Manipur University and other Faculty Members of the Department for encouragement and valuable advice.
I would like to give special thanks to Dr. N. Shantibala Devi, Guest Faculty... and Research Scholars Miss S. Sumit Kumari Devi and Miss Mm Shabnam Scholar for their continuous support.
Gongchampou Kamei
Roll no.: 2315017
Metal coordination chemistry is a demanding field that will tax our skills as a scientist. Metals, as a group, can exhibit coordination numbers from two to fourteen, and formal oxidation states that range from negative values to as high as eight.
Because coordination chemistry is the chemistry of the vast majority of the Periodic Table, it is central to the proper study of chemistry. Moreover, since many coordination compounds incorporate organic molecules as ligands, an understanding of organic chemistry is also necessary.
Ethylenediamine is a chemical compound that is widely used in the synthesis of metal complexes with anticancer properties. It can also exhibit various other activities such as antimicrobial, antifungal, antibacterial, etc. Metal complexes containing ethylenediamine can stimulate cytotoxic function in various cancer cell lines.
Nickel is known primarily for its divalent compounds since the most important oxidation state of the element is +2. Blue and green are the characteristic colours of nickel compounds and they are often hydrated. Nickel is a hard silver white metal, which occurs as cubic crystals.
Nickel (II) Complex refers to compounds in which nickel is in the +2-oxidation state, often exhibiting notable biological activity. These complexes can involve nickel ions coordinated with thiosemicarbazone ligands, each exhibiting unique spectral and physical characteristics.
Nickel is an essential element which is used in the body and in industries as well. It regulates metabolism, fights oxidative stress, and strengthens the immune system. It forms coordination complexes with amino acids within enzymes.
Several researchers have investigated Ni(II) complexes of ethylenediamine... The interest was focused on the examination of the effects of the substituents on the stabilities of the complexes as well as the determination of magnetic properties. The bis(ethylenediamine)nickel (II) complex of permethylpolyazine is reported.
Order-disorder structural phase transitions and translations from static to dynamic Jahn-Teller distortions are of wide interest. The complexes [M(ethylenediamine)3]SO4, M=Cu, Ni, have been extensively studied...
To relate thermoanalytical data on this system to the crystal and molecular structures, we have determined the structure of [Ni(en)3]SO4 at 110 K.
In this project work, our aim is to synthesize a new mixed ligand Ni(II) complex of Tris-ethylenediamine Ni(II) Chloride dihydrate with ammonium Sulphate and to see the properties of the complex by spectroscopic investigations.
3.1(a) Conductivity Meter: Molar conductance was measured on EUTECH CON 700. This measurement was used to measure the conductance i.e. the ability to of the solution to conduct current.
3.1(b) IR Spectroscopy: The IR spectra were recorded on IR Affinity-1S SHIMADZU. From the IR spectra we can get sufficient information about the functional group and structure of the compound.
3.1(c) UV Spectroscopy: Solid and solution electronic spectra were recorded on spectrophotometer at the range of 200-900nm and involved the promotion of electron to the higher energy molecular orbital.
3.1(d) XRD: Structural characterisation of the sample was performed by using X-ray diffraction method. Angle range between 10° < 2θ < 90°.
3.1(e) EDAX: This technique gives an overall mapping of the sample by analysing near surface elements and estimates the elemental proportion at different positions. It is used in conjunction with SEM.
Step 1: Preparation of Tris-ethylenediamine nickel (II) chloride dihydrate, [Ni(en)₃]Cl₂.2H₂O
Prepared by reacting 3.5 ml of ethylenediamine with a solution of 3.0g of NiCl₂.6H₂O in 25 ml of water. Filtered to remove hydrous oxide. Evaporated to ~10ml, added drops of en, cooled on ice-bath. Separated as purple crystals. Yield: 80%, MP: 255°C.
Step 2: Preparation of Tris ethylenediamine nickel (II) Sulphate [Ni(en)₃]SO₄
Prepared by reacting tris-ethylenediamine nickel (II) chloride dihydrate (1mol) in ~20 ml methanol with Ammonium Sulphate (2 mol) in 20ml of water. Mixed and stirred for 2 hrs, mixture turns light pink. Filtered, washed with acetone and dried.
The reciprocal of specific resistance is called conductance (Kappa). Molar conductance is the tendency of all ions in a given volume (μ = Λ × V).
| Complex | Molar conductance (0.002M) |
|---|---|
| [Ni(en)₃]Cl₂.2H₂O | 205 Ω⁻¹cm²mol⁻¹ (1:2 electrolyte) |
| [Ni(en)₃]SO₄ | 80 Ω⁻¹cm²mol⁻¹ (1:1 electrolyte) |
Result: Values confirm the expected electrolyte nature of the synthesized complexes.
In IR spectrum of [Ni(en)₃]SO₄, all absorption bands corresponding to the ethylenediamine are observable. The absorption bands at about 520cm⁻¹ can be attributed to Ni-N stretching bands, CH₂ stretching bands at 2924 cm⁻¹ and 2879cm⁻¹, and NH₂ stretching bands at 3259cm⁻¹ and 3163cm⁻¹.
The antisymmetric S=O stretching vibration of sulphate ion appears at 1060 cm⁻¹ while bending vibrations are observed at 609 cm⁻¹.
The UV-Vis spectrum typically shows two d-d transition bands in the visible region, indicating an octahedral geometry. These bands appear around 346nm and 547nm, assigned to ¹A₁g → ¹T₂g and ¹A₁g → ¹T₁g transitions.
Energy Dispersive X-Ray Analysis confirms the elemental composition.
| Elem | Wt % | At % |
|---|---|---|
| CK | 7.87 | 20.37 |
| NK | 9.40 | 20.86 |
| OK | 0.06 | 0.12 |
| ClK | 42.86 | 37.57 |
| NiK | 39.80 | 21.07 |
| Total | 100.00 | 100.00 |
Above: EDAX table for [Ni(en)₃]Cl₂.2H₂O. Confirms presence of Ni, Cl, N, C.
| Elem | Wt % | At % |
|---|---|---|
| CK | 10.69 | 24.67 |
| NK | 14.45 | 28.60 |
| OK | 1.07 | 1.85 |
| SK | 25.54 | 22.09 |
| NiK | 48.25 | 22.79 |
Decomposed with conc. HNO₃ and H₂SO₄. Estimated gravimetrically as [Ni(DMGH)₂].
| Complex | Theoretical % Ni | Exp. % Ni |
|---|---|---|
| [Ni(en)₃]SO₄ | 16.62 | 16.59 |
Result: Good agreement with theoretical values.
From the experimental estimation of Nickel, the percentage of nickel is found to be in good agreement with theoretical values. Octahedral geometrical complex may be suggested from the observed electronic spectra.
The IR spectra indicate the presence of ligand ethylenediamine and the sulphate ion in the synthesized complex.
Proposed Structure:
[Ni(en)₃]²⁺ (SO₄)²⁻
Tris-ethylenediamine nickel (II) sulphate
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