APPLIED SCIENCE FACULTY

APPLIED CHEMISTRY DEPARTMENT

STUDENT PROJECT ON:-

SYNTHESIS AND CHARACTERIZATION OF SCHIFF BASE METAL

COMPLEX DERIVED FROM AMINO ACID AND NINHYDRIN

ADVISOR: ATO BELETE YILMA(M.Sc)

BY TESFAYE TEBEKA in Partial Fulfillment of the Requirements for the of Bachelor

of Degree in applied chemistry.

JUNE, 2009

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 TABLE OF CONTENT

CONTENT PAGE
Abbreviation i
Acknowledgement ii
Abstract iii
CHAPTER ONE ............................................................................................................... 8
1 INTRODUCTION.......................................................................................................... 8
1.1 Synthesis of Schiff base metal complexes.............................................................. 8
CHAPTER TWO ............................................................................................................ 11
Literature review ............................................................................................................ 11
2. Schiff bases components under investigation ........................................................... 11
2.1. Amino acids .......................................................................................................... 11
2.2 NINHYDRIN ......................................................................................................... 14
2.2 1 REACTIVITY ................................................................................................ 15
2.2.2 The ninhydrin reaction with amino acids and their mechanism............... 15
2.2.3 Mechanism reaction of ninhydrin and amino acids ................................... 17
2.3 Schiff Bases............................................................................................................ 18
2.3.1 Biological Important Of Schiff Base ............................................................ 19
2.3.2 Catalytic applications of Schiff bases........................................................... 20
2.4 The chemistry of metal ions ................................................................................. 21
2. 4.1 Cobalt II) complexes ..................................................................................... 22
2.4.2 Nickel (11) complexes .................................................................................... 23
2.5 Objectives and the scope of the present studies ................................................. 24
2.5.1General objective ............................................................................................ 24
2.5.2 Specific objectives .......................................................................................... 24
CHAPTER THREE .......................................................................................................... 25
3 Materials and methodology....................................................................................... 25
3.1 Apparatus and instruments ............................................................................... 25
3.2 General procedures............................................................................................... 25
3.2.1 Synthesis of Schiff base derived from cystein with Ninhydrin ............... 25
3.2.2 Synthesis of Ruhmann’s purple.................................................................... 25
3.2.3 Synthesis of Schiff base metal complex........................................................ 26
3.2.4 Synthesis of Ruhmann’spurple metal complexes...................................... 26
3.2.5 Ruhmann’s purple metal complex of lysine and ninhydrin....................... 26
3.3 Characterization of complexes........................................................................... 27
3.3.1 Thin layer chromatography .......................................................................... 27
3.3.2 Solubility ......................................................................................................... 27
3.3.3 Melting (decomposition points) .................................................................... 27
3.3.4 Conductivity measurements.......................................................................... 27

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 3.3.5 Electronic absorption spectra ....................................................................... 27
3.3.6 Flame atomic absorption spectroscopy........................................................ 27
CHAPTER FOUR......................................................................................................... 28
4 RESULTS ..................................................................................................................... 28
4.2 DISCUSSION ........................................................................................................ 32
4.2.1 Molar conductance studies............................................................................ 32
4.2.2 UV-Visible spectroscopic analysis ................................................................ 32
4.2.3 Atomic absorption spectroscopy................................................................... 33
5 Conclusions................................................................................................................... 35
6 Recommendations ........................................................................................................ 37
7 REFERENCES........................................................................................................... 38
8 Appendixes.................................................................................................................... 39

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List of tables Pages

Table-1 Physical characteristics………………………………… 21

Table- 2 soluble test of complex indifferent solvent…………… 21
Table -3 – molar conductance values Ruhmann’s purple metal complex. 22
Table-4 Spectral data of metal complexes of Ruhmann’s purple….. 23
Table - 5 A for Ni complex……………………………………… 23
Table - 5 B for Ni complex………………………………………… 23
Table- 5 C for Co-complex……………………………………… 24

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 ABBREVIATION

Abs. = absorbance
UV. Vis = ultra violet visible spectroscopy
Sch. = Schiff base
Ruhm’s = Ruhmann’s purple
Λm = molar conductivity
Ω-1 = Ohm inverse
Ns = Nano semin
Ml = Milliliter
Mmol = mili mol
Cm~1 = centimeter inverse
Co = degree cent grade
gm = gram
Co = Cobalt
Ni = Nickel
ε = Molar absorbtivity
AAS = Atomic absorption spectroscope
TLC = Thin layer chromatography
Fig = figure

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 Acknowledgement
I would like to express our sincere gratitude and indebted ness to our advisor Mr. Belete
Yilma (M.Sc) for giving reference Material and making himself available for advice at
time I need. The untiring guidance during the project work and available for advice at
time I need. The untiring guidance during the project work and valuable comments on
how to write the final project report were unforgettable I have really enjoyed working
under his supervision.
I extend special thank to Wondimegn, Solomon, Behailu to share their knowledge and
experiences during the experiments was done in their individual laboratory.
A specific acknowledgement and grateful application goes to librarians and Wondimegn
for their generous cooperation in providing me the necessary books and equipment when
required. I also really appreciate Mrs.AlexT.Kuvarega who supported us in instrumental
operation.
Above all, thanks to the Almighty God, nothing can make us forget his loving care during
our stay in Arbaminch University. Finally, I never forget the generous help of our
department and all other who have helped me giving us morals and material during three
years stay in AMU.

ii

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 Abstracts
Complexes of Co(II) and Ni(II) with Ruhmann’s Purple derived from three amino acids
namely, Iso-Leucine, Glutamine and lysine with ninhydrin and metal complexes of
Schiff base derived from cystein with ninhydrin was synthesized. The complexes were
distinctly colored and stable to atmospheric conditions. The complexes were
characterized by molar conductance and electronic studies (U V-vis and Atomic
absorption spectroroscopy)
The ligands were shown to behave as a monodentate, bidentate (ON or OO) and
tridentate (ONO) donor and the ketimine (the Schiff base) being to relatively greater
potential, because it can act as tridentate and forming two stable five membered ring on
complexation with metal ions.
After using all the characterization parameter, the Schiff base and Ruhmann’s purple
complexes of CO (II) and Ni (II) were proposed to an octahedral, geometry and 1: 2
metals to ligands ratio was suggested, in addition to this the molar conductance value is
in the range between 17.6-120 Ω-1 cm2mol-1 ,indicates that the synthesized Schiff base
and ruhmanns purple metal complexes were non electrolytic nature .

iii

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CHAPTER ONE
1 INTRODUCTION
1.1 Synthesis of Schiff base metal complexes
The term complex in chemistry is usually used to describe molecules formed by the
combination of liquid and metal ions. Originally a complex implied a reversible
association of molecule, atoms, or ions thorough weak chemical bond [1].
As applied to coordination chemistry this meaning has evolved some metal complexes
are formed virtually irreversibly and many are bind together by bonds that are quite
strong [1].
Metal complex also known as coordination compounds, coordination complex were
known although not understood in any sense. Since the beginning of chemistry, example
Prussian blue and copper vitrid. The key break through occurs when Alfred Werner
proposed; among other things that Co (III) bears six ligands in an octahedral geometry.
The theory allows one to understand the different between coordinated many ionic
chloride in the cobalt ammine chloride and to explain many of the previously in
applicable isomerism.
Schiff base is any derivative of the condensation of aldehydes or ketones with primary
amines. It is colorless, crystal and weakly basic, hydrolyzed by water and strong acids to
form carbonyl compounds and amine. It will be used as chemical intermediates and
perfume bases in dyes and rubber accelerator and liquid crystal for electronics.
Schiff base is a functional group that contains a C-N double bond (C=N) with the
nitrogen atoms connected to an aryl or alkyl group but not hydrogen.
They usually formed by condensation of primary amine with a carbonyl compound
according to the following scheme:
O

R- NH2 + R CR' R- N = CH-R+H2 where R’ =H or CH3

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Where R may be aliphatic or aromatic group .Schiff bases of aliphatic aldehydes are
reality unstable and are readily polymerizable while those of aromatic aldehydes, having
an effective conjugation system, are more stable [2].
Schiff base and its complexes have a variety of application including biological, chemical
and analytical. Earlier work has shown that some drugs showed increase activity when
administrated as metal chalets rather than as organic compounds. But, recently a
particular attention has given to the synthesis and study of diamino tetra dentate Schiff
base and their complexes. This is due to a variety of reasons, not the least of which in
their crucial role in some biological process such as the biological function of
bacterohodospin. These complexes are used in some chemical processes as catalyst and
as biological models in understanding the structure of bimolecular and biological process
in addition to this, transition metal complexes with Schiff base having a varied theoretical
and practical applications: some of them are capable of reversibly binding molecular
oxygen , oxidative catalyst and sensor designs .
A wide variety of ligands may be obtained via the Schiff base condensation reaction
which varies in identity ,flexibility ,nature of donor atoms and electronic properties .the
azomethine ( > C=N ) stretching frequencies of the ligands occur in the region between
-1
1680 and 1603 cm depending up on the nature of subsistent present either on nitrogen
or on carbon .alkyladimines absorb in the 1675 – 1665 cm -1 region and this falls by 10 –
-1
20 cm for any substitution at either end of the double bond. less data are available on
ketimine, but derivatives of biphenyl ketimine absorb near 1620 cm -1 in polar solvent the
monomer forms give rise to absorption in the 1630 – 1620 cm-1 region, but in non polar
-1
solvent s such as hexane the band is at 1590 cm or less due the dimmer .up on
coordination to the meat ions through both oxygen and nitrogen a decrease of > C=N
frequency is generally observed [3]. One of the most components that used to synthesize
Schiff base metal complexes is amino acid.
Proteins are one of the major macromelules in living system. The function of a protein is
primarily determine by its structure, which in turn is determined by the sequence of
aminoacides making up the protein .the amino acid sequence is genetically determined
and is responsible for the slope, physical characterized ,and biological activity of the
protein .

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The qualitative and quantitative determined of amino acids, peptides and protein is major
and growing importance in many a reas of biochemical investigations. The most sensitive
reaction is that between amino acids and Ninhydrin, which produces a characteristic
purple closed compound, called Ruhmann’s purple or diketohydrinedylene amine.
The reaction however, is not selective enough because all amine acids except protein (an
amino acid) give the same color .the investigation on the metal complex ( divalent Co,Ni
and Zn ) of glycine Schiff base indicates that in the presence of the meta ion, Ruhmann’s
purple is not formed ,rather a product with specific color could be isolated .

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 CHAPTER TWO
Literature review
2. Schiff bases components under investigation
2.1. Amino acids
Proteins are polymers of amino acids, with each acid residence joined to its neighbor by a
specific type of covalent bond. Protein can be broken down, hydrolyzed to their
constituent aminoacides by a variety of methods, and the earliest studies of proteins
naturally focused on the free amines acids derived from them. Twenty different amino
acids are commonly found in proteins, all the amino acids have trivial or common names,
in some cases derived from the source which they were first isolated. Asparagines were
first found in asparagus, and glutamate in wheat gluten; tyrosine was first isolated from
cheese and glysine was so named because of its sweet taste.
Amino acid share common structural features.

All the 20 amino acids are α– amino acids .They have a carboxyl group bonded to the
same carbon atom [the x carbon]. They differ from each other in their side chains, or R
groups, which vary in structure, size, and electric change, and which influence the
solubility of the amino acids in water.
The common amino acids of proteins have been assigned three letter abbreviations and
one letter .the general structure of amino acid:
COO-

+N3H C H

R Where R =hydrocarbon chain and sulphur containing carbon

Amino acids can be classified R group.
The amino acids can be group into five main classes based on the properties of their R
group, in particularly, their polarity or tendency to interact with water at biological PH
value, near PH 7.0. The polarity of the R groups varies widely, from non polar and
hydrophobic, water hating to highly polar and hydrophilic; water loving.

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.
Free amino acids at near PH 7.0.where the species NH2-CHR-COO-
is predominant , are good ligand and from stable five member chelate rings .under other
PH condition s this may not be the case .an amino acid molecules has three donor groups

The amine group of the N- terminus

The carboxyl group of the C- terminus and

The functional group of the side chain are some times potential candidates.
The non-protein associated amino acids perform specialized function. Several of the
amino acid found in proteins also lese functions distinct from the formation of peptides
and proteins, example, tyrosine in the formation of thyroid hormones or glutamate acting
as a never transmitted.
The amino acid under the present investigation being Iso Lucien glutamine, cystein in
and lysine. Same of their general characteristics are presented here.
Glutamine-or-/S/-2-amino-4-carbamoye botanic acid is a polar amino acid and soluble in
water (hydrophilic). Glutamine (C5H10ON2O3) has boiling point of 653 k and melting
point 507.66k.The empirical formula of C5H10ON2O3 with the composition of the
constituent elements carbon 41.09% hydrogen 6.8%, nitrogen 19.178%, and oxygen
32.87%. This amino acid has a molecular mass of 146g/mol. The structure and
designation of the stereoisomer is the following:

COOH COOH

H2N C H H C NH2

CH2 CH2

CH2 CH2

C O C O

NH2 NH2
L- 2-amino-4-carbamoylbutanoic acid D- 2-amino-4-carbamoylbutanoic acid

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Iso-leucine –(2S, 3S)-2- amino -3- matched pentatonic acid (C6H,3NO2) it has melting
point of 370.74k and boiling point is 554.04k.
This amino acid has an empirical formula of C6H, 3NO2 with the constituent elements:
carbon 54.941., hydrogen 9.99%, nitrogen 10.68% and oxygen 24.39%. This amino acid
has molecules mass of 131.18 gm/mol it has the following structure and designation:

COOH COOH

H2 N C H H C NH2

CH CH
H2 C CH3 H2C CH3
H3C H3C
L-2-amino-3-methylpentanoic acid D-2-amino-3-methylpentanoic acid

Cystein-/S/-2-amino-3-mercapto propanioc acid has an empirical formula of C3H7NO2S

with the constituent elements; carbon 29.752%, hydrogen 5.78%, nitrogen 11.570%,
oxygen 26.44% and sophism 26.44%. it has melting point of 683,4k and boiling point
909.64k. The structure and designation of the stereo isomer is the following.
COOH COOH

H2 N C H H C NH2

CH2 CH2

SH SH
L-2-amino-3-mercaptopropanoic acid D-2-amino-3-mercaptopropanoic acid

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Lysine-2-6-di -aminohexanoic acids.
COOH COOH

H2N C H
H C NH2

CH2
CH2

CH2
CH2

CH2
CH2

CH2
CH2

NH2
NH2
L-2,6-diaminohexanoic acid D-2,6-diaminohexanoic acid

C6H14N2O2
Mol. Wt.: 146.188
m/e: 146.106 (100.0%), 147.109 (6.5%)
C, 49.30; H, 9.65; N, 19.16; O, 21.89
2.2 NINHYDRIN
Ninhydrin (2-2-Dihydroxylindane -1-3-dione) is a chemical used to detect ammonia or
primary and secondary amines. When reacting with these free amines, a deep blue or
purple color known as Ruhmann’s purple is evolved. Ninhydrin is most commonly used
to detect finger prints, as amines left over from peptides and proteins terminal amines or
lysine residues/ sloughed off in finger prints react with ninhydrin [4].
Ninhydrin is also used in amino acid analysis of proteins. Most of the amino acid are
hydrolyzed and reacted with Ninhydrin except proline; also certain amino acid chains
degraded. There fore separate analysis required for identifying such amino acids that
either react differently or don’t react at all with Ninhydrin. The rest of amino acids are
then quantified calorimetrically after separation by chromatography.

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2.2 1 REACTIVITY
O

O
ninhydrin
Properties
Molecular formula-C9H4O3 density=1.482g/cm3
Molar mass-160.1263g/mog boiling point =338.4oc
Appreance-white powder
The carbon atom of a carbonyl bears a partial positive charge of the central carbon of a 1,
2, and 3;-tri carbonyl is less stable and more electrophilic than simple ketones. In most
compounds a carbonyl is more stable than the dihydroxy /hydrate / form. How ever nine
hydrogen is stable hydrate of the central carbon because this from does not have the
destabilizing effect of adjacent carbonyl partial- positive centers. Indane 1, 2, 3, trione
reacts readily with nucleophiles.
Note that in order to generate the Ninhydrin chromophore, the amine is condensed with a
molecule of Ninhydrin to give as Schiff base. Thus only ammonia and primary amines
can proceed past this step .at this step, there must also be an alpha proton for Schiff base
transfer, so an amine adjustment to tertiary carbon cannot be detected by the ninhydrin
test .the reaction of ninhydrin with secondary amines gives an iminum salt, which is also
colored, and this is generally yellow –orange in color.
2.2.2 The ninhydrin reaction with amino acids and their mechanism
The most important reaction of amino acids is the reactions that are utilized in the
formation of peptides and proteins. Proteins analysis requires determination of the
identity and quantity of each constituted amino acid is the major or step include:
- Hydrolyzing with acids
- Separation with chromatography
- Identification and quantification of the individual amino acids

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Ninhydrin which is easily dissolved in ethanol with yellow color solutions reacts with
free alpha amino groups of primary amines and gives blue purple product. The blue
Compound was found to form metal complexes, the blue usually being converted to red.
A 1:2 metal to ligand ratio was suggested [5].
The Ninhydrin reaction is a major method in amino acid analysis. However, the reaction
is not selective. All amino acids, except proline and other amine group containing
compounds also produce the same product. The final product being the same feral the
amino acids, this test does not merit for distinguishing one acid from the other.
There are four important steps is the reactions sequence of Ninhydrin with amino acids:
1. Condensation 3. Hydrolysis
2. Decarboxylation 4. Condensation
From the reactions of 2:1 ratio of ninhydrin to amino acids results in the Ruhmann’s
purple product (look at page 10).

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2.2.3 Mechanism reaction of ninhydrin and amino acids

The ketimine (the Schiff base) being of relatively greater potential because it can act ass a
tridentate ligand forming two stable five membered rings on complexation with metal
ions [6, 7]
The stability of these complexes deceases with
- increase in ring size
- increase in the length of the side chain

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 - Increase in distance between the amino and carboxyl group it also showed that
the complexes are distinctly colored, which is important in identifying and
quantifying amino acids, in addition to the above the length of the amino acid
side chain has an influence on the complexing properties of the amino acid to
wards the common transitional metal ions. [7]
This is the basis for studying the reaction between ninhydrin and a variety of amino acids
in the presence of metal ions, particularly transition metal ions.

The metal complexes are distinctly colored. A specific correlation of metal ion amino
acid colors can thus be developed on the result which can from a basis for amino acid
identification and determination
2.3 Schiff Bases
They are compounds containing an amino or azomethine group (R-C=N-) and are usually
formed by the condensation of a primary amine with an active carbonyl compound. The
reaction to prepare Schiff base is reversible, progressing through a carbine amine
intermediate and requires the removal of water.
Schiff bases which are effective as coordinating ligands have a functional group OHNH2,
SH etc, sufficiently, near the site of condensation so as to form five or six membered
chelating ring on reaction with metal ions
-
O
R
R R'
C O + R' NH 2 C NH2+
R
R

R HO
R
H2O C N R
+ C NR H2+

- R R

Where R is H and R’ alky aryl OH, NHR and OR group Reaction mechanism for the
formation of Schiff base. Schiff bases have played an important role in the development

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of coordination chemistry as they form stable complexes with most of the transition
metals.
In the area of bio-inorganic chemistry, interest on Schiff base metal complexes has been
due to the role such complexes play in providing synthetic models for metal containing
sites in metalloproteinase and enzymes.

A wide variety of ligands may be obtained via the Schiff base condensation reactions
which vary in dent city, flexibility, and nature donor atoms, and in electronic properties.
Metal complexes of Schiff bases have varied geometries and magnetic properties.
Multidentate ligand having oxygen and nitrogen donor system reveal a number of ‘ONN’
and ‘ONO’ donor sequence which have resulted in the formation of multinuclear metal
cheated.
As the chelating function is found in different environment, they are likely to provide a
verity of donor system, like ONN, OO and ONO for efficient metal binding reactions.
2.3.1 Biological Important Of Schiff Base
Schiff base appear to be important intermediates in a number of enzymatic reactions
interaction of enzymes with an amino or a carbonyl group of the sub state .one of the
most prevalent types of catalytic mechanisms in an enzyme to form an imines, or Schiff
base [12]
Stereo chemical investigation carried out with the aid of molecular models showed that
schiff base formed between methylglyoxal and the amino groups of the lysine side chains
of proteins can bend back in such away towards the nitrogen atoms of peptide groups that
a charge transfer can occur between these groups and oxygen atoms of the schiff bases .
In this respect, pyridoxal Schiff bases derived from amino acids have been prepared and
studied. Schiff bases derived from pyridoxal and amino acids are considered very
important ligand from the biological point of view .transition metal complexes of such
ligand is important enzyme models. The rapid development of these ligand are important
and resulted in an enhanced research activity in the filed of coordination chemistry
leading to very interesting, conclusions[8].
Certain polymeric Schiff bases have been reported which possess anti tumor activity .the
schiff bases have the highest degree of hydrolysis at PH= 5 and the solubility in water it is

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also high at this PH. The astictumors activity of the bases towards astictumors increases
considerable with slight increase in water solubility .Another important role of Schiff
bases structure is in transmination. Tranaminases are found in mitochondria and cytosal
of eukaryotic cells .All the Tranaminases appear to have the same prosthetic group, i.e.
pyridoxal phosphate, which is non- covalently linked to the enzyme protein.
The biosynthesis of porphyrin,for which glysine is a precursor and another important
pathway ,which involves the intermediate formation of schiff base between keto- group
of one molecules of α-amino acid and α – amino group of lysine residence of an enzyme .
2.3.2 Catalytic applications of Schiff bases
Schiff bases are condensation products of primary amines with carbonyl compounds and
they first reported by Schiff in 1864. The common structural features of these compounds
is the azomethine group with a general formula RHC = N- R’ where R and R ‘ are alkyl
,aryl, cycloalkyl or heterocyclic groups which may be various substituted .these
compounds are also known as imines or azomethine Several studies showered that the
presence of alone pair of electrons in an sp2hybridized orbital of biological importance
.Because of the relative easiness of preparation ,synthetic flexibility ,and the special
property of C=N group, Schiff base are generally excellent chelating agents especially
when a functional group like - OH or –SH is present close to the azomethine group so as
to form a five or six member ring with the metal ion. Versatility of schiff base their
complex makes further investigations in this area highly desirable.
Recent studies showed that transition metal complex of Schiff bases have emerged as
highly efficient in various fields of synthesis and other useful reactions. Synthetic
chemists some times seek imitate the efficiency and elegance of he biosynthetic
machinery by designing biomimetic reactions on path ways. Probably the most
astonishing biometric reactions are processes, which combine several transformations in
sequence and produce complicated structure from comparably simple stating materials, in
a simple laboratory operation.
The role of schiff base catalysts in the synthesis of quality polymers is also equally
important. A serious Schiff base ruthenium complexes which acted as catalysts in the
filed of atom transfer radical polymerization were reported to be synthesized transfer
radical polymerization were reported to be synthesized.

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When activated with trimethylsilyl azomethine polymerization of Norborene and
cyclooctene. The activities for both types of reaction were reported to be depending up
on the satiric ,bulk and electron donating ability the Schiff base ligand and optimal
equilibrium in atom transfer radical polymerization could be established adjusting the
steric and electron properties of the a schiff base ligand.
2.4 The chemistry of metal ions
Cobalt always occurs in nature association with nickel. the oxidation of cobalt increased
stability of II to state the III state is the relatively unstable simple , compounds but the
low spin complex are exceedingly numerous and stable , especially where donor atoms (
usually nitrogen)make strong contribution to the ligand field .Cobalt ( II ) forms
numerous complex mostly either octahedral or tetrahedral but five -coordinate square
spices are also known .the tetrahedral complex of Cobalt ( II) are more .This is due to the
fact that for a d7 ion,ligand field stabilization energies disfavor the tetrahedral
configuration relative to the octahedral one to smallest extent that for any other dn
(1<n<9) configuration[9].
The maximum coordination number of nickel (II) is six. nickel ( II) forms a large number
of complex with coordination number three to fix , a considerable number neutral ligands
,especially amines displace some or all of the water molecules in the octahedral Ni(H20)+2
form complexes such as trans Ni(H20)2 (NH3)4)(No3) 2, [NiNH3)6] (Clo4)2 and [Ni(en)3
]SO4 . These complexes are characteristically blue or purple in contrast to the bright green
of the hexa aqua nickel ion. This is because of shift in the observation band when water
ligands are replaced by other ring towards the stronger and of the spectrochemical series
.on the other hand softer ligands, such as phosphors and sulphur ligands, generally have
four coordinate species, with a strong preference for square planar. Nickel does, how
ever, have a tendency to add a further ligand to give five coordinate compounds. Most cu
(II) salts dissolve readily in water and give the aqua ion,
Addition of ligands to such aqua ions solution leads to the formation of complex by
successive displacement of water molecules with NH3, for example the spices [CU (NH3)
(H2O)6] 2+ --- [ cu (NH3)4(H2O )2 ] 2+ are formed in the normal way. Addition of the fifth
NH3 can occur in aqueous solution, but the sixth occur only in liquid ammonia .the
reason for this unusual behavior is connected with the John- Teller effect.

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Because of Cu (II) ion does not bind the fifth and sixth ligands strongly (even the H2O)
when this intrinsic weak binding of the fifth and sixth is added to the normally, expected
decreases in the step wise formation constants. Many amine complex of Cu (II are
known ,and all are much more intensely blue than the aqua ion .This is because amines
produces a strong ligand filed ,which case the absorption band for example ,in he aqua
ion the absorption maximum is at -800nm where as in [ CU (NH3) (H2O)2] 2] it is at
~600nm .the reversal of the shifts with increasing take up of NH3 for the fifth ammonia
is to be noted ,indicting again the weaker boding of the fifth ammonia molecule
Zinc forms stable complex with ligands containing N,S,O halides and CN -1 .compounds
of zinc (II ) ions are characteristically diamagnetic ad are color less .the d10 configuration
affords no crystal filed stabilization .stereochemistry of the a particular and satiric
2+
requirements of the ligands .Thus zinc (II ) favors four stage of zinc is because of its
complete d shell and two additional S electrons .There is no evidence that it is oxidized
or reduced or reduced in biological reactions. It forms planar complexes but many
octahedral complexes are also known the stereochemistry of the zinc (II ) complexes
largely determined by the ligands size ,electrostatic and the type of bonding .Due to
similarity of size ,charge electronic configuration zinc (II ) tends to act as a metabolic
antagonists to zinc (II )[10].

The coordination chemistry of transition metal ions considered in the investigation:

cobalt (II) and nickel (II) will be presented in terms of dn configuration.
2. 4.1 Cobalt II) complexes
Cobalt with a d7 configuration is known four coordinate ( tetrahedral ) and six coordinate
( octahedral ) stereochemistry .the electronic spectra of tetrahedral cobalt ( II) complexes
are intense than those of the octahedral ones[11].
In octahedral cobalt (II) complexes 4T1g and 2
A1g are the spin free and spin paired
ground state respectively. For high octahedral geometry, a band near 8000-1000 Cm-1 can
be assigned to 4T1g 4
T2g transition A multiple band observe around 2000 cm -1
is
attributed . 4T1g 4
T2g transition
The 4T1g 2
Eg transition is interesting in that it represents configurationally t2g5
eg2 t2g6eg1 and should be brood and it maximum should shift to lower frequencies

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with decreasing temperature, since its energy curve plotted against of has a larger
negative slope than the curve for the ground tern [12]
Some other transitions of CO (II) are 4T1g (F) 4T1g 4
T2g, 4
T1g 2
Eg, 4
T1g
4 4 4 -1 -1
A2g (F) and T1g T1g (P) which are observed at 8000-9000cm 11 000cm ,1600-
-1
18000cm And 2000 -21000cm-1 respectively.

Tetrahedral complexes of Co (II) with 4A2 ground state are expected to have three
transitions. 4A2 4
T2, 4T2 4
T1 (F) and 4A2 4
T2 (P) low spin square planar
complexes exhibit a narrow band near 8500cm-1 and a stronger bounder band near
20000cm -1.
2.4.2 Nickel (11) complexes
Octahedral Ni (II) complexes with 3A2g ground state are expected to have three spin
allowed transitions. 3A2g 3
T1g (F) (7000-13000cm-1) 3A2g 3
T1g (F) (1000-
2000cm) and 3A2g 3
T1g (P) (19000-27000cm).
The octahedral usually consist of a bend in the 1R at 8600cm -1 with ~ 2.5, a close pair
of bands in thread (¬14000cm with 1.8) followed by a weaker band (<1) at 18500cm and
a some what stronger (~4 transition in the blue at 25500cm-1 .
In addition, two spin forbidden transitions 3A2g 1
E1g And 3A2g 1
T2g Are also
observed, the fist near the second spin allowed truncation and the other band between
second and third spin allowed transitions that is approximations around 15400cm -1 and
18500cm-1 respectively.

Tetrahedral Ni (II) complexes with 3T1g ground state, generally exhibit four transitions.
They are 3T1 3
A2, 3T1 1
E, 3T1 3
T1 (P) and 3T2 1
T1 (P) the band 3T1
1
T1 (P) is a strong the band of high intensity when compared with others.
Square planar Ni (11) complexes have three spin allowed –d bands corresponding to 1A1g
1 1 1
A2g, A1g B1g and 1A1g 1
Eg transitions are expected. The square planar Ni (II)
complexes do not have any absorption band below clearly distinguished from octahedral
and tetrahedral complexes [12].

Prepared by Tesfaye Tebeka 23

2.5 Objectives and the scope of the present studies
Schiff base and its complexes have a variety of application including biological, chemical
and analytical. Earlier work has shown that some drugs showed increase activity when
administrated as metal chalets rather than as organic compounds. But, recently a
particular attention has given to the synthesis and study of diamino tetra dentate Schiff
and their complexes in addition to this ninhydrin is most commonly used to detect finger
print. Thus synthesizing and characterizing Schiff base and Ruhmann’s purple that are
derived from different amino acid(Glutamine Iso-leucine ,Cystein Lysine) with ninhydrin
will be studied however recent studies were synthesized and characterized.
2.5.1General objective
• To synthesis and characterize schiff base and Ruhmann’s purple
transition metal complexes derived from ninhydrin and amino acids.
2.5.2 Specific objectives
• To identify the synthesized ligand is unidentate or bidentate
ligands.
• To run the UV-visible of the synthesized metal complexes
• To measure the molar conductance of synthesized metal
complexes

Prepared by Tesfaye Tebeka 24

 CHAPTER THREE
3 Materials and methodology
All chemicals used in this work Ninhydrin, Amino acids likes;isolucine, lysine, cystein
and glutamine, metals salt Co(NO3)2, Ni (NO3)2, Ethanol, chloroform, methanol, distilled
water, Acetone cobalt standard, Nickel standard, perchloric acid .All the chemical used
are analytical graded(BDH)
3.1 Apparatus and instruments
The apparatus we used in these projects are melting point apparatus condenser, mantle
heater, round bottom flask, rotator evaporator beakers, measuring cylinder, ice bath,
desiccators, sunction pump, funnel, filter paper and stirrer
3.2 General procedures
3.2.1 Synthesis of Schiff base derived from cystein with Ninhydrin
0.007 mole of cystein (1gm) was dissolved in 15 ml of absolute ethanol (99.6%) on
heating 0.007 mol of Ninhydrin (1gm) was dissolved in 15ml of ethanol and the above
two solution mixed together.
The ethanolic solution was refluxed for about 3 hours at 60-70 Co The volume of the
solution were reduced to one third by rotatory evaporator. The violet blue solution was
cooled at ice bath (0oC) until it forms a solid crystal. Then the crystal was filtered on
Suction filtration and washed with ethanol and dried over desiccators for further use in
metal complex.
3.2.2 Synthesis of Ruhmann’s purple
Synthesis of Ruhmann’s purple derived from Iso-leucine and Ninhydrin
0.006 mol (7.6 mmol) of Iso- leucin (1gm) was dissolved in 15ml absolute ethanol 0.012
mole of ninhydrin (2gm) was dissolved in 15ml absolute ethanol.
The ethanol solution was mixed and refluxed for 3 hours at 60-70 0Co the volume of the
solution was reduced to one third of the total solution by rotatory evaporator. The purple
color product was filtered on sunction filtration for further use in Ruhmann’s purple
metal complex
Synthesis of ruhmann’s purple derived from lysine and glutamine with ninhydrin

Prepared by Tesfaye Tebeka 25

The same procedure were used for the synthesis of Ruhmann’s purple derived from
lysine and glutamine with ninhydrin as that of Iso-leucine and ninhydrin
3.2.3 Synthesis of Schiff base metal complex
3.2 mmol of Schiff base (0.5gm) previously synthesized was dissolved in 15ml of ethanol
and 3mmol metal nitrate salt of Ni (II) and Co (II) of 0.5gm was dissolved in 15ml of
ethanol. The two solutions was mixed and refluxed for2-3hrs 50_60. oc After refluxing
the volume of the solution was reduced to one third and cooled at 0oc the solid crystal
complex was filtered, washed with ethanol and dried in desiccators
3.2.4 Synthesis of Ruhmann’spurple metal complexes
Ruhmann’s metal complexes of Iso leucine and ninhydrin (0.82 mmol) of Ruhmann's
purple (R1) derived from isolation (0.58gm) was measured and dissolved in 15ml ethanol.
4.37 mmol of metal nitrate salt Ni (NO3)2 (0.8gm) was dissolved in 15ml of absolute
ethanol. The solution was mixed and refluxed for 2.5 hours at 65 oc.filtered and stored the
crystal in desiccators .the same ruhmann’s purple (1.6 mmol =lgm) was dissolved in
ethanol and 8.37 mmol of CoNO3)2
1.6 gm was dissolved and the resulting ethanolic solution was mixed and refluxed for
about 2.5 hours at 65 oc .then filtered and stored in desiccators.
Ruhmann’s purple metal complex of glutamine and ninhydrin (0.82mmol) of Ruhmann’s
purple (R2) derived from glutamine and Ninhydrin, 0.5mg was dissolved in 15ml of
absolute ethanol. 4.37 mmol of metal nitrate salt Ni (NO3)2=0.8gm was dissolved in 15ml
absolute ethanol ad the resulting ethanolic solution was mixed another the same
ruhmann’s purple (1.6mmol =1gm was dissolved in ethanol and 8.37 mmol of Co (NO3)2
was mixed and refluxed for 2.5 hrs at 65 oc and reduce the volume by rotary evaporator,
cooled and filtered and washed the crystal with cold ethanol and stored in desiccators
3.2.5 Ruhmann’s purple metal complex of lysine and ninhydrin
1.32 mmol of Ruhmann’s purple derived from lysine and ninhydrin (R3 ) was dissolved
in ethanol and mixed 2.2mmol of Co(NO3)2 =0.4gm ) was dissolved in ethanol and mixed
well .Another the same Ruhmann’s purple( 1.2mmol = 0.7gm ) was dissolved in ethanol
and 2mmol of Ni(NO3)2 was dissolved in the same solvent .The resulting ethanolic
solution was refluxed separately for 2:30 hrs at 65 oc and reduce the volume by rotatory

Prepared by Tesfaye Tebeka 26

evaporator. After the volume was reduced it was cooled, filtered and washed the crystal
with cold ethanol and stored in desiccators.
3.3 Characterization of complexes
The complex were Characterized by the following parameters; solubility, melting
decomposition points, conductivity measurement, electronic absorption spectra
(UV_Vis), TLC and AAS
3.3.1 Thin layer chromatography
The completeness of the reaction was tested using thin layer chromatography precoated
with silica gel plates were used for stationary phase and ethanol was used as a mobile
phase. The completeness of the reaction was determined by the appearance of single spot
(blue or violet –blue color that of the reaction between amino acid and ninhydrin.)
3.3.2 Solubility
The Solubility of the complexes was cheeked by various organic solvents: Diethyl ether,
acetone, and methanol, chloroform (CHCl3) Benzene, ethanol by stirring a small amount
of the complex a test tubes
3.3.3 Melting (decomposition points)
The melting point (decomposition points) was determined by placing a finely powdered
sample in a capillary tube and heating by melting point apparatus.
3.3.4 Conductivity measurements
The conductivity measurements were performed using conductometres in acetone, aprotic
solvent having 10-3 M at room temperature (Philip Harris Conductometres)
3.3.5 Electronic absorption spectra
Electronic absorption spectra in the UV- Visible range were recorded in 200-1100nm
using acetone as solvent (SPECTRONIC GENESEYC 2PC)
3.3.6 Flame atomic absorption spectroscopy
Metal complex was pre pared by heating the complex in 5ml of HNO3 and 10ml of
perchloric acid. For sample analysis four series of working standard metal solution were
prepared by dilution of the metal stocks solution with water and reading the absorbance
(Buck Scientific)

Prepared by Tesfaye Tebeka 27

 CHAPTER FOUR
4 RESULTS
The composition of the complexes are indicated in each case by metal and (R1, R2, R3) or
s or a combination in which R1= Ruhmann’s purple derived from Iso-leucine and
ninhydrin, S = Schiff base of cystein and ninhydrin
R2 = Ruhmann’s purple of ninhydrin and glutamine, R3 = Ruhmann’s purple of Ninhydrin
and lysine .The compositions are judged from the analytical and spectral data which will
be presented and discussed in the following sections
Table-1 melting point of complexes
Complex Color Appearance Yield (%) Mp (dec.t )0c
CoS Shiny white crystalline 50.13 330
NiS Shiny white crystalline 20.9 330
CoR1 red powder 63.4 236
NiR1 Brick read powder 72.4 220
CoR2 red powder 45.5 229
NniR2 Brick read powder 54.3 241
CoR3 Grey powder 79.24 235-244
NiR3 Grey powder 77.6 238-243
Where S is Schiff base
R1=Ruhmann’s purple derived from Iso-leucine and ninhydrin
R2= Ruhmann’s purple of glutamine and ninhydrin
R3=Ruhmann’s purple of lysine and ninhydrin
Solubility test of metal complex
Solubility of complexes was checked in acetone, chloroform, ethanol solvents by shaking
small amount of the complex in test tube.

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Table- 2 Soluble test of complex indifferent solvent

Complex Acetone CHCL3 CH3OH

COS X X X
NIS X X X
CoR1 X  
R2Ni   
COR2  X 
NiR2  X 
COR3   X
NiR3   X

Where s- Schiff derived form cystein ninhydrin

R1= Ruhmann’s purple of Iso-leucine and ninhydrin
R2= Ruhmann’s purple of glutamine and ninhydrin
R3=Ruhmann’s purple lysine and Ninhydrin
 - Soluble
X – Insoluble

Table -3 – molar conductance values Ruhmann’s purple metal complex.

Complex Temperature(C0) PH Conductance In acetone Λm
Ω-1 cm2mol -
Blank ( acetone ) 27 0.008 -
CoR1 27 5.177 0.0075 120
Ni R1 27.3 5.69 0.007 56
COR2 27 5.62 0.0065 34.66
NiR2 27 5.63 0.006 24
COR3 27 5.63 0.0055 17.6
NiR3 27 5.393 0.0055 17.6
R1= Ruhmann’s purple of Iso-leucine and ninhydrin
R2= Ruhmann’s purple of glutamine and ninhydrin
R3= Ruhmann’s purple lysine and ninhydrin

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Table-4 Spectral data of metal complexes of Ruhmann’s purple
Complex Band position (cm-1) ε Assignments
CoR1 18518.,20618.6 2130,2200 Bands of the coordinated
azomethine group
NiR1 20833.34 1808 d-d transition
CoR2 24691.34,17391.3 2622,2189 Bands of uncoordinated
Azomethine group
NiR2 17391.5 1916 The aromatic group
CoR3 17543,38,20408.16 2250,2320 d-d transition
NiR3 17857.14,20202.02 2240,2320 d-d transition

Atomic absorption spectroscopic studies result

Table - 5 A for Ni complex
No Standard Absorbance
1 0.5ppm 0.03
2 1ppm 0.06
3 2ppm 0.11
4 4mpp 0.22

Table - 5 B for Ni complex

Sample Absorbance Concentration
results
R1Ni 0.041 0.74sppm
R2Ni 0.055 11ppm
R3Ni 0.072 1.3ppm
SNi 0.085 1.54ppm

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Table- 5 C for Co-complex

Standard Absorbance Concentration

0.5ppm 0.05 -
1ppm 0.09 -
2ppm 0.184 -
4ppm 0.350 0.5ppm
Sample = R1Co 0.006 1ppm
R2Co 0.092 -
R3Co 098 10.8ppm
Sco 0.12 1.44ppm

Prepared by Tesfaye Tebeka 31

4.2 DISCUSSION
The metal complexes isolation from different amino acids namely: Iso-leucine,lysine
,cystein and glutamine are all distinctly colored , stable to atmospheric condition and are
soluble in organic solvent like methanol and ethanol but only partially soluble in solvents
like chloroform and insoluble in petroleum ether
From table 1 the Schiff base metal complexes of Ni (II) Co (II) that is derived from
cystein and ninhydrin neither melt nor decompose up to 330 oc, while the ruhmann’s
purple metal complexes of Ni (II) and Co (II) that are derived from lysine and Ninhydrin
start melting at a temperature around 236 degree centigrade and also complex of Ni (II)
derived from iso-lecine and ninhydrin which melts at lower temperature around 220 oc
Generally the two ligands prepared are Schiff base ligand which is synthesized from
cystein and ninhydrin and Ruhmann’s purple ligands those synthesized from ninhydrin
and iso-lecine sine and glutamine amino acids .
4.2.1 Molar conductance studies
The molar conductance values were calculated from conductivity measurements in
acetone( aprotic non-polar solvent ).The molar conductance values of the products
obtained from all complexes are very small in the range of 17.6 – 120 Ω-1 cm2mol -1

this shows that they are non_electrolyte nature.

From the above table 3 the conductivity of the metal complexes of ruhmann’s purple is
very low indicates that, these complexes are non- electrolyte and this support,
their neutral nature of the complex and the obtained value suggests that in the
coordination sphere their is no anions present outside
4.2.2 UV-Visible spectroscopic analysis
The spectra of transition metal complexes depends on the transition of unpaired electrons
from the ground state to an excited state most of the transition metal complexes are
colored ,a color is observed due to d-d transition in the visible region
The ninhydrin and the amino acid ( Iso-leucin, glutamine , lysine ) from a deep blue
purple colored compound which maximally absorbs at 2469.36 and 17543.36cm-1
The compounds formed via four steps condensation, decarboxylation, hydrolysis and
further condensation.

Prepared by Tesfaye Tebeka 32

The electronic specter data of the metal complexes are given in table 4. For CoR3 and
NiR3 complex, the spectral data displays two bands at 17543.38, 20408.16 and 1785.14,
20202.02cm-1. The first band is due to charge transfer.
Avery strong at 2000cm-1Is assigned of π to π* is due to a molecule π bonds with C= O
group and n to π* transition is due to a compound containing an azomethine group (-
CH=N-) which absorbs between 17391.5 -24691.34cm-1
The band between 24691.34 17391.5cm-1Is also associated with the transition of n to π*
this is due to d-d transition of the complex in the region
The literature data reveals that the band around 32000cm-1 and are assigned to the n to π *
transition of the carbonyl group
The electronic spectrum of the metal complexes of Co (II) and Ni (II) complexes show
common bands at 18518.5cm-1 And 20833.34cm-1 which are the characteristics band of
exocyclic azomethine chromophore in the coordination, which in the free state absorbs at
24691.36cm-1 In Ruhmann’s.
The complex prefers a low spin configuration, which is exhibited due to the presence
strong field ligands; such as the azomethine and carbon groups. The Ni (II) complex
exhibited an octahedral geometry with two unpaired electrons.
The valve of magnetic moment obtained corresponds to the literature valve, indicating
the coordination of the metal in an octahedral geometry and the complexes of Co (II) of
the metal in an octahedral geometry with a low spin configuration.
In octahedral cobalt (II) complexes 4T1g and 2
A1g are the spin free and spin paired
ground state respectively. For high octahedral geometry, a band near 8000-1000 Cm-1 can
be assigned to 4T1g 4
T2g transition A multiple band observe around 2000 cm -1
is
attributed . 4T1g 4
T2g transition
4.2.3 Atomic absorption spectroscopy
The determination of Ni (II) and CO (II) concentration.
0.04gram of metal complex of CO (II) and Ni (O) were digesting in 5ml nitric acid and
10ml of perchloricacid. Four serious of Working standard having 0.5,1,2 and 4 ppm were
prepared by appropriate dilution of metal stock solution with distilled water. The
calibration graph (concentration Vs absorbance) was drown in the appendix part.

Prepared by Tesfaye Tebeka 33

From this calibration curve, the concentration of the metal ions in the complex are
determined having 93.12% Ni (II) and 90.36% Co (II) were found by composition

Prepared by Tesfaye Tebeka 34

 5 Conclusions
Metal complexes such as Co(II) and N (II) were synthesized by using the Schiff base and
Ruhmann’s purple formed from by the condensation of ninhydrin with cystein and
ninhydrin with three amino acids like; Iso-Leucine, Glutamine and lysine respectively.

Even if there is an absence of spectrometer instruments such as; IR, NMR,MS that can
provide substantial evidence for determination of structure of the complexes which is
formed from Ninhydrin - amino acids reactions with transition metals such as Co(II)
Ni(II) will be proposed. The following structure will be drawn based on the central view
of the nature of the ligand_metal complex

I) The proposed structure of Ruhmann’s purple with Ni(II) and Co(II)

Prepared by Tesfaye Tebeka 35

 II The proposed structure for Schiff base with Ni (II) and Co(II).

The complexes formed with Co (II) and Ni (II) is powders in nature and obtained in good
yield. As can be seen from the result data the complexes are distinctly colored; they have
different percentage yields and appearances. The elemental analysis data of the
complexes are given in tables. The analytical data matches with 1:2 metals to Ruhmann’s
purple and1:1schiff base complexes in an octahedral geometry for the complexes of Ni
(II) and Co (II).
The molar conductance (Λ m) values were calculated from conductivity measurements of
the solvent (Acetone) and a metal complex in acetone. The molar conductance values of
the products obtained from all the complexes are very small, in the range of 17.6-120Ω-1
cm-2 mol-1. These show their non-electrolyte nature.
Ninhydrin and Iso-Leucine, glutamine or lysine form a deep blue purple colored
compound known as the Ruhmann’s purple, which maximally absorbs at 20833.34 cm-1
The compound is formed via four steps; condensation, decarboxylation, hydrolysis and
further condensation. The electronic spectral data of the metal complexes are given in
table 4. The bands observed at 2000cm-1 and 21691.34 cm-1 in the complexes are
assigned to the π→π * transition of the benzene moiety. The electronic spectrum of the
Co (II) & Ni (II) complexes show common bands around 18518.5cm-1 and 20833.34cm-1
which are characteristics bands of the exocyclic azomethine chromopher.

Prepared by Tesfaye Tebeka 36

 6 Recommendations
Our project work concerned with preparation, structural determination & characterization
of Schiff base & Ruhmann’s purple which are the condensed from the reaction of
ninhydrin & amino acids and then complexing this residue with transition metals such
as cobalt & nickel complexes. While we doing our experimental analysis we had been
faced the problem such as lack of IR, H-NMR and C-NMR to know the complete
structure of ligands and complexes. And we were also faced lack of chemicals like
DMSO & DMF to dissolve our complexes. So the structure of the complexes & ligands
was proposed using only UV-VIS spectroscopy & from the theoretical back ground. By
taking into consideration these mentioned and other related problems the concerned
body shall give and provide solution.

Prepared by Tesfaye Tebeka 37

 7 REFERENCES

1 FAlbert cotton Advanced Inorganic chemistry, 6th edition.

2. Belete Yilma June 2004 , synthesize and characterization of metal complexes, Office
Research and graduate programs, Addis Ababa University.
3. Skoog Holler BIEMAN, principles of instrumental Analysis, 5th edition.
4 Namsun Wang1996, Amino acid Assay by Ninhydrin colorimetric method,
Department of chemical Engineering universities.
5. Ruhmann, 1911, S.J chem. Soc 99, 792.
6 Jolly, W.L preparative inorganic Reactions, Vol.I.
7. Marry, R, KHarpers1996, Biochemisteary, 24th edition; John wiler New York.
8. J. Lewis and R.G Wilk, 1967, Modern coordination chemistry, principles and methods,
New York.
9 J. Lewis and R.G Wilk, 1967, Modern coordination chemistry, principles and methods,
New York.
10. J. Chemsol Dalton, 2001 Trans, 2850-2857.
11 .Bodie Douglas, Darla mc Daniel, John Alexander, 1995 concept and models of
inorganic chemistry, 3rd edition, USA.
12. J.E. Huheer, EA keiter and R.L Keiter, inorganic chemistry, principle of structure
and Reactivity, 4th edition Harper Collins college publisher USA.

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8 Appendixes
Calculation of the Results

Results obtained from Ruhmann’s purple (R1) and ninhydrin with cobalt (II) taken for
simplicity 1.Determination of molar conductivity having 10-3M
preparation of 10-3M
0.033
mole = mass ⁄molecular weight = −1
=4.95*10-5mol
666.93glmo

Conc. = mol ⁄Vol. of soln , where Volume of Solvent (acetone) =50ml

4.95 *10 −5
C= −3
= 0.99*10-3Mol≈*10-3 mollit
50 * 10 λ
1000k
M(Ω-1cm2mol-1)=
C
Where M -Molar conductivity
K -specific conductance
C - Concentration
1 1  λ
K=  − b where b -call constant=
 R Racetone  ∆
R- Resistance
1 1 0.008 − 0.0075
K= − = = 8.34 ∩ 5
0.0075 0.008 0.0075 * 0.008
8.34 Ι s
M (Ω-1Cm2Mol-1) = 1000* − 3 ,
10 mol / λi
8.34 * 10−9 1
=1000* − 3 −3 −3
where S-Siemens ands=
10 mol / λit * 10 λit / cm Ω
8.34 * 10−9
= 10*
Mol * 10− 3 lit / Cm3
8.34 S *10−3 S * 103 Cm3
=
Mol Cm
( )
M Ω Cm −2η 01−1 =8.34SCm2η01-1
Determination of concentration of standard sample from Absorbance Measurements
2. Determination concentration of Ruhmann’s (R1) Ni Complex
First From the calibration curve the equation must be calculated
Y= mx+ b
m=Slope
x=conc.
b- Intercept
y =Absorbance of sample

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 ∆Y 0.22 − 0.11
Slope (m) = =0.055
∆x 4−2
The equation of calibration curve become
Y=0.055x (The graph pass through origin)
Then from the equation, the concentration of R1 Ni calculated as:
0.041=0.055x
0.041
=X
0.055
x=0.745ppm,
Determination of concentration of Ruhmann’s (R1) Co (II) complex
First From the calibration the equation obtained is
Y=Mx+b
∆Y 0.35 − 0.184
Slope = = =0.083
∆x 4−2
The equation of calibration curve become,
Y=0.083x (pass through the origin) is the equation calibration curve of R1 Co complex
calculated as follow.
Y=0.083x, where Y-is the absorbance of R1 Co complex
0.086= 0.083x
0.060
X= =0.722ppm Concentration of R1Co
0.083
3. Determine the percentage of the metals in the complexes.
From the calibration graph (concentration versus absorbance), the percentage of metals
calculated as follow.
Volumedisted to 100
M (II) % =Absorbance (A1ppm)* *
Mass ofthe sample 1000
Known Data Concentration of Ni Ri= 0.745ppm
Volume diluted to =50ml
Mass of the sample (R1Ni) =0.049m
50mλ 100
Ni (II) %= 0.745ppm* *
0.04 gm 1000
Ni (II) % =93.125%
• Similarly the percentage of Co(II) in Ruhmann’s (R1) Co Complex Was
calculated as
Volume dilluted to 100
Co (II) % = Absorbance (∆ppm) * *
mass of the sample 1000

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 Known data :
Concentration of R1 Co
Calculated from absorbance = 0.722ppm
Volume diluted to=50ml
Mass of the sample (R1Co) = 0.04 gm
50ml 100
Co (II) %= 0.722ppm= *
0.04 gm 1000
Co (II) %=90.36%

4. Percentage yield on of the complexes.

The percentage yield of the complexes are determined as
∆Ctual yield
% yield = *100
theoretical yield
For example the percentage of Ni Ruhmann’s purple complex
A Y of complex=0.49M

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T.Y of R1Ni can obtained from the limiting Reaction

O O

2 N +M(II)
C 0.8g

O- O
0.5g
-
O O

N
O-

O- O
M
-
O O

O- O

From this reaction 2:1moleratio of Ruhmann's purple metal complex the following result was
obtained

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From this rxn 2:1 mol ration
Ruhmann’s purple with the metal

0.59m 0.88
60ηgm 182.71g / mo /
0.82mmol 4.3mmol
The limiting reactant is the Ruhmann’s purple
0.59m X
=
6059mol 666.719 / mol
0.5(666.73)
X= = 0.559m
604
A.Y 0.49m
%Yield= *100 = * 100 = 72%
T /Y 0.559m

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 Graph of calibration curve

Calibration curve of Ni

0.25
y = 0.0553x
2
0.2 R = 0.9986
Absorbance

0.15

0.1

0.05

0
0 2 4 6
Concentration

Where; concentration in ppm

Absorbance in nm

Fig 1; calibration curve of Ni

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 Calibration curve of Co

0.25
y = 0.0553x
2
0.2 R = 0.9986
Absorbance

0.15

0.1

0.05

0
0 2 4 6
Concentration

Where ; Concentration in ppm and

Absorbance in nm

Fig 2; calibration curve of Co

Prepared by Tesfaye Tebeka 45

Prepared by Tesfaye Tebeka 46