Farah's Thesis

Republic of Iraq
Ministry of Higher Education

and Scientific Research
Al-Nahrain University
College of Science
Department of Chemistry
Coordination of some transition metal ion

complexes in choline chloride/tartaric acid
room temperature ionic liquid
A Thesis
Submitted to the College of Science Al-Nahrain
University in partial fulfillment of the requirements
for the Degree of Master of Science in Chemistry
By
Farah Awad Ahmed
(B.Sc.2006) Al.Nahrain University
Supervised by
Dr. Hadi M.A. Abood
September 2008 Ramadhan 1429

Supervisor certification
I certify that this thesis was prepared under my supervision at the

Department of Chemistry, College of Science, Al-Nahrain University as a
partial requirements for the Degree of Master of Science in Chemistry.
Signature:
Name: Dr. Hadi M. A. Abood
Date: / /2008
In view of the available recommendation, I forward this thesis for debate

by the examining committee.
Signature:
Name: Assist. Prof. Dr. Salman A. Ahmed

Head of the Department
of Chemistry College of
Science Al-Nahrain
University
Date: / /2008
Committee certification
We, examining committee, certify that we have read this thesis and
examined the student in its content, and that in our opinion it is adequate
with standing as a thesis for the Degree of M. Sc. in Chemistry.
Chairman Member
Signature: Signature:
Name: Name:
Date: / /2008 Date: / /2008
Member Supervisor / Member
Signature: Signature:
Name: Name: Dr. Hadi M. A. Abood
Date: / /2008 Date: / /2008
Approved for the council of the College of Science.
Signature:
Name: Assist. Prof. Dr. Laith Abdul Aziz Al-Ani
Dean of the College of Science
Date: / /2008
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Acknowledgement
I wish to express my deepest gratitude and great appreciation

to my Supervisor, Dr. Hadi M. A. Abood for suggesting the
problem, his valuable guidance and advice, and continuous
encouragement throughout my study.
Sincere thanks are due to the Chemistry department, Al-

Nahrain University and to Staff of the department, specially the
head of the department Dr. Salman A. Ahmed.
My deepest thanks and appreciation are also due to my lovely

family, for their patience with me, and for their financial and
moral support.
Finally, sincere thanks and deep respect go to all my teachers,

and my friends for their help and support.
Farah Awad Ahmed

2008
Abstract:
Some transition metal chlorides, CrCl3.6H2O, FeCl3.4H2O,

CoCl2.6H2O, NiCl2.6H2O and CuCl2.2H2O were investigated
spectroscopically in the newly prepared choline chloride/ tartaric acid
ionic liquid at room temperature. They were found to be soluble as their
solubilities were determined by measuring the dissolved metal in ionic
liquid by atomic absorption.
The UV-Visible measurements of the transition metal cations of
Cr3+, Fe3+, Co2+, Ni2+ and Cu2+ showed a complex formation with the
above ionic liquid solvent giving an octahedral geometry shape for (Cr3+)
and tetrahedral for the (Fe3+, Co2+, Ni2+ and Cu2+). The solutions were
found to be conductive. It was difficult to obtain the result by the infrared
measurements because of the viscose nature of this solvent; therefore the
complexes are the same as the ionic liquid in measurements.
The resultant solutions were also investigated by substitution of
solvent ligands by oxalic acid and EDTA salt. The added ligands showed
an increase in the absorption energies indicating the occurrence of
substitution reaction and weak coordination of the ionic liquid to their
metal.
Jorgenson rule was used to assist the suggestion of the type of
ligands coordinated to transition metal cations. The nature of the bonding
between the metal ions and the donor ligands was demonstrated through
the Jorgenson rule and calculation of Racah parameters was obtained
from appropriate dn Tanabe-Sugano diagrams together with the
qualitative assistance of Orgel diagrams.
Subject Page
Abstract
Chapter One:
Introduction
1.1. Molten salts and Room Temperature Ionic Liquids (RTILs). 1
1.2. Ionic liquids, literature review. 3
1.3. Green chemistry and green solvents. 5
1.4. Some Physical properties of ionic liquids. 6
1.5. Advantages of Ionic liquids. 8
1.6. Applications of Ionic liquids. 8
1.7. Ionic liquid of choline chloride. 10
1.8. The chemistry of the first transition metal elements. 11
1.8.1. Chromium (III), (d3). 11
1.8.2. Iron (III), (d5). 12
1.8.3. Cobalt (II), (d7). 13
1.8.4. Nickel (II), (d8). 15
1.8.5. Copper (II), (d9). 17
1.9. Interaction of the ligands with the metal ions. 20
1.10. Aim of present work. 25
Chapter Two:
Experimental part
2.1. Chemicals and Instruments. 26
2.1.1. Chemicals. 26
2.1.2. Instruments. 27
2.1.2.1. Metal analysis. 27
2.1.2.2. Electronic absorption spectra measurements. 27
2.1.2.3. Conductivity measurements. 27
2.1.2.4. Fourier transform infrared spectrophotometer (F.T.IR) 27
measurements.
2.2. Setting of heating apparatus. 28
2.3. Practical methods. 28
2.3.1. Drying method. 28
2.3.2. Preparation of choline chloride / tartaric acid room 28
temperature ionic liquid.
2.3.3. Solubility determination. 29
2.3.4. Determination of spectra. 30
2.3.4.1. Orgal diagrams. 30
2.3.4.2. Tanabe-Sugano diagrams. 31
2.3.4.3. Equations. 32
2.3.4.4. Example of calculations. 34
Chapter Three:
Results & Discussion
3.1. Electronic absorption of transition metal chloride in room 37
temperature ionic liquid.
3.1.1. Spectroscopic investigation of Chromium (III) chloride
37
solutions.
3.1.1.1. Chromium (III) chloride in choline chloride /tartaric acid
37
room temperature ionic liquid solution.
3.1.1.2. Substitution Reaction with Oxalic acid. 44

3.1.1.3. Substitution Reaction with EDTA salt. 46
3.1.2. Spectroscopic investigation of Iron (III) chloride solutions. 49
3.1.2.1. Iron (III) chloride in choline chloride /tartaric acid room
49
temperature ionic liquid solution.
3.1.3. Spectroscopic investigation of Cobalt (II) chloride solutions. 56
3.1.3.1. Cobalt (II) chloride in choline chloride / tartaric acid room
56
3.1.4. Spectroscopic investigation of Nickel (II) chloride solutions. 64
3.1.4.1. Nickel (II) chloride in choline chloride / tartaric acid room
64
3.1.5. Spectroscopic investigation of Copper (II) chloride
72
solutions.
3.1.5.1. Copper (II) Chloride in choline chloride / tartaric acid
72
room temperature ionic liquid solution.
3.1.5.2. Substitution with oxalic acid. 77
3.1.5.3. Substitution with EDTA salt. 79
3.2. The conductivity in choline chloride/ tartaric acid ionic liquid
81
and with addition of metal chlorides.
3.3. The F.T.IR spectra of choline chloride/ tartaric acid ionic
82
liquid and metal chlorides.
3.3.1.A. The infrared spectra of choline chloride. 82
3.3.1.B. The infrared spectra of tartaric acid.
83
3.3.1.C. The infrared spectra of choline chloride/ tartaric acid ionic
83
liquid.
3.3.2. The infrared spectra of {Cr (III), Fe(III), Co(II), Ni(II) and
83
Cu(II) chlorides} in choline chloride/ tartaric acid ionic liquid.
3.4. Conclusions. 93
3.5. Suggestions for future work. 94
References 95-101
Arabic Abstract
NO. Figures Page

1.1 Spectra of NiCl2, (curve A) c = 0.046 mol dm-3 in acetamide-
potassium nitrate at 90 ºC, (curve B) c = 0.012 mol dm-3 in 17
butyramide-sodium nitrate at 140 ºC.
The splitting of free-ion D terms in octahedral and
2.1 30
tetrahedral fields.
2.2 The splitting of free-ion F and P term in octahedral and
31
tetrahedral fields.
2.3 Splitting of terms for dn configurations in to (a) and (b) 32
3.1 The UV-Vis spectra of CrCl3.6H2O in choline chloride /
tartaric acid ionic liquid curve (A), in aqueous solution curve
38
(B), with addition of oxalic acid curve (C) and with addition
of EDTA salt curve (D).
The UV-Vis spectra of chromium (III) of (0.06 m) in choline
3.2 38
chloride / tartaric acid room temperature ionic liquid.
3.3 Tanabe – Sugano diagram for d3 ion configuration. 39
Crystal field splitting of 4F term of d3 ion octahedral
3.4 40
configuration.
The UV- Vis Spectra of CrCl3.6H2O in choline chloride /
3.5 tartaric acid ionic liquid (0.096 M) (curve A) and in aqueous 41

solution (0.1M) (curve B).
3.6 Suggested structure for chromium (III) in choline
44
chloride/tartaric acid ionic liquid.
3.7 The UV-Vis Spectra of CrCl3.6H2O in choline chloride
45
/tartaric acid ionic liquid with addition of oxalic acid.
3.8 Suggested structure for chromium (III) in choline chloride
46
/tartaric acid ionic liquid with addition of oxalic acid.
3.9 The UV- Vis spectra of CrCl3.6H2O in choline chloride /
47
tartaric acid ionic liquid with addition of EDTA salt.
Suggested structure for chromium (III) in choline
3.10 chloride/tartaric acid ionic liquid with addition of EDTA 48

salt.
The UV– Vis. spectra of pale yellow solution of FeCl3.4H2O
of (0.373 m) in choline chloride / tartaric acid ionic liquid at
3.11
50
room temperature A- with normal scan and B- magnified at
the absorbance scale.
Tanabe- Sugano diagram for octahedral and tetrahedral d5
3.12 51
ion configuration.
Suggested structure for Iron (III) in choline chloride / tartaric
3.13 52
acid ionic liquid.
The UV-Vis. spectra of pale yellow solution of FeCl3.4H2O

in choline chloride/tartaric acid room temperature ionic
53
3.14
liquid with addition of oxalic acid A- with normal scan and
B- magnified at the absorbance scale.
Suggested structure for Iron (III) in choline chloride/tartaric
3.15 54
acid ionic liquid with addition of oxalic acid.
3.16 The UV- Vis. Spectra of pale yellow solution of FeCl3.4H2O 55
in choline chloride / tartaric acid room temperature ionic
liquid with addition of EDTA salt.
3.17 Suggested structure for iron (III) in choline chloride / tartaric 55

acid ionic liquid with addition of EDTA salt.
Spectra of CoCl2.6H2O in choline chloride/ tartaric acid
ionic liquid at room temperature curve (A), with addition of
3.18 57
oxalic acid curve (B), and with addition of EDTA salt curve
(C).
3.19 57
ionic liquid at room temperature.
Crystal field splitting of 4F term of d7 ion tetrahedral
3.20 58
configuration.
Suggested structure for cobalt (II) chloride in choline
3.21 59
chloride/ tartaric acid ionic liquid.
3.22 61
ionic liquid at room temperature with addition of oxalic acid.
Suggested structure for cobalt (II) in choline chloride/
3.23 62
tartaric acid ionic liquid with addition of oxalic acid.
3.24 63
ionic liquid at room temperature with addition of EDTA salt.
Suggested structure for cobalt (II) chloride in choline
3.25 64
chloride/tartaric acid ionic liquid with addition of EDTA salt
Spectra of NiCl2.6H2O in choline chloride/ tartaric acid ionic
3.26 liquid at room temperature curve (A), with addition of oxalic 65

acid curve (B), and with addition of EDTA salt curve (C).
The UV- Vis. Spectra of NiCl2.6H2O (0.217 m) in choline
3.27 66
chloride/ tartaric acid ionic liquid at room temperature.
Tanabe-Sugano diagram for d8 tetrahedral electronic
3.28 67
configuration.
Suggested structure for nickel (II) chloride in choline
3.29 69
The UV- Vis spectra of NiCl2.6H2O in choline chloride /
3.30 tartaric acid ionic liquid with addition of oxalic acid. 70
3.31 chloride/ tartaric acid ionic liquid with addition of oxalic 70

acid.
The UV-Vis spectra of NiCl2.6H2O in choline chloride /
3.32 71
tartaric acid ionic with addition of EDTA salt.
3.33 chloride/ tartaric acid ionic liquid with addition of EDTA 72
salt.
UV-Vis spectra of copper (II) chloride in choline chloride /
tartaric acid ionic liquid at room temperature curve (A), with
3.34 74
addition of oxalic acid curve (B), and with addition of EDTA
salt curve (C).
The UV-Vis. Spectra of CuCl2.6H2O in choline chloride/
3.35
74
tartaric acid ionic liquid at room temperature.
Suggested structure for copper (II) in choline chloride/
3.36 75
tartaric acid ionic liquid.
The UV- Vis. Spectra of Cupric chloride in choline chloride/
tartaric acid ionic liquid at room temperature with addition
3.37 78
of oxalic acid.
3.38 78
The UV- Vis. Spectra of Cupric chloride in choline chloride/
3.39 tartaric acid ionic liquid at room temperature with addition 80

of EDTA salt.
3.40 80
3.41 F.T.IR spectrum of choline chloride. 85

3.42 F.T.IR spectrum of tartaric acid. 86
3.43 F.T.IR spectrum of choline chloride/tartaric acid ionic liquid. 87
3.44 F.T.IR spectrum of chromium (III) chloride. 88
3.45 F.T.IR spectrum of iron (III) chloride. 89
3.46 F.T.IR spectrum of cobalt (II) chloride. 90
3.47 F.T.IR spectrum of nickel (II) chloride. 91
3.48 F.T.IR spectrum of cupper (II) chloride. 92
NO. Tables Page

The chemicals used in this work with their purities and
2.1 26
suppliers.
Solubilities of transition metal chlorides in choline chloride/
2.2 tartaric acid ionic liquid with added number of moles of 29

oxalic acid and EDTA salt at about 42:1 ligand to metal ratio.
2.3 Splitting of terms for dn configuration. 33

2.4 Values of g and f factors for metal ions and various ligands. 33
2.5 Peak position of chromium (III) ions in choline 34
chloride/tartaric acid room temperature ionic liquid.
3.1 Electronic spectra for complexes of chromium (III) ions in 42
aqueous solution, ionic liquid and with addition of ligands.
3.2 Electronic spectra of complexes of iron (III) ions in choline
chloride/ tartaric acid ionic liquid and with addition of 52
ligands.
3.3 Electronic spectra of complexes of cobalt (II) ions in aqueous
59
solution, ionic liquid and with addition of ligands.
3.4 Electronic spectra for complexes of cobalt (II) chloride in
60
various room temperature ionic liquids.
Electronic spectra for complexes of nickel (II) ions in choline
3.5 68
chloride/tartaric acid ionic liquid and with addition of ligands.
3.6 Electronic spectra of complexes of copper (II) chlorides in
choline chloride/ tartaric acid ionic liquid and with addition of 76
ligands.
3.7 Conductivity of room temperature ionic liquid and with 82
addition of metal chlorides at different concentrations.
Abbreviation Name
A. A. Atomic absorption
UV-Vis Ultraviolet-Visible
B' Racah parameter
β Nephelauxetic facter
RTILs Room temperature ionic liquids
Oh Octahedral
Th Tetrahedral
Solv. Solvent
Fig Figure
Ox Oxalic acid
EDTA Ethylenediamine Tetraacetic Acid
Tetrasodium Salt Dihydrate
VOC Volatile organic compound
CFT Crystal field theory
DES Deep eutectic solvents
nm Nanometer
M Molarity
m Molality
ms Mili siemens
µs Micro siemens
CHAPTER
Chapter one Introduction
Chapter one
Introduction
1.1. Molten salts and Room Temperature Ionic Liquids

(RTILs):
Molten Salt is a rather dreadful name for an otherwise useful
category of materials and processes. The term ''Molten Salt'' is self-
descriptive; it is melted salt(s). Another common name is Fused
Salt(s).(1,2)
Salts are simple, usually ionic (that is the chemical bonds are a
simple ionic type) and stable compounds. The most common example of
molten salt is "table salt", or sodium chloride (NaCl). Both sodium and
chlorine are reactive; sodium is one of the most electropositive substances
(tends to lose an electron) and chlorine one of the most electronegative
(tends to take an electron). These two opposite substances readily join to
form stable sodium chloride via a strong ionic bond. The melting point of
sodium chloride is 801 ºC. At this point it becomes a liquid, and thus a
"molten salt". (3)
Molten salts are of considerable interest, not only from the
technological point of view, but also from the standpoint of satisfying a
fundamental curiosity. Structural studies of molten salts (such as alkali
halides) by x-ray and neutron diffraction have been undertaken as part of
a general program to determine the properties of molten salts. (3)
Room temperature ionic liquid is one type of molten salts which are
liquid that contain essentially ions only.
1
Some ionic liquids, such as ethyl ammonium nitrate, are in a

dynamic equilibrium where at any time more than 99.99 % of the liquid is
made up of ionic rather than molecular species (3). In the broad sense, the
term includes all molten salts, for instance, sodium chloride at
temperatures higher than 800 ºC. Today, however, the term "ionic liquid"
is commonly used for salts whose melting point is relatively low (below
100 ºC). In particular, the salts that are liquid at room temperature are
called room-temperature ionic liquids, or RTILs. (4,5)
Ionic liquids are attractive solvents as they are non-volatile, non
flammable, have a high thermal stability and are relatively inexpensive to
manufacture. They usually exist as liquids well below room temperature
up to a temperature as high as 200oC. (6,7)
Ionic liquids are highly solvating, non-coordinating medium in
which a variety of organic and inorganic solutes are able to dissolve.
They are outstandingly good solvents for a variety of compounds, and
their lack of a measurable vapor pressure makes them a desirable
substitute for Volatile Organic Compounds (VOCs).
The key point about ionic liquids is that they are liquid salts, which
means they consist of a salt that exists in the liquid phase and have to be
manufactured, they are not simply salts dissolved in liquid. Usually one
or both of the ions is particularly large and the cation has a low degree of
symmetry, these factors result in ionic liquids having a reduced lattice
energy and hence lower melting points. (8)
2
1.2. Ionic liquids, literature review:

The early history of ionic liquids began in 1914 when the first report
(9)
of a room temperature molten salt was reported by Walden . He
reported the physical properties of ethyl ammonium nitrate, [C2H5NH3]
NO3, which has a melting point of 12 ºC, formed by the reaction of
(10)
ethylamine with concentrated nitric acid. Then, Hurley and Weir
stated that a room temperature ionic liquid could be prepared by mixing
and warming 1-ethyl pyridinium chloride with aluminum chloride. In
(11) (12)
1970s and 1980s, Osteryoung et al. and Hussey et al. respectively
carried out extensive research on organic chloride–aluminium chloride
ambient temperature ionic liquids and the first major review of room
(12)
temperature ionic liquids was written by Hussey . It was about in the
(13,14)
middle of the 1990s when it was decided in the community to
replace the term "room temperature molten salt'' by "ionic liquid", and an
ionic liquid is defined today as a liquid consisting solely of cations and
anions with a melting point of 100 ºC and below . Although any high
temperature molten salt is an ionic liquid, too, this novel term for the
room temperature liquids clearly made a distinction.
The ionic liquids based on AlCl3 can be regarded as the first
generation of ionic liquids. The hygroscopic nature of AlCl3 based on
ionic liquids has delayed the progress in their use in many applications
since they must be prepared and handled under inert gas atmosphere.
Thus, the synthesis of air and water stable ionic liquids, which are
considered as the second generation of ionic liquids, attracted further
interest in the use of ionic liquids in various fields. (9)
3
In 1992, Wilkes and Zaworotko (15) reported the first air and moisture
stable ionic liquids based on 1-ethyl-3-methylimidazolium cation with
either tetrafluoroborate or hexafluorophosphate as anions. Unlike the
chloroaluminate ionic liquids, these ionic liquids could be prepared and
safely stored outside of an inert atmosphere.
Accordingly, this may be the birth of new and important industrial
materials, or we are witnesses to a renaissance of molten salt chemistry.
One fairly general feature of ionic liquids that is not part of the definition
is that most have organic cations and inorganic anions. There are many
(16,17)
synonyms used for ionic liquids that complicate a literature search.
‘
Molten salts’ is the most common and most broadly applied term for
ionic compounds in the liquid state. Unfortunately the term ‘ionic liquids’
was also used to mean the same thing long before there was much
literature on low melting salts. It may seem that the difference between
ionic liquids and molten salts is just a matter of degree (literally);
however the practical differences are sufficient to justify a separately
(18)
identified niche for the salts that are liquid around room temperature.
That is, in practice the ionic liquids usually may be handled like ordinary
solvents. There are also some fundamental features of ionic liquids, such
as strong ion-ion interactions that are not often seen in higher temperature
molten salts. Synonyms for materials that meet the working definition of
ionic liquid are ‘room temperature molten salt,’ ‘low temperature molten
salt’, ‘ambient temperature molten salt’, ‘ionic fluid’and ‘liquid organic
salt’. The link between ionic liquids and green chemistry is clearly related
to the solvent properties of ionic liquids. (19,20)
4
1.3. Green chemistry and green solvents:

Green chemistry is the use of chemistry for pollution prevention
more specifically, green chemistry is the design of chemical products and
processes that reduce or eliminate the use and generation of hazardous
substances. Green chemistry is a highly effective approach to pollution
prevention because it applies innovative scientific solutions to real-world
environmental situations. (21-24)
Green solvents are environmentally friendly solvents or bio solvents,
which may be derived from the processing of agricultural crops. Ethyl
lactate, for example is a green solvent derived from processing corn. (25)
Ethyl lactate is a particularly attractive solvent for the coatings
industry as a result of its high solvency power, high boiling point, low
vapour pressure and low surface tension. It is a desirable coating for
wood, polystyrene and metals and also acts as a very effective paint
stripper and graffiti remover. Ethyl lactate has replaced solvents including
toluene, acetone and xylene, which has resulted in the workplace being
made a great deal safer. (26)
The uses of petrochemical solvents are the key to the majority of
chemical processes but not without severe implications on the
environment. The use of toxic solvents contributes to air emission of
volatile organic compounds (VOCs); they are now considered as
environmentally unacceptable. (27)
The Montreal Protocol identified the need to re-evaluate chemical
processes with regard to their use of VOCs and the impact theses VOCs
has on the environment. Green solvents were developed as a more
environmentally friendly alternative to petrochemical solvents. (28)
5
Alternative promising areas of research in the replacement of the use

of VOCs in industry include the application of supercritical carbon
dioxide and ionic liquids as alternative solvents. Both of which have
proved to have valuable applications. (29)
1.4. Some Physical properties of ionic liquids:

1-Density: Ionic liquids in general are denser than water with values
ranging from 1 to 1.6 g cm-3 and their densities decrease with increase in
the length of the alkyl chain in the cation. The densities of ionic liquids
are also affected by the identity of anions. (30,31)
2-Viscosity: Generally, ionic liquids are more viscous than common

molecular solvents and their viscosities are ranging from 10 mPa s to
about 500 mPa s at room temperature. (32,33) The viscosity of ionic liquids
is determined by Van der Waals (VDW) (21) force and hydrogen bonding.
Electrostatic forces may also play an important role. Alkyl chain
lengthening in the cation leads to an increase in viscosity. This is due to
stronger Van der Waals forces between cations leading to increase in the
energy required for molecular motion. Also, the ability of anions to form
hydrogen bonding has a pronounced effect on viscosity. (34)
3-Melting point: Ionic liquids have been defined to have melting point
below 100 ºC and most of them are liquid at room temperature. Both
cations and anions contribute to the low melting points of ionic liquids.
(35)
The increase in anion size leads to decrease in melting point. Cations
size and symmetry make an important impact on the melting point of
ionic liquids. Large cations and increased asymmetric substitution results
in a melting point reduction. (31)
6
4-Conductivity: Ionic liquids have reasonably good ionic conductivities

compared with those of organic solvents/electrolyte systems (up to 10 mS
cm-1) (21)
. However, at room temperature their conductivities are usually
lower than those of concentrated aqueous electrolytes. Based on the fact
that ionic liquids are composed solely of ions, it would be expected that
ionic liquids have high conductivities. This is not the case since the
conductivity of any solution depends not only on the number of charge
carriers but also on their mobility. The large constituent ions of ionic
liquids reduce the ion mobility which in turn leads to lower
conductivities. Furthermore, ion pair formation and/or ion aggregation
lead to reduced conductivity. The conductivity of ionic liquids of higher
viscosity exhibit lower conductivity. Increasing the temperature increases
conductivity and lowers viscosity. (36)
5-Thermal stability: Ionic liquids can be thermally stable up to

temperatures of 450 oC. The thermal stability of ionic liquids is limited by
the strength of their heteroatom-carbon and their heteroatom-hydrogen
bonds, respectively. (35)
6-Electrochemical window: By definition, the electrochemical window

is the electrochemical potential range over which the electrolyte is neither
reduced nor oxidized at an electrode. This value determines the
electrochemical stability of solvents. As known in aqueous solution, the
electro-deposition of elements and compounds is limited by the low
electrochemical window of water (about 1.2 V). On the contrary, ionic
liquids have significantly larger electrochemical windows, e.g. 4.15 V for
[BMIm] BF6 at a platinum electrode, 4.10 V for [BMIm] BF4 and 5.5 V
for [BMP] Tf2N at a glassy carbon electrode. (37)
7
1.5. Advantages of ionic liquids:

It is generally accepted that ionic liquids possess relatively low
melting points and are less viscous than molten salts. Ionic liquids have
low vapor pressures, are considered by many authors to be
environmentally friendly and can be applied in many organic reactions
(24, 38)
.
The very low vapor pressure of ionic liquids has led to their use as a
green solvent in environmentally friendly reactions and separation
processes. (14)
This feature of ionic liquids permits their repeated use as benign
solvents for green chemical syntheses without solvent loss to the
environment due to evaporation (39). Due to these excellent characteristics
of ionic liquids which makes them superior to other organic solvents,
scientists have done much work on their applications in electrochemistry,
liquid-liquid extraction and catalysis, including biocatalysis and
polymerization (40).
1.6. Applications of ionic liquids:

Ionic Liquids provide benefits particularly in the production area,
since they optimize the reaction and preparation steps. They are very well
suited as solvents for organic syntheses, because traditional solvents are
for the most part toxic, volatile and readily combustible. (6,41)
They are being used in a wide variety of applications such as
chemical engineering, synthesis, catalysis, batteries, fuel cells,
biotechnology or analytical science (42,43). Numerous new combinations of
Ionic liquids are available.
8
They can be designed specifically for every type of application since

the selection of the ions determines their chemical and physical
properties. The “unlimited” combination of the cations and anions is
opening up new opportunities. (44,45)
Ionic liquids have become very popular in recent years and have
proven to be versatile alternatives to classic synthetic procedures using
common organic solvents. Application in organic synthesis is enormous
and still increasing. They have become of great importance in
(46)
development of laboratory or industrial catalytic processes and
biocatalysis (47). They have been used in various polymerization processes
and preparation of ion conductive polymer electrolytes (48,49).
Technical applications of ionic liquids present big diversity including
preparation of photosensitizers (50), solar cells (51) , lubricants for steel (52),
improvement of aerogels production (53) and HPLC methods (54), and even
embalming and tissue preservation for biological purposes (55).
(56)
B. Weyershausen and K. Lehmann believe that due to their
unique properties ionic liquids have a great potential to be used as
performance additives in many materials and applications. The
application of ionic liquids is in accordance with the chemical industry's
guidelines and principles concerning the initiatives sustainable
development and responsible care.
9
1.7. Ionic liquid of choline chloride:

Choline chloride [Ethanaminium, 2-hydroxy-N, N, N-trimethyl-,
chloride], is a quaternary amine salt, with the chemical formula
[HOCH2CH2N (CH3)3Cl] it dissociates in water into the corresponding
positively charged quaternary hydroxyl alkylammonium ion and the
negatively charged chloride ion.
Choline chloride is a white crystalline solid but is marketed as an
aqueous solution (70–75 % w/w in water) which is a colorless liquid with
an amine-ike odor (32,57).
Choline chloride or trimethyl (2- hydroxyethyl) ammonium chloride
is an essential feed ingredient for optimum animal growth. Choline is
classified as a vitamin and belongs to the group of water soluble B-
vitamins. (58)
Deep eutectic solvents (DES) can be formed between a range of
carboxylic acids and choline chloride.
The physical properties are significantly affected by the structure of
the carboxylic acid but the phase behavior of the mixtures can be simply
modeled by taking account of the mole fraction of carboxylic acid in the
mixture. So, the physical properties and phase behavior are dependent
upon the number of acid functionalities, the aryl/alkyl substitutions and
the composition of mixture. The ease of synthesis, availability and
biodegradability of the components makes these DES versatile
alternatives to ionic liquid (59).
10
1.8. The chemistry of the first transition metal elements:

1.8.1. Chromium (III), (d3):
Chromium (III) forms stable salt with all the common anions and its
complexes with virtually any species capable of donating an electron-
pair. These complexes may be anionic, cationic, or neutral and, with
(60)
hardly any exceptions are octahedral . There is also a multitude of
complexes with two or more different ligands such as pentammines [Cr
(NH3)5X] n+1 which have been extensively used in kinetic. These various
complexes are notable for their kinetic inertness, which is compatible
with the half-filled t2g level arising from an octahedral d3configuration,
ligand displacement or rearrangement reaction of Cr (III) complexes are
only about 10 times faster than those of Co (III), with half-times in the
range of several hours.
This is the reason why many thermodynamically unstable complexes
of Cr (III) can be isolated as solid and that they persist for relatively long
time in solution, even under conditions of marked thermodynamic
instability.
[CrX6] 3- (X=halide, CN, SCN, N3, H2O, NH3).

[Cr (L-L) 3] (L-L= amino acid anions).
The hexaaqua ion [Cr(H2O)6]3+, which is regular octahedral, occurs

in aqueous solution and in numerous solid salts such as the green [Cr(
H2O)6] Cl3. Chromium (III) is the arch type d3 ion and the electronic
spectra and magnetic properties of its complexes have been exhaustively
studied (61).
11
The magnetic properties of the octahedral Cr (III) complexes are

uncomplicated. All such complexes must have three unpaired electrons
irrespective of the strength of the ligand field, and this has been
confirmed for all known mononuclear complexes. The spectra of Cr (III)
complexes are also well understood in their main features, in an
octahedral field, the splitting of free ion ground 4F term, along with the
presence of the excited 4P term of the same multiplicity, provides or
indicates the possibility of three spin-allowed d-d transition, and these
have been observed in a considerable number of complexes, the
spectorchemical series was originally established by using data for Cr
(III) and Co (III) complexes (61).
In molten salt anhydrous chromium (III) chloride dissolved only
slowly forming pale green solutions after more than 15h for 10-3 mol dm-3
concentrations at 90 ºC in acetamide-potassium nitrate and 8h at 140 ºC
in butyramide-sodium nitrate melts (62) .
1.8.2. Iron (III), (d5):

Iron (III) occurs in salts with most anions, except those that are
incompatible with it because of their character as reducing agent. In
aqueous solution Fe (III) is one of the most conspicuous features of ferric
ion in aqueous solution. Its tendency is to hydrolyze and/ or form
complexes. It has been established that the hydrolysis (equivalent in the
first stage to acid dissociation of the aqua ion) is governed in its initial
stage.
12
The various hydroxo species, such as [Fe(OH)(H2O)5]2+, are yellow

because of charge transfer band in the ultraviolet region, which has tails
coming into the visible region. Thus aqueous solutions of ferric salts even
with noncomplexing anion are yellow unless strongly acid. (61,63)
Iron (III) chloride was is very soluble in the acetamide-potassium
nitrate eutectic at 90 ºC giving initially a pale yellow solution which
darkened rapidly to a strong brown color within 15 min. The pale yellow
solution gave one absorption band at υ = 16900 cm-1 (ε = 35 mol-1 dm3
cm-1) close to an absorption edge at υ = 21000 cm-1, while the dark brown
solution showed only the absorption edge.
The pale yellow solution may be due to a tetrahedral complex
perhaps containing some chloride (FeCl4- in LiNO3-KNO3 eutectic at 160
ºC, band at υ = 16000 cm-1, ε = 32 mol-1 dm3 cm-1) which was replaced
over 15 min by more stable simple complexes containing acetamide
and/or nitrate, or perhaps by more polymerized solvolyzed iron specie. (62)
1.8.3. Cobalt (II), (d7):

There is a very marked contrast in this oxidation state between
cobalt (II) on the one hand and the two heavier member of the group on
the other hand, for cobalt (II) it is one of the two most stable oxidation
state. Complexes of configuration comparable to stability with the t2g6
eg1 of Co (II), show a greater diversity of types and are more labile.
13
The aqua ion [Co(H2O)6]2+ is the simplest complex of cobalt (II). In

aqueous solution containing no complexing agents, the oxidation to CoIII
is very unfavorable. Cobalt (II) forms numerous complexes, mostly either
octahedral or tetrahedral but five-coordination and square species are also
known.
There are tetrahedral complexes of cobalt (II) more than other
transition metal ions. This is in accord with the Fact that for a d7 ion,
ligand field stabilization energies disfavor the tetrahedral configuration
relative to the octahedral one to a smaller extent than for any other dn (1≤
n ≤9) configuration. Because of the small stability difference between
octahedral and tetrahedral CoII complexes, there are several cases in
which the two types with the same ligand are both known and may be in
equilibrium.
As already noted, cobalt (II) occurs in a great variety of structural
environments. Because of this the electronic structures, hence the spectral
and magnetic properties of the ion, are extremely varied. In each case of
high-spin octahedral and tetrahedral complexes, there is a quartet ground
state (4F) and three spin-allowed electronic transitions to the excited
quartet state (4P). (60,63)
The absorption spectra of cobalt (II) chloride complexes, contained
variable concentrations of chloride ligand also reported, in a molten
mixture of 80% acetmide -20% calcium nitrate tetrahydrate, in range of
temperature 313 to 363 K, in the wavelength rang 400-800 nm. The melt
contained three ligands (CH3CONH3, H2O, and NO3¯) for competition
with added chloride.
14
Addition of chloride caused a shift of the absorption maximum of

octahedral cobalt (II) nitrate towards lower energies and pronounced
changes in shape of the initial spectrum of cobalt (II) nitrate. The effect of
temperature changes on the molar absorption of the Co (II) species was
attributed to structural changes occurring in the cobalt (II) species. (64,65)
In the LiCl-KCl melt the absorption spectrum of Co (II) chloride is
that of the tetrahedral CoCl42- species.
The occurrence of the CoCl42- rather than the CoCl64- species in this
highly ionic melt can be rationalized in terms of large (- 30 Kcal )
electrostatic repulsion energies favoring the four- over the six –
coordinated . (65)
1.8.4. Nickel (II), (d8):

This is undoubtedly the most prolific oxidation state for this group of
elements. The stereochemistry of Ni (II) has been a topic of continuing
interest, and kinetic and mechanistic studies on complexes of Ni (II). The
absence of any other oxidation state of comparable stability for nickel
implies compounds of Ni (II) which are largely immune to normal redox
reactions. (60)
Ni (II) forms salts with virtually every anion and has extensive
aqueous solutions chemistry based on the green hexaaquanickel (II), [Ni
(H2O)6]2+ ion which is always present in the absence of strongly
complexing ligands.
15
The coordination number of Ni (II) rarely exceeds 6 and its principal

stereochemistries are octahedral and square planer, tetrahedral (4-
coordinate) with rather fewer examples of trigonal bipyramidal, square
pyramidal (5-coordinate).
Octahedral complexes of Ni (II) are obtained often from aqueous
solution by replacement of coordinating water, especially with neutral N-
donner ligands such as NH3, en, bipy, and phen, but also with NCS-, NO2-
, and O-donner such as DMSO (Me2SO). (61,63)
Nickel (II) forms a large number of complexes encompassing
coordination numbers 4, 5, and 6 in structural types of neutral ligands. It
is characteristic of Ni (II) complexes that complicated equilibria, which
are generally temperature dependent and sometimes concentration
dependent.
Anhydrous Nickel (II) chloride was soluble in both eutectics, giving
yellow solutions. The spectra Fig.(1.1) curve A and B showed three
absorption maxima indicating octahedral coordination of the nickel (II)
cations. The bands are shifted to slightly lower energies than those found
in pure molten acetamide suggesting some coordination by chloride, or
less likely by nitrate. Jorgensen's rule suggested 4 acetamides and 2
chlorides could give the observed bands and the less symmetrical
complexes resulting would explain the higher extinction coefficients
found. There are no data on the bands positions of butyramide complexes,
but if its ligand field is similar to that of acetamide, then the calculated
coordination would also be 4 amide and 2 chloride ligands. (62)
16
Fig. (1.1):- Spectra of NiCl2, (curve A) c = 0.046 mol dm-3 in acetamide-potassium

nitrate at 90 ºC, (curve B) c = 0.012 mol dm-3 in butyramide-sodium nitrate at
140 ºC (62).
1.8.5 Copper (II), (d9):

Simple salts are formed with most anions, except CN- and I- instead
of forming covalent Cu (I) compounds which are insoluble in water. Most
Cu (I) compounds are fairly readily oxidized to Cu (II) compounds. There
is a well-defined aqueous chemistry of Cu2+, and large number of salts of
various anions, many of which are water soluble. The blue color of their
solution arise from the [Cu(H2O)6]2+ ion, and they frequently crystallize
as hydrates.
17
The aqueous solutions are prone to slight hydrolysis and, unless

stabilized by a small amount of acid, are liable to deposit basic salts. The
most common coordination numbers of Copper (II) are 4,5, and 6, but
regular geometries are rare and the distinction between square-planer and
tetragonally distorted octahedral coordination is generally not easily
made. The reason for this is ascribed to the Jahn-Teller effect arising
from the unequal occupation of the Eg pair of orbitals (dz2 and dx2-y2)
when a d9 ion is subjected to an octahedral crystal field. The d9
configuration makes CuII subject to Jahn-Teller distortion if placed in an
environment of cubic (i.e. regular octahedral or tetrahedral) symmetry,
and this has a profound effect on all its stereochemistry. The d9
configuration can be thought of as an inversion of d1, relatively simple
spectra might be expected, and it is indeed true that the great majority of
Cu (II) compounds are blue or green because of a single broad absorption
band in the region 11000-16000 cm-1, however as already noted, the d9
ion is characterized by large distortion from octahedral symmetry and the
band is unsymmetrical, being the result of a number of transitions which
are by no means easy to assign unambiguously.(60)
The free-ion ground 2D term is expected to split in a crystal field in
the same way as the 5D term of the d4 ion, (2Eg → 2T2g) and a similar
interpretation of spectra is like wise expected. Unfortunately this is now
more difficult because of the greater overlapping of bands which occurs
in the case of Cu (II).
18
The T ground term of the tetrahedrally coordinated ion implies an

orbital contribution to the magnetic moment, but the E ground term of the
octahedrally coordinated ion is caused by ‘mixing’ of the excited T term
into the E ground term with compounds whose geometry approaches
octahedral having moments at the lower end, and those with geometries
approaching tetrahedral having moments at the higher end, but their
measurements can not be used diagnostically with safety unless supported
by other evidence . (60,63)
Anhydrous copper (II) sulfate dissolved readily in the acetamide-
potassium nitrate eutectic to give blue-green solutions. Spectroscopy
showed two bands at υ = 20700 cm-1 (ε = 43 mol-1 dm3 cm-1) and υ=
14000 cm-1 (ε = 73 mol-1 dm3 cm-1) with a shoulder at υ = 11000 cm-1.
The copper cations appear to be in an octahedral coordination, though
with a higher extinction coefficient, and thus probably a lower symmetry
(perhaps D4h), than those found for the regular octahedral complexes in
aqueous solution (band maxima at υ = 12600 cm-1, ε = 12 mol-1 dm3 cm-
1
), or in anhydrous alkali metal nitrate melts (υ = 13000 cm-1, ε = 14 mol-1
dm3 cm-1), because in this binary eutectic coordination is by both
acetamide and nitrate. The higher energy band is anomalous for a D4h
complex and may be due to small amounts of a square pyramidal (C4υ)
complex. (66)
19
1.9. Interaction of the ligands with the metal ions:

The tendency of metal ion to form a stable complex with ligands
depends on many rules such as the hard and soft acids and bases (HSAB)
(54)
rule of Pearson which imply that metal ion tend to coordinate with
certain functional groups of the ligand to from a stable complex. On the
other hand, the tendency of transition metal ion of a special oxidation
states is affected by the coordination to certain ligands. This phenomenon
(60,63)
is called (symbiosis) . Increasing the positive charge on the central
transition metal ions strengthens the metal-ligands bond. .
The metal ion prefers to bind with atoms of high electron density
such as N3- , O2- , P3- , S2- and C4- . The ligand should have certain
characteristic properties to make it convenient to form stable complex
with transition metal ions. .
The size, geometrical shape, number and geometrical arrangement of
ligand and donor atoms play the important role in the stability of the
resultant complex. Metal centers, being positively charged, are favored to
bind to negative charged biomolecules, the constituents of proteins and
(63)
nucleic acid offer excellent ligands for binding to metal ions . The
Irving Williams series of stability for a given ligand shows a good
criterion for the stability of complexes with dipositive metal ions which
follows the order: .
Ba2+ < Sr2+ < Ca2+ < Mg2+ < Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ >Zn2+
20
This order arises in part from a decrease in size across the series and
in part from ligand field effect. A second observation is that certain
ligands form their most stable complexes with metal ions such as Ag+,
Hg2+ and Pt2+, but other ligands seem to prefer ions such as Al3+, Ti4+, and
Co3+.
Ligands and metal ions were classified as class (a) or (b) according
to their preferential bonding. Class (a) metal ions includes those of alkali
metals, alkaline earth metals, and lighter transition metals in higher
oxidation states such as Ti4+ ,Cr3+ , Fe3+ ,Co3+ and the hydrogen ion, H+.
Class (b) metal ions include those of the heavier transition metals, and
those in lower oxidation states such as Cu+, Ag+, Hg2+, Pd2+, and Pt2+.
According to their preference toward either class (a) or class (b) metal
ions, ligands may be classified as type (a) or (b), respectively.
Stability of these complexes may be summarized as follows (61,63):
Tendency of ligands to complex with Tendency of ligands to complex
Class (a) metal ions Class (b) metal ions

N>>P> As >Ab N<<P< ِAs >Sb
O>>S>Se>Te O<<S<Se~Te
F>Cl>Br>I F<Cl<Br<I
The ligand should have certain characteristic properties to make it

convenient to form a stable complex with transition metal ions.
21
The size, geometrical shape, number and geometrical arrangement of

ligand donor atoms play the important role in stability of the resultant
complex (61).
One of the important aspects of CFT is that all ligands are not
identical when it comes to a causing separation of the d-orbitals. For
transition metal compounds, we are well aware of the multitude of colors
available for a given metal ion when the ligands or stereochemistry are
varied. In octahedral complexes, this can be considered a reflection of the
energy difference between the higher dz2, dx2-y2 (eg subset) and the dxy,
dyz, dxz (t2g subset).
It has been established that the ability of ligands to cause a large
splitting of the energy between the orbitals is essentially independent of
the metal ion and the spectrochemical series is a list of ligands ranked in
order of their ability to cause large orbital separations.
A shortened list includes:

I- < Br- < SCN- ~ Cl- < F- < OH- ~ ONO- < C2O4 2-
< H2O < NCS- <
EDTA4- < NH3 ~ pyr ~ en < bipy < phen < CN- ~ CO
When metal ions that have between 4 and 7 electrons in the d orbitals
form octahedral compounds, two possible electron allocations can occur.
These are referred to as either weak field- strong field or high spin - low
spin configurations.
22
The CFT method has provided a quantitative measure of the d-

splittings. The t2g /eg splitting (called the octahedral ligand field splitting
∆0= 10Dq) Follows the general trend. Point to consider about the ∆0
splitting:
1- Charge on the metal:

As charge increase, electrostatic attraction between M and L increases,
M-L bond distance decreased and SML increased. Also as charge increase,
metal becomes more electronegative, decreasing ∆EML. Both trends lead
to greater field strength for the more highly charged ion.
2- The nature of the metal ion, radial extension of 2nd and 3rd row
transition metals are greater, thus SML larger, leading to the following
trend in ∆0: 1st row transition metal << 2nd row transition metal ~ 3rd row
transition metal.
3- Nature of ligand:
Different ligands have different SML for a given metal ion. Can assess by
measuring ∆0 for different ligands about a given metal ion of given
charge
Cl-< F-< OH2 < CN - Cl-< OH2 < NH3 < CN-
23
From experiments such as these, may deduce a general ranking of

ligands in terms of field strength. This ranking is called the
spectrochemical series:
I-<Br-<S2-<SCN-<Cl-<S2-<F-<O2- <OH-<H2O <NH3 < CN-<CO<NO+
Weak field strength (small ∆0) Strong field strength (large∆0)

π-donors σ-only π-accepter
In the above series, the ligand type has been overlayed onto the
spectrochemical series. As is readily apparent from the energetic
disposition of ∆0, π-donors give weak ligand fields, σ-only ligands give
intermediate fields and π-acceptors ligands give strong fields. (60-63)
24
1.10. Aim of present work:

The aim of the present work is to study the coordination behavior of
some first row transition metal chlorides of different oxidation states of
Cr (III), Fe (III), Co (II), Ni (II) and Cu (II) in the newly prepared choline
chloride /tartaric acid ionic liquid of room temperature melting point.
The coordination is to be studied further by adding different
carboxylic ligands such as oxalic acid and EDTA salt to establish their
coordination geometry and strength. In addition such investigation would
indicate whether mixed or pure coordinated ligands would be formed
with the metal cations.
Such coordination would likely be established by UV-Vis
spectroscopy in an attempt to deduce their geometrical coordination. To
enhance the evaluation of their behavior in the melt, the resulted solution
would better be studied by other techniques such as infrared spectra and
conductivity. These techniques would carried out successfully to add
more information to the coordinated ligands with the metal ions and to
refer to the number of unpaired electrons in the d-shell of transition metal
ions. In addition the conductivity measurements would indicate number
of ions formed by the metal complexes.
25
CHAPTER
Chapter two Experimental part
Chapter Two
Experiment Part
2.1. Chemicals and Instruments:

2.1.1. Chemicals:
All the chemicals used in this work were of highest purity available
and used without further purification. Table (2-1) shows the reagents,
their purities and suppliers.
Table (2.1):- The chemicals used in this work with their purities and suppliers.
Chemical compounds Purity % Company
D-Tartaric acid 99.5 BDH
Oxalic acid 99 BDH
Ethylenediamine 98 BDH
Tetraacetic Acid
Tetrasodium Salt Dihydrate
Iron (III) chloride 99 BDH
tetrahydrate
Nickel (II) chloride 99 BDH
hexahydrate
Chromium (III) chloride 97 Chem-Supply
hexahydrate
Cobalt (II) chloride 98 Chem-Supply
hexahydrate
Copper (II) chloride 95 Fluka
dihydrate
Choline chloride 99 Merck
26
2.1.2. Instruments:
There were some instrumental analysis and procedures were applied
in this work which will be described in the following section:
2.1.2.1. Metal analysis:
The metal content in complexes was measured by atomic absorption
technique in PERKIN-ELMER-5000 Atomic Absorption
Spectrophotometer for the determination of (Cr3+, Fe3+, Co2+, Ni2+ and
Cu2+), using air-acetylene lamp, of 357.9, 248.3, 240.7, 232 and 324.8 nm
wavelength respectively. .
2.1.2.2. Electronic absorption spectra measurements:
The electronic spectra of complexes were obtained by using
SHIMADZU (Japan), UV-Vis 1650 PC Ultraviolet Visible
spectrophotometer at room temperature using quartz cells of 1.0 cm path
length and ionic liquid as solvent in the range of wavelength 190-1100
nm (52632 – 9091 cm-1).
2.1.2.3. Conductivity measurements:
The conductivity measurements were obtained using HANNA
instruments 5000 µs/ cm.
2.1.2.4. Fourier transform infrared spectrophotometer (F.T.IR)
measurements:
The Infrared spectra of the prepared compounds were recorded using
(F.T.IR- 8400) Fourier Transform Infrared spectrophotometer as CsI for
solid (choline chloride and tartaric acid) and liquids were measured by
thin layer of KBr slide in the range (4000-200) cm-1 in Baghdad
University, College of Science, Department of chemistry.
27
2.2. Setting of heating apparatus:

Working in room temperature ionic liquid solvents offer a simplicity
of apparatus arrangements in contrast to high temperature molten salts
apparatus which requires heating equipments that withstand the high
temperature used (i.e. heating to > 100 ºC). The apparatus consisted of
hot plate, oil path, stand, clamp, thermometer, reaction beaker and glass
rod.
2.3. Practical Methods:
2.3.1. Drying method:

The drying method was carried out by placing appropriate weight of
samples in the oven under temperature range of 80-85 ºC, to reduce the
moisture from the compound and kept in sealed descicater for further use.
2.3.2. Preparation of choline chloride/tartaric acid room

temperature ionic liquid (67):
Solid mixture of dry choline chloride (HOC2H4N (CH3)3+Cl-)
and tartaric acid ([CHOHCOOH] 2) in mole ratio of 2:1 (2.79 g and
1.50 g) respectively was milled, well mixed and heated gradually to 80oC,
using the apparatus described in Fig. (2.1) with continuous gentle stirring
until both choline chloride and tartaric acid melted together producing
colourless liquid. The resulted melt then was gradually cooled to room
temperature and remain liquid at this temperature. Finally the prepared
melt was kept sealed in a dry descicator for further use. (67,68)
28
2.3.3. Solubility determination:

Metal solubility was determined by adding a known weight of
chromium (III) chloride hexahydrate, iron (III) chloride tetrahydrate,
cobalt (II) chloride hexahydrate, nickel (II) chloride hexahydrate, and
copper (II) chloride dihydrate to 5 ml (Beaker) of choline chloride/
tartaric acid ionic liquid Table (2.2). Each solution was left for one week
with occasional stirring and on the 7th day (0.2 g portion) was taken from
the clear part of the solution by inserting a glass rod in the beaker
reaching the upper layer of the solution to withdraw several drops which
were put in a volumetric Flask with a known volume of 10 ml, and
dissolved in water. Finally, the determined metal content in these samples
by Atomic absorption analysis, was used to calculate the metal chloride
concentration in the original ionic liquid solution.
In addition, during the investigation of coordination reaction, oxalic
acid and Ethylenediamine Tetraacetic Acid Tetrasodium Salt Dihydrate
was added to above solution in Table (2.2).
Table (2.2):- Solubilities of transition metal chlorides in choline chloride/ tartaric

acid ionic liquid with added number of moles of oxalic acid and EDTA salt at
about 42:1 ligand to metal ratio.
Metal chlorides Moles of metal Molality Molarity Moles of Ox.

chloride (A.A.) (A.A.) (A.A.) And EDTA salt
CrCl3.6H2O 1.1 × 10-5 0.060 0.096 4.8 × 10-4
FeCl3.4H2O 6.9 × 10-5 0.373 0.596 2.9 × 10-3
CoCl2.6H2O 6.7 × 10-6 0.035 0.056 2.8 × 10-4
NiCl2.6H2O 4.1 × 10-5 0.217 0.347 1.7 × 10-3
CuCl2.2H2O 8.5 × 10-6 0.019 0.070 3.5 × 10-4
29
2.3.4. Determination of spectra:
2.3.4.1. Orgel diagrams:

Orgel diagrams are useful for showing the number of spin-allowed
absorption bands expected, and their symmetry state designations, for Td
and weak field Oh - complexes (d5 not included). The two diagrams (one
for d1, 4, 6, 9 the other for d2, 3, 7, 8) pack a lot of information in very little
space, as shown in Fig.(2.1) and (2.2). Nevertheless, there are three major
limitations to using Orgel diagrams:
(1) They are restricted to weak field/high spin conditions and offer no
information for d4, 5, 6, 7 strong fields/ low spin cases.
(2) They only show symmetry states of same highest spin multiplicity
(3) They are qualitative, and therefore energy values cannot be obtained
or calculated from them. (69,70)
Fig. (2.1):- The splitting of free-ion D terms in octahedral and tetrahedral

fields. (69)
30
Fig. (2.2):-The splitting of free-ion F and P term in octahedral and tetrahedral

fields. (69)
2.3.4.2. Tanabe-Sugano diagrams:

Appear different than Orgel diagrams because they use the ground
symmetry state as a straight-line horizontal base, whereas Orgel diagrams
place the parent term in a central location and direct ground symmetry
states below it. Appear "split" for d 4, d 5, d 6, d 7; cases because both low
and high spin symmetry states are included. Consequently, these
diagrams appear to be discontinuous - having two parts separated by a
vertical line. The left part pertains to the weak field /high spin condition
and the right to strong field/ low spin.
31
1 9
First note why d and d cases have no T-S diagrams. A term
description for an atom/ion is more information than its electron
configuration because terms account for e-e repulsion energies.
However there is no e-e repulsion for one "d" electron so the d1
configuration gives rise to a single term, 2D.In Oh and Td ligand fields
this single term is split into T2g, Eg, or E, T2 symmetry states. Only one
absorption band is expected and energy of the observed band gives the Δo
or ΔTd value directly. No calculations are necessary, so no T-S diagram
for d 1 (and d9). (69,70)
2.3.4.3. Equations:
The equations that have been used in the determination of spectra of
each complex were different from metal to another according to the
splitting of terms for dn configurations as shown in Fig. (2.3) and in Table
(2.3).
Fig. (2.3):- Splitting of terms for dn configurations in to (a) and (b). (61)
32
Table (2.3):- Splitting of terms for dn configuration. (61)
Configuration of Ground state of Energy level Predicted in Fig.

free-ion free-ion diagram (2.3)
d3 4
F 4P Inverted (b) ν1=10 Dq
ν2=18Dq-x
ν3=12Dq+15B`+x
d5 6
S No splitting
d7 4
F P 4
(b) ν1=8Dq
ν2=18Dq
ν3=6Dq+15B`
d8 3
F 3P Inverted (b) ν1=10 Dq
ν2=18Dq-x
ν3=12Dq+15B`+x
d9 2
D Inverted (a) ν1=10Dq
Also Jorgenson rule have been used to measure the tendency of

metal ion to form a complex, the g factors provide an estimate of the
value of 10Dq for an octahedral complex when combined with the f value
for the appropriate ligans:
10Dq = f ligand × g ion × 1000 ---------------------------------------- (2-1)
Table (2.4):- Values of g and f factors for metal ions and various ligands. (61)
Transition metal ion Value of g factor Various ligands Value of f factor
Cr(III) 17.4 Cl- 0.78
Fe(III) 14.0 Oxalic acid 0.99
Co(II) 9.00 H2O 1.00
Ni(II) 8.7 EDTA ≈ 1.24
Cu(II) 12.5
33
If all three transitions are observed, it is a simple matter to assign a

value to B` (Racah parameters), since the following equation must hold;
(B` is in cm-1 units).
15B`= ν3+ ν2–3 ν1 ------------------------------------------------------------------------ (2-2)

The nephelauxetic ratio β is given by:
β= B`/B. ----------------------------------------------------------- (2-3)
Where ‘B' ’ is Racah parameter.
2.3.4.4. Example of calculations:
Consider an example application of a Tanabe- Sugano diagram for d3

case. The absorption spectral data of a Cr+3 solution is shown below in
table (2.5). For example, the mathematical calculation of spectra,
CrCl3.6H2O in choline chloride/tartaric acid room temperature ionic
liquid.
Table (2.5):- Peak position of Chromium (III) ions in choline chloride/tartaric

acid room temperature ionic liquid.
Ion ν1 cm
-1
ν2 cm
-1
ν3 cm
-1
ν2/ ν1 ν1/ ν2 Δ/B Ref.
Cr3+ 15243 20920 ? 1.37 0.728 27 This work
34
Two bands are observed within the range of measurement. They

have maxima at 15243 and 20920 cm-1. These are spin- allowed laporte-
forbidden d-d transfers. Chromium is in the +3 oxidation state, so this is a
d3 system. Reference to Orgel diagram informs that 3 d-d bands are
expected and they can be assigned as:
ν1 = 4A2g (F) 4
T2g (F)
4 4
ν2 = A2g (F) T1g (F)
ν3= 4A2g (F) 4
T1g (P)
Δo is taken to equal the absorption energy of 15243 cm-1, and the

intersect on the x-axis of Tanabe-Sugano diagram equal Δo/B. and by
drawing a vertical line from this point it will intersect with other allowing
electronic state of Tanabe-Sugano diagram for d3 .
There are several goals sought in analyzing spectra using Tanabe-Sugano
diagram:
1- To make correct band assignments. The two bands observed could
be the first and second, or the second and third. Their assignment
cannot be made by inspection.
2- To determine the magnitude of the ligand field splitting parameter ,
Δo
3- To determine the magnitude of the e-e repulsion parameter (called
a racah B' parameter).
Assumes bands are the first and second (so third band is not observed).
Compare the two results. Tanabe-Sugano diagrams are unit less graphs
showing energy ratios. The abscissa shows values for the ratio Δo/B (i.e.,
ligand field splitting parameter / e-e repulsion parameter).
35
Step (1): the calculated ratio of experimental band energy is: E (υ2), E
(υ1),
Δ/B' intersection with 4T2g at (E/B') = 27
Δ/B' intersection with 4T1g at (E/B') = 37.18
B' via ν1 =15243 cm-1 /27.00 = 564.55 cm-1.
B' via ν2 =20920 cm-1 /37.18 = 562.66 cm-1.
Then B' = 563.6 cm-1.
B free-ion =918 cm-1.
To determine the ν3; Δ/B' intersection with 4T1g (P) at (E/B') = 58.82
ν3 = 58.82× 563 cm-1
= 33115 cm-1
= 301 nm
To determine the nephelauxetic ratio β:

β = B`/B,
Then β = 563.6 cm-1 / 918 cm-1 → β=0.61
Measurement of the tendency of metal ion to form complex with the

probable existing ligand, using Jorgenson rule: 10Dq= f ligand ×g ion
As shown in Table (2.4).
3+
If ligand was total mixture of (chloride and tartarate ion) with Cr
then:
15243 = f ligand ×17.4 ×1000 cm-1
f ligand = 0.87 cm -1
36
CHAPTER
Chapter three Result and Discussion
Chapter Three
Results and Discussion
3.1. Electronic absorption of transition metal chloride in room

temperature ionic liquid:
Electronic absorption spectra of transition metal complexes are
usually attributed to the partially filled d-orbital of the metal. The energy
required for such transitions is that of the near ultraviolet and visible
region. Charge transfer spectra are due to transitions between metal and
ligand. Studies of electronic spectra of complexes help in the
determination of structure of the complexes through the electronic
interaction of the metal d-orbital and ligand orbital (60-63). The range of the
spectra is (190-1100) nm, choline chloride/ tartaric acid ionic liquid was
used as a solvent. .
3.1.1. Spectroscopic investigation of Chromium (III) chloride

solutions:
3.1.1.1. Chromium (III) chloride in choline chloride / tartaric
acid room temperature ionic liquid solution:
Chromium (III) chloride hexahydrate was found to be soluble in
choline chloride /tartaric acid room temperature ionic liquid, in
concentration of 0.06 m at room temperature producing a deep green
colored solution. The recorded ultraviolet visible spectrum of the solution
-1
showed two absorption bands at (656 nm) 15243 cm and at (478 nm)
20920 cm-1, Fig.(3.1). The UV-Vis spectrum Fig. (3.2) indicates that the
chromium (III) ion is consistent with octahedral coordination.
37
Fig. (3.1):- The UV- Vis spectra of CrCl3.6H2O in choline chloride / tartaric acid
ionic liquid curve (A), in aqueous solution curve (B), with addition of oxalic acid
curve (C), and with addition of EDTA salt curve (D).
Fig.(3.2):- The UV-Vis spectra of chromium (III) of (0.06 m) in choline

chloride/tartaric acid room temperature ionic liquid.
38
The third band which normally occurred at the high charge transfer
energy region was deduced by using Tanabe-Sugano diagram Fig. (3.3)
for d3 electronic configuration and found to be 33115 cm-1. The term
symbol for the ground state of Cr (III) ion 4F can split in octahedral
crystal field and the bands may be assigned as illustrated in Fig. (3.4) as
follows:- .
4
υ1 = A2g (F) → 4T2g (F) =10Dq
4
υ2 = A2g (F) → 4T1g (F)
4
υ3 = A2g (F) → 4T1g (P)
Fig. (3.3):- Tanabe - Sugano diagram for d3 ion configuration.
39
m ix in g
4
T 1g (P )
4
P
15 B
4
T 1g (F)
6D q
4
F
4
T 2g
12D q 2D q
4
A 2g
Fig. (3.4):- Crystal field splitting of 4F term of d3 ion octahedral configuration.
The band energies of chromium (III) ions in choline chloride/tartaric

acid observed in this work were found to be shifted to lower energies than
those obtained in aqueous solution, as shown in Table (3.1). This might
be due to water molecule which is known to be stronger ligand than
chloride ions according to the spectrochemical series. In addition the
absorbance of Cr (III) ions in choline chloride/tartaric acid ionic liquid
were found to be smaller than that observed in aqueous solution, as
shown in Fig. (3.5) and Table (3.1). .
40
Fig. (3.5):- The UV- Vis Spectra of CrCl3.6H2O in choline chloride / tartaric acid
ionic liquid (0.096 M) (curve A) and in aqueous solution (0.1M) (curve B).
The calculated values of interelectronic repulsion parameter (Racah

parameter, B') in the complex formed in choline chloride/tartaric acid
ionic liquid with chromium (III) ion and that of nephelauxetic factor (β)
were represented in Table (3.1).
41
Table (3.1):- Electronic spectra for complexes of chromium (III) ions in aqueous
solution, ionic liquid and with addition of ligands. .
Chromium Absorption Transition B' Cal. 10 Suggested ε L Refere

(III) Band cm-1 β Dq Structure /mol nce
chloride (cm-1) cm
4
Aqueous υ1 =16299 A2g→ 4T2g(F) Octahedral This
4
solution υ2 =23255 A2g→ 4T1g(F) 709 0.77 16299 (6 H2O) Work
4 -
υ3cal'd=36314 A2g→ 4T1g(P)
4
Choline υ1 =15243 A2g→ 4T2g(F) Octahedral 4.90 This
4
chloride/ υ2 =20920 A2g→ 4T1g(F) 563.6 0.61 15243 ( 4 Cl- and 1 Work
4
tartaric acid υ3cal'd=33115 A2g→ 4T1g(P) tartarate
ion )
4
Choline υ1 =16556 A2g→ 4T2g(F) Octahedral 8.90 This
4
chloride/ υ2 =22471 A2g→ 4T1g(F) 571.0 0.62 16556 ( 2Cl-, Work
4
tartaric υ3cal'd=35781 A2g→ 4T1g(P) 1oxalate ion
acid+ oxalic and
acid. 1tartarate
ion )
4
Choline υ1 =17636 A2g→ 4T2g(F) dis. 20.45 This
4
chloride/ υ2 =24691 A2g→ 4T1g(F) 705.4 0.76 17636 Octahedral Work
4
tartaric υ3cal'd=38797 A2g→ 4T1g(P) ( 2Cl-, and 2
acid+ EDTA
EDTA Salt. ions )
4
Acetamide- υ1=16760 A2g→ 4T2g(F) Octahedral 62
4
KNO3 υ2=22450 A2g→ 4T1g(F) - - - (6 -
4
at 90 ºC A2g→ 4T1g(P) acetamide)
42
It is noticed that the value of Racah parameter (563.6 cm-1) was

found to be much smaller than that in free ion (918 cm-1) which was
attributed to the expansion of d-electron over the complex and resulted in
reducing the metal inter electronic repulsion.
In addition, the apparent value of B' in complexes is always smaller
than that of free ion. This phenomenon is known as nephelauxetic effect
and is attributed to delocalization of the metal electrons around the ligand
as well. As a result of this delocalization (cloud expansion) the average
inter electronic repulsion is reduced and therefore B` is usually smaller(61).
Calculation by Jorgenson rule of average environment for Cr (III)
ions in choline chloride/tartaric acid ionic liquid did not support that the
coordination is either of 6 chloride ions or three tartarate ions. The field
factor value of the total mixture of (chloride and tartarate ions) with Cr3+
was calculated and found to have a value of 0.876, calculated from
observed (υ1) and the (g) value of Cr3+ ion.
However, the calculation revealed that the coordination of chromium
(III) ion as of 4 Cl- and 1 of the solvent (tartarate ion), the latter ion
bonded to the metal as bidentate ligand (67). This calculation indicated a
less-uniform coordinated ligand around the Cr (III) ions as shown in Fig.
(3.6). This suggestion is supported by the smaller molar absorption value
of (4.90 L/mol-1cm-1) Table (3.1), since the normal octahedral normally
show a small value of molar absorptivity (<10). (71)
43
3-
Cl
Cl
O
S o lv . Cr
O Cl
Cl
Fig. (3.6):- Suggested structure for chromium (III) in choline chloride/tartaric

acid ionic liquid.
3.1.1.2. Substitution Reaction with Oxalic acid:

When Oxalic acid (H2C2O4) was added to the chromium (III)
chloride hexahydrate in choline chloride /tartaric acid ionic liquid
solution at room temperature, it didn’t show any change in color of the
solution. However, when the mixture was examined by ultraviolet visible
spectra of the chromium (III) ion, the observed peaks shifted to higher
energies than those obtained in pure melt and have the following values
(604 nm) 16556 cm-1 and (445 nm) 22471 cm-1, as shown in Fig. (3.7).
The addition of oxalate ion also showed an increase in the maximum
intensity of those bands in comparison with those obtained in choline
chloride/ tartaric acid alone as shown in Fig. (3.1). The changes might
indicate some interaction of the added Oxalate ion with chromium (III)
ions. The third energy band was calculated from the Tanabe-Sugano
diagram for d3 ion configuration Fig. (3.3) and it was found to be equal to
35781 cm-1, Table (3.1). .
44
Fig. (3.7):- The UV- Vis Spectra of CrCl3.6H2O in choline chloride /tartaric acid
ionic liquid with addition of oxalic acid.
Calculation using Jorgenson Rule of average environment was found

to be in agreement with replacement of two chloride molecules by one
oxalate ion in octahedral coordination as represented in Fig.(3.8); oxalate
ion is considered to be stronger than chloride as ligand according to the
spectrochemical series .(72)
This suggestion is supported by the increased molar absorption value
to (8.90 L/mol-1 cm-1), since the complex coordination shifted from the
almost normal octahedral geometry of the metal ion in pure ionic liquid,
Table (3.1).
The Racah parameter was calculated for the complex and was found
to be equal to 571.0 cm-1, this value is also much smaller than that of free
ion 918 cm-1.
45
However, it was higher than that value calculated for chromium (III)
complex in choline chloride/ tartaric acid ionic liquid alone 563.6 cm-1,
the increased value indicate that there is some kind of interaction with the
added oxalate ion, the high value normally indicated a more repulsion in
d-electron, due to less expansion of d-electron over a smaller cloud space.
3-
Cl
O O
S o lv. Cr Ox
O O
Cl
Fig. (3.8):- Suggested structure for chromium (III) in choline chloride /tartaric
acid ionic liquid with addition of Oxalic acid.
3.1.1.3. Substitution Reaction with EDTA salt:

When EDTA salt (C10H12N2O8Na4.2H2O) was added to the
chromium (III) chloride hexahydrate in choline chloride /tartaric acid
ionic liquid solution at room temperature, it did show a color change from
deep green into violet solution. However, when the mixture was
examined by ultraviolet visible spectra of the chromium (III) ion, the
observed peaks shifted to higher energies than those obtained in pure melt
or that of added oxalate ion as shown in Fig. (3.1).
The recorded ultraviolet visible spectra of the solution showed two
absorption bands at (567 nm) 17636 cm-1 and at (405 nm) 24691 cm-1 as
shown in Fig. (3.9). .
46
The color change in solution could be attributed to the absorption at

the blue end of the visible region producing the violet color.
The addition of EDTA salt also showed an increase in the maximum
intensity of those bands in comparison with those obtained in choline
chloride/ tartaric acid alone as shown in Fig. (3.1). The changes indicates
some interaction of the added EDTA salt with chromium (III) ions. The
third energy band was calculated from the Tanabe-Sugano diagram for d3
ion configuration Fig. (3.3) and it was found to be equal to 38797 cm-1,
Table (3.1). .
.
Fig. (3.9):- The UV - Vis spectra of CrCl3.6H2O in choline chloride / tartaric acid
ionic liquid with addition of EDTA salt.
47
Calculation using Jorgenson Rule of average environment was found

to be in agreement with replacement of two chloride ions and one
tartarate ion by two EDTA ions in octahedral coordination as shown in
Fig. (3.10); EDTA salt is considered to be stronger than chloride and
tartarate ion as ligand according to the spectrochemical series (72).
This calculation indicated non-uniform coordinated ligands around
the Cr (III) ions. Therefore, it may show much less uniform octahedral
shape. This suggestion is supported by the large molar absorption value
of (20.45 L/mol-1 cm-1), as shown in Table (3.1).
The Racah parameter B' was calculated for the complex and was
found to be equal to 705.4 cm-1, this value is smaller than that of free ion
918 cm-1. However, it was higher than that value calculated for chromium
(III) complex in choline chloride/ tartaric acid ionic liquid alone 563.6
cm-1. The higher value indicate that there is some kind of interaction with
the added EDTA salt, the higher value normally indicated a more
repulsion in d-electron, due to less expansion of d-electron over a smaller
cloud space.
7-
Cl
O O
EDTA Cr EDTA
O O
Cl
Fig. (3.10):- Suggested structure for chromium (III) in choline chloride/tartaric

acid ionic liquid with addition of EDTA salt.
48
3.1.2. Spectroscopic investigation of Iron (III) chloride

solutions:
3.1.2.1. Iron (III) chloride in choline chloride / tartaric acid
room temperature ionic liquid solution:
Iron (III) chloride tetrahydrate was found to be soluble in choline
chloride / tartaric acid room temperature ionic liquid in a concentration of
0.37 m, producing a pale yellow solution. The pale yellow solution was
examined by ultraviolet visible spectroscopy and showed absorption band
at (447 nm) 22371 cm-1 and expected to be responsible for the yellow
color as it cover the blue end of the visible region. As shown in Fig.
(3.11-A). In addition the instruments also recorded a bands at (878 nm)
1389 cm-1 and (698 nm) 14326 cm-1 with a small absorbance of (0.444)
which are shown in Fig.(3.11-B) which was magnified to present the
latter bands which are normally expected to have a much smaller
absorbance due to its non-allowed d5 transition. The bands can be
assigned as shown below according to the term symbol for the ground
6
state of Fe (III) ion S for tetrahedral crystal field:-
υ1= 6A1 → 4T1

υ2= 6A1 → 4T2
υ3= 6A1 → 4A1 + 4E
49
Fig. (3.11):- The UV– Vis. spectra of pale yellow solution of FeCl3.4H2O of (0.373
m) in choline chloride / tartaric acid ionic liquid at room temperature A- with
normal scan and B- magnified at the absorbance scale.
The ultraviolet visible spectra of the solution indicates tetrahedral

coordination of Fe (III) in this solution. According to Tanabe–Sugano
diagram for d5 Fig. (3.12) the band that appeared between the assigned
bands was related to forbidden transition that probably occurred between
6 4
A1 and A1, as it is the lowest energy term, Table (3.2).
50
Fig. (3.12):- Tanabe- Sugano diagram for octahedral and tetrahedral for d5 ion
configuration.
Because of Fe3+ is in oxidation state with half-filled d orbital with

term symbol of 6S that has no splitting. It could be suggested that the
environment of the ligands for Fe3+ are of mixed ligands of one tartaric
acid and two chlorides in tetrahedral geometry(73), as shown in Fig. (3.13).
51
1-
O
S o lv. Fe
O Cl
Cl
Fig. (3.13):- Suggested structure for iron (III) in choline chloride / tartaric acid
ionic liquid.
---------------------------------------------------------------------
Table (3.2):- Electronic spectra of complexes of iron (III) ions in choline chloride/
tartaric acid ionic liquid and with addition of ligands.
Iron (III) Absorption Transition Suggested ε L /mol Reference

chloride Band Structure cm (υ3)
(cm-1)
6
Choline υ1=11389 A1→ 4T1 Tetrahedral
6
chloride/ υ2=14326 A1→ 4T2 one tartarate ion This
6 3.00
tartaric acid υ3=22371 A1→ 4A1+4E and two work
chloride ions
6
6
chloride/ υ2=14836 A1→ 4T2 one tartarate ion This
6
tartaric acid+ υ3=23255 A1→ 4A1+4E and one oxalate 2.56 Work
oxalic acid ion
Choline υ1 = - Tetrahedral
chloride/ υ2 = - Two EDTA ions This
6
tartaric acid+ υ3=24937 A1→ 4A1+4E 3.84 Work
EDTA salt.
LiNO3/KNO3 υ= 16000 Tetrahedral

160 ºC FeCl4¯ -
71
6
6
chloride/ υ2=14771 A1→ 4T2 one malonic 1.7 73
6
malonic acid υ3=18762 A1→ 4A1+4E acid and two
chloride ions
52

The addition of oxalic acid (H2C2O4) to the Iron (III) in choline
chloride /tartaric acid solution at room temperature did not show visual
change in color of the solution. However, it was examined by ultraviolet
visible spectroscopy and it indicated some changes in the ultraviolet
visible spectra of the solution. And showed absorption band at (478 nm)
20920 cm-1 as shown in Fig. (3.14-A) In addition the instruments also
recorded bands at (869 nm) 11507 cm-1 and (674 nm) 14836 cm-1 with a
very small absorbance of (0.150) which are shown in Fig.(3.14-B) which
was magnified to present the latter bands which are normally expected to
have a much smaller absorbance due to its non-allowed d5 transition. The
observed bands shifted to higher energy than those obtained in pure melt,
as illustrated in Table (3.2). .
Fig. (3.14):- The UV-Vis. spectra of pale yellow solution of FeCl3.4H2O in choline
chloride/tartaric acid room temperature ionic liquid with addition of oxalic acid
A- with normal scan and B- magnified at the absorbance scale.
53
It could be suggested that the environment was found to be in

agreement with replacement of two chloride ions by one oxalate in
tetrahedral coordination; oxalate is considered to be stronger than
chloride as ligand according to the spectrochemical series, as shown in
Fig. (3.15). .
1-
O
S o lv . Fe
O O
O
Ox
Fig. (3.15):- Suggested structure for Iron (III) in choline chloride / tartaric acid
3.1.2.3.Substitution Reaction with EDTA salt:

The addition of EDTA salt (C10H12N2O8Na4.2H2O) to the Iron (III)
chloride in choline chloride /tartaric acid solution at room temperature
also did not show visual change in color of the solution. However, when
it was examined by ultraviolet visible spectroscopy, indicated some
changes in the ultraviolet visible spectra of the solution, as shown in Fig.
(3.16). The band at 24937 cm-1, was shifted to higher energy of the
charge transfer region than those obtained in pure melt or with added
oxalic acid, as summarized in Table (3.2).
54
Fig. (3.16):- The UV- Vis. spectra of pale yellow solution of FeCl3.4H2O in
choline chloride / tartaric acid room temperature ionic liquid with addition of
EDTA salt.
It could be suggested that the environment of the ligand for Fe3+ are
of EDTA ions in tetrahedral geometry, when the two chloride and one
solvent were replaced with two EDTA ions that is stronger ligand
according to the spectrochemical series, as shown in Fig.(3.17).
5-
O
EDTA
Fe
O O
O
EDTA
Fig . ( 3.17) :- Suggested structure for iron (III) in choline chloride / tartaric acid
55
3.1.3. Spectroscopic investigation of Cobalt (II) chloride

solutions:
3.1.3.1. Cobalt (II) chloride in choline chloride / tartaric acid
When cobalt chloride dissolved in choline chloride/ tartaric acid ionic
liquid, it showed a blue color solution. The ultraviolet visible spectra of
the solution of the cobalt chloride shows one absorbance maxima band at
(697 nm) 14347 cm-1 which represent υ3, and two other absorbance at
(671 nm) 14903 cm-1 and (635 nm) 15748 cm-1, Fig. (3.18) and Fig.
(3.19).
Therefore, cobalt chloride in choline chloride/tartaric acid ionic
liquid considered to consists of tetrahedral coordination complex of
cobalt (II) ions.
The term symbol for the ground state of Co (II) ion 4F can split in
tetrahedral crystal field as follows:
4 4
υ1 = A2 (F) → T2 (F) (10Dq)
4 4
υ2 = A2 (F) → T1 (F)
4 4
υ3 = A2 (F) → T1 (P)
Fig. (3.20) shows the assigned electronic transition of the term symbol for
the ground state of CO (II) ion 4F.
56
Fig. (3.18): Spectra of CoCl2.6H2O in choline chloride/ tartaric acid ionic liquid
at room temperature curve (A), with addition of oxalic acid curve (B), and with
addition of EDTA salt curve (C).
at room temperature
57
mixing
4
T1(P)
4
P
15 B
4
T1 (F)
6Dq
4
F
4
T2
12Dq 2Dq
4A
2
.
4 7
Fig. (3.20) Crystal field splitting of F term of d ion tetrahedral configuration.
In this case, υ1 should be active in the IR region and υ2 in near IR

region. Examination of this part of the IR has sometimes indicated the
presence of a band, though overlying vibrational bands make
interpretation difficult.
Jorgenson calculations of average environment for Co (II) ions in
choline chloride / tartaric acid ionic liquid suggest that the coordination is
of four chloride ions. This calculation indicates uniform coordinated
ligands around the Co (II) ions; therefore, it may show a regular
tetrahedral shape as represented in Fig. (3.21).
This suggestion is supported by the large molar absorption value of
(31.28 L/mol-1 cm-1) since the normal tetrahedral would show large value
(>10) as shown in Table (3.3).
58
2-
Cl
Co
Cl Cl
Cl
Fig. (3.21): Suggested structure for cobalt (II) chloride in choline chloride/
Table (3.3):- Electronic spectra of complexes of cobalt (II) ions in aqueous

solution, ionic liquid and with addition of ligands.
Ionic Solution Transition 10 Dq ε L /mol Suggested Reference
liquid color Band cm structure
Aqueous Pink υ1= 8100 8100 - Octahedral 61- 63

solution solution υ2= 16000 [Co(H2O)6]2+
υ3=19400
Choline chloride/ Blue υ1 = - - 31.28 Tetrahedral This

tartaric acid υ2 = - CoCl4 2- Work
υ3 ava=(14999)

tartaric acid υ2 = - two oxalic Work
+ ox υ3 ava=(15082) acid

tartaric acid + υ2 = - two EDTA Work
EDTA salt υ3 ava=(15380) salt
59
Table (3.4):- Electronic spectra for complexes of cobalt (II) chloride in various
room temperature ionic liquids.
Ionic Percents of Co (II) formed Absorption Temp. Suggested Reference

Liquids IL. complexes Band ( ºC) structure
Component. (cm-1)
LiCl-KCl CoCl4 2- υ=14700 447- Tetrahedral 74

- υ=15150 480
υ=16700
Acetamide- 80%-20% [Co(NO3)4]2- υ=19430 40-90 Octahedral 64-65

Ca(NO3)2.4H2O Addition of [Co(NO3)2Cl2]2- Shifted to tetragonal
Cl- [CoCl4]2- Lower or
energy tetrahedral
KCl-AlCl3 (50.3-49.7)% CoCl4 2- 25 Tetrahedral 75

(50.3-49.7)% CoCl6 4- or 300 Octahedral
Co(Al2Cl7)2
(49.9-50.1)% [Co(AlCl4)2] 300 tetragonal

When oxalic acid (H2C2O4) was added to the cobalt (II) chloride
hexahydrate in choline chloride / tartaric acid ionic liquid solution at
room temperature, it did not show any change in color of the solution.
However, when the mixture was examined by ultraviolet visible spectra
of the cobalt (II) ion, the observed peaks shifted to higher energies than
those obtained in pure melt, as shown in Fig. (3.18).
60
The ultraviolet visible spectra of the solution of the cobalt (II) chloride
shows one absorbance maxima band at 14409 cm-1 which represent υ3, and
two other absorbance singlet at (667 nm) 14992 cm-1 and (631 nm) 15847
cm-1 as shown in Fig. (3.22). Also, in this case, υ1 should be in the IR
region and υ2 in near IR region. .
.
at room temperature with addition of oxalic acid.
Jorgenson calculations of average environment for Co (II) ions in

choline chloride / tartaric acid ionic liquid with addition of oxalic acid it
suggested that the coordination is two oxalate ion according to the
spectrochemical series, as shown in Fig. (3.23).
61
This suggestion is also supported by the large molar absorption value

of the solution (37.05 L/mol-1 cm-1) as shown in Table (3.3).
2-
O
Ox
Co
O O
O
Ox

When EDTA salt (C10H12N2O8Na4.2H2O) was added to the cobalt (II)
chloride hexahydrate in choline chloride / tartaric acid ionic liquid
solution at room temperature, it also did not show any change in color of
the solution. .
However, when the mixture was examined by ultraviolet visible
spectra of the cobalt (II) ion, the observed peaks shifted to higher
energies than those obtained in pure melt or in presence of oxalic acid,
Fig.(3.18). .
The ultraviolet visible spectra of the solution of the cobalt chloride

shows one absorbance maxima band at (680 nm) 14705 cm-1 which
represent υ3, and two other absorbance at (651 nm) 15360 cm-1 and (622
nm) 16077 cm-1 , as shown in Fig. (3.24). Also, in this case, υ1 expected
to be in the IR region and υ2 in near IR region.
.
62
Fig. (3.24): Spectra of CoCl2.H2O in choline chloride/ tartaric acid ionic liquid at
room temperature with addition of EDTA salt. .
Again Jorgenson calculations of average environment for Co (II) ions

in choline chloride/ tartaric acid ionic liquid with addition of EDTA salt
suggested that the Co (II) ion coordinated to EDTA ions. Therefore, it
may show a tetrahedral shape as shown in Fig. (3.25). This suggestion is
supported by the large molar absorption value of (40.30 L/mol-1 cm-1), as
shown in Table (3.3). .
63
6-
O
EDTA
Co
O O
O
EDTA
3.1.4. Spectroscopic investigation of Nickel (II) chloride

solutions:
3.1.4.1. Nickel (II) chloride in choline chloride / tartaric acid
Nickel (II) chloride hexahydrate was found to be soluble in choline
chloride/ tartaric acid ionic liquid at room temperature, in a concentration
of 0.21 m, producing a bluish green solution.
The ultraviolet visible spectra of the solution showed two absorption
maxima bands at (706 nm) 14164 cm-1, (658 nm) 15197 cm-1 in
additional band at (436 nm) 22935 cm-1, as shown in Fig. (3.26) and
Fig.(3.27). The ultraviolet visible spectra indicated that nickel (II) in
choline chloride/ tartaric acid consisted of tetrahedral complex or
distorted octahedral complex of nickel (II), but the tetrahedral complex is
more preferable because it is closer to the value of absorbance bands in
aqueous solution of nickel (II) chloride with high concentration of
chloride ions which indicates tetrahedral coordination as shown in Table
(3.5). .
64
The transitions of the nickel (II) in choline chloride/ tartaric acid melt
were assigned as follows: .
υ1 = 3T1→ 3T2 (F)

υ2 = 3T1 → 3A2 (F)
υ3 = 3T1 → 3T1 (P)
The appeared band in the spectra was assigned to be the third

allowed transition that occurs in the visible region with a splitting due to
the forbidden transition from 3T1 ground state to singlet state. While the
first and second transitions were in near infrared spectra region.
Fig. (3.26): Spectra of NiCl2 .6H2O in choline chloride/ tartaric acid ionic liquid
at room temperature curve (A), with addition of oxalic acid curve (B), and with
addition of EDTA salt curve (C).
65
Fig. (3.27):- The UV- Vis. Spectra of NiCl2.6H2O of (0.217 m) in choline chloride/
tartaric acid ionic liquid at room temperature.
Nickel (II) formed tetrahedral complex in choline chloride/ tartaric

acid, and when referred to Tanabe-Sugano diagram of d2 octahedral
electronic configuration, and Orgel diagram d8 tetrahedral and d2
octahedral have the same transition as in Fig. (3.28). The most likely
suggestion is that nickel (II) formed a tetrahedral coordination complex in
choline chloride/tartaric acid.
Suggestion of the average environment of nickel (II) in choline
chloride/ tartaric acid was based on the spectra of the solution, where
nickel (II) was bonded with one tartaric acid molecule and two chlorides
in tetrahedral coordination, where the two chlorides were replaced with
tartaric acid molecule, which according to the electrochemical series this
replacement is preferable because tartaric acid is stronger than chlorides
as shown in Fig. (3.29).
66
The observed bands are of the third transition with a split is similar
to that results in aqueous solution of NiCl2.6H2O containing high
concentration of chloride ions as in Table (3.5).
Fig. (3.28):- Tanabe-Sugano diagram for d8 tetrahedral electronic configuration.
67
Table (3.5):- Electronic spectra for complexes of nickel (II) ions in choline
chloride / tartaric acid ionic liquid and with addition of ligands.
Solution Solution Transition B' 10Dq Suggested εL Referen

color (cm-1) (cm-1) (cm-1) Structure /mol ces
cm
Aqueous Pale υ1=8500 1042 8500 Octahedral - 61
solution green υ2=13800 2+
[Ni(H2O)]
υ3=25300
Aqueous Yellow υ1= - Tetrahedral

solution with υ2=7549 1030 4070 - 60
[NiCl4]2-
high conc. of υ3= 14250- 15240
chloride ions
Choline Bluish υ1= - Tetrahedral This
chloride / green υ2= - - - one tartarate work
tartaric acid υ3 ava=14680 ion and two 1.89
-------------------- chloride
another band at ions
22935 probably
of Oh
chloride / green υ2= - one tartarate 2.39 work
tartaric acid+ υ3 ava=14690 ion and one
- -
ox --------------------- oxalate ion
another band at
23980 probably
of Oh
chloride / green υ2= - Two EDTA 4.44 work
tartaric acid+ υ3 ava=14702 ions
- -
EDTA salt ----------------------
also another band
at 26109 probably
of Oh
CsCl υ1=7500 Tetrahedral 76
864 ºC ( Ni 2+ υ2=14000 - - -
formed - υ3=15700
complexes
NiCl4 2- )
LiCl / KCl υ1=8000 Dis. Tet. 77
700-1000 ºC υ2=14200 - - -
( Ni 2+ formed - υ3=15300
complexes
NiCl4 2-)
68
2-
O
S o lv. Ni
O Cl
Cl
Fig. (3.29):- Suggested structure for nickel (II) chloride in choline chloride/

When Oxalic acid was added to the nickel (II) chloride hexahydrate
in choline chloride/tartaric acid ionic liquid solution at room temperature,
it did not show any change in color of the solution. However, when the
mixture was examined by ultraviolet visible spectra of the nickel (II) ion,
the observed peaks shifted to higher energies than those obtained in pure
melt as shown in Fig. (3.26), and showed two absorption maxima bands
at (705 nm) 14184 cm-1, (658 nm) 15197 cm-1 and the other bands at (417
nm) 23980 cm-1 as shown in Fig.(3.30). .
69
Fig. (3.30):- the UV - Vis spectra of NiCl2.6H2O in choline chloride / tartaric acid
Suggestion of the average environment of nickel (II) chloride in

choline chloride/ tartaric acid ionic liquid after added oxalic acid, where
the two chlorides were replaced with oxalate ion, which according to the
electrochemical series this replacement is preferable because oxalic acid
is stronger than chlorides 1as shown in Fig.(3.31).
2-
O
S o lv. Ni
O O
O
Ox
Fig.(3.31):- Suggested structure for nickel (II) chloride in choline chloride/

70

When EDTA salt (C10H12N2O8Na4.2H2O) was added to the nickel (II)
chloride hexahydrate in choline chloride /tartaric acid ionic liquid
solution at room temperature, it did not show any change in color of the
solution. However, when the mixture was examined by ultraviolet visible
spectra of the nickel (II) ion, the observed peaks shifted to higher
energies than those obtained in pure melt and in addition of oxalic acid as
shown in Fig. (3.26) and showed two absorption maxima bands at (705
nm) 14184 cm-1, (657 nm) 15220 cm-1 and the other bands at (383 nm)
26109 cm-1 , as shown in Fig. (3.32). .
Fig. (3.32):- the UV - Vis Spectra of NiCl2.6H2O in choline chloride / tartaric acid
ionic liquid with addition of EDTA salt. .
Suggestion of the average environment of Nickel (II) in choline

chloride/ tartaric acid ionic liquid after added EDTA salt, where the two
chlorides and one solvent were replaced with EDTA ions.
71
Which according to the spectrochemical series this replacement is

preferable because EDTA salt is stronger than chlorides and tartaric acid,
as shown in Fig. (3.33).
6-
O
EDTA
Ni
O O
O
EDTA
Fig. (3.33):- Suggested structure for nickel (II) chloride in choline chloride/
3.1.5. Spectroscopic investigation of Copper (II) chloride

solutions:
3.1.5.1. Copper (II) chloride in choline chloride / tartaric acid
Copper (II) chloride dihydrate was found to be soluble in choline
chloride /tartaric acid ionic liquid at room temperature in a concentration
of 0.019 m, producing a deep yellow solution. .
The ultraviolet visible spectra of the solution showed one broad

absorption maxima at (1089 nm) 9182 cm-1, as shown in Fig.(3.34) and
Fig.(3.35). .
72
The results of copper (II) in choline chloride/ tartaric acid is similar

to those taken for copper (II) in molten chloride of LiCl/KCl at 400 ºC
which showed one absorption maxima at (1052 nm) 9500 cm-1, where
copper (II) prosed to be in distorted octahedral to tetrahedral
coordination. Table (3.6) showed all the results taken for Cu (II) in
choline chloride based ionic liquids. .
Copper (II) chloride of d9 electronic configuration, could be
suggested to have an environment of the ligands bonded with Cu2+ are of
mixed ligands molecules of one tartaric acid and two chlorides in
distorted octahedral or tetrahedral geometry, as shown in Fig.(3.35).
This suggestion is supported by the value of molar absorption (10.6
L/ mol cm) since the normal tetrahedral (~100). Copper (II) in choline
chloride/ tartaric acid was bonded with two chlorides and one tartarate
ion. This replacement of two chlorides with tartarate ion is preferable
according to the spectrochemical series tartaric acid is stronger than
chloride as ligand.
73
Fig .(3.34) :- UV- Vis spectra of copper (II) chloride in choline chloride / tartaric
acid ionic liquid at room temperature curve (A), with addition of oxalic acid
curve (B) and with addition of EDTA salt curve (C).
Fig. (3.35):- The UV-Vis. Spectra of CuCl2.2H2O in choline chloride/ tartaric

acid ionic liquid at room temperature. .
74
The d9 configuration makes Cu II subjected to Jahn-Teller distortion

if placed in an environment of cubic (i.e. regular octahedral, or
tetrahedral) symmetry, and this has a profound effect on all its
stereochemistry.
Also the d9 ion is characterized by large distortion from octahedral
symmetry and the bond is unsymmetrical, being the result of a number of
transitions, which are by no means easy to assign unambiguously.
The high absorption of copper (II) in choline chloride/ tartaric acid
ionic liquid may indicates a large distortion in its geometry, as shown in
Table (3.6). .
2-
O
Solv. Cu
Cl
O
Cl
Fig. (3.36): Suggested structure for copper (II) chloride in choline chloride/
75
Table (3.6):- Electronic spectra of complexes of copper (II) chloride in choline

Solvents Solution Absorption Transition Suggested ε L /mol References
color Band structure cm
(cm-1)
2
Aquous solution υ=(11000- E → 2T2 Octahedral 60-61
Pale 13000) [Cu(H2O)6] 2+ -
blue
2
Choline υ = 9182 B1→ 2B2 Tetrahedral This work
2
yellow B1→ 2E Two chloride 10.6
chloride/tartaric
ions and one
acid tartarate ion
2
Choline υ=9569 B1→ 2B2 Tetrahedral This work
2
yellow B1→ 2E One oxalate 11.9
chloride/tartaric
ion and one
acid + ox tartarate ion
2
Choline υ=9606 B1→ 2B2 Tetrahedral This work
2
yellow B1→ 2E Two EDTA 13.0
chloride/tartaric
ions
acid +EDTA
salt
2
LiCl/ KCl - υ= 9500 B1→ 2B2 Dist. Oct. 78
2
B1→ 2E to Tetrahedral -
2
AlCl3- 1,methyl - υ= 34139 B1→ 2B2 Tetrahedral 79
2
υ=24570 B1→ 2E CuCl4 2 - -
3ethylimidazoli
um chloride
76
3.1.5.2. Substitution with oxalic acid:

Addition of oxalic acid to the solution of Cu (II) in choline chloride /
tartaric acid at room temperature did not show any visual change in color
of the solution, but it showed some changes in the ultraviolet visible
spectra of the copper (II) ions, as the absorbance and the position of the
peak relatively changed, as shown in Fig. (3.34). The band was shifted to
higher energy band of (1045 nm) 9569 cm-1, as shown in Fig. (3.37).
The absorbance and molar absorptivity of the solution when oxalate
ion was added showed little higher absorbance than in pure melt solution
which indicated that the added oxalate ion had interacted copper (II)
chloride, as shown in Table(3.6). .
Copper (II) is ionic state with d9 electronic configuration , it could be

suggested that the environment of the ligands bonded with Cu2+ are mixed
ligands molecules of one tartaric acid and one oxalic acid in tetrahedral
geometry, as shown in Fig.(3.38). This replacement of chloride ions with
oxalate ion is preferable according to the spectrochemical series; oxalic
acid is stronger than chloride ions.
77
Fig. (3.37) The UV- Vis. Spectra of Cupric chloride in choline chloride/ tartaric
acid ionic liquid at room temperature with addition of oxalic acid.
2-
O
S o lv . Cu
O O
O
Ox
Fig. (3.38): Suggested structure for copper (II) chloride in choline chloride/
78
3.1.5.3. Substitution with EDTA salt:

Addition of EDTA salt to the solution of Cu (II) chloride in choline
chloride/tartaric acid at room temperature did not show any visual change
in color of the solution, but it showed some changes in the ultraviolet
visible spectra of the copper (II) ions, as the absorbance and the position
of the peak had changed, as shown in Fig. (3.34). The band was shifted to
higher energy band at average of (1041 nm) 9606 cm-1, as shown in Fig.
(3.38). .
The absorbance of the solution when EDTA salt was added showed
higher absorbance than in pure melt solution or with addition of oxalic
acid which indicated that the added EDTA salt had interacted copper (II)
chloride as shown in Table(3.6). .
Copper (II) chloride of d9 electronic configuration, it could be

suggested that the environment of the ligands bonded with Cu2+ all of this
was EDTA salt in tetrahedral geometry as shown in Fig.(3.40), This
replacement of chloride ions and oxalate ion is preferable according to
the spectrochemical series EDTA is stronger than chloride and oxalate
ions as ligands. .
79
Fig. (3.39) The UV- Vis. Spectra of Cupric chloride in choline chloride/ tartaric
acid ionic liquid at room temperature with addition of EDTA salt.
6-
O
EDTA
Cu
O O
O
EDTA
Fig. (3.40): Suggested structure for copper (II) in choline chloride/ tartaric acid
Previous studies of copper (II) in ionic liquids, aqueous solution and

with addition of ligands showed that copper (II) behaved differently from
one solution to other, Table (3.6) showed the results of copper (II) in
arious solvents. .
80
3.2. The conductivity in choline chloride/ tartaric acid ionic

liquid and with addition of metal chlorides:
Ionic liquids have reasonably good ionic conductivities compared
with those of organic solvents/ electrolyte systems (up to 10 ms cm-1), as
showed in section (1.4).
To determine the conductivities of the transition metal chloride
solution in choline chloride/ tartaric acid ionic liquid of the
concentrations stated in Table (3.7) the dissolved amount of these
compounds was aided by heating the solution to 80 ºC and the
measurements were commenced when the solution reached room
temperature. The determined values of conductivities were shown in
Table (3.7).
It can be said that the conductivity of these solutions were only
exceeded that of ionic liquid by small value and did not reveal the
assistance of such measurements to deduce the number of unpaired
electrons in the d-orbitals of the cations. This is probably due to the high
viscosity nature of ionic liquid or its solutions with the metal chloride,
thereby reducing the mobility of the ions carrying the charges.
However, at higher temperature the viscosity of these solutions
(36,80)
expected to be less as it is inversely related to temperature . Hence,
the conductivity of choline chloride/ tartaric acid ionic liquid showed an
increased value from (0.02 ms/cm) at 25 ºC to 0.14 ms/ cm at 100 ºC
when measured in this work.
81
This is in agreement with the same trend of increased conductivity of

ionic liquids, for example choline chloride/ urea of 2:1 mole ratio
(freezing point of 12 ºC) have anoticable increased value at 19 ºC of 325
µs/cm (81).
Table (3.7):-Conductivity of room temperature ionic liquid and with

addition of metal chlorides at different concentrations.
Complexes ms/cm µs/cm Concentrations

(M)
Ionic liquid 0.02 20 -
CrCl3.6H2O 0.01 10 0.037
FeCl2.4H2O 0.04 40 0.050
CoCl2.6H2O 0.05 50 0.042
NiCl2.6H2O 0.03 30 0.042
CuCl2.2H2O 0.04 40 0.058
3.3. The F.T.IR spectra of choline chloride/ tartaric acid ionic

liquid and metal chlorides:
3.3.1. A. The infrared spectra of choline chloride:
The infrared spectra of this compound (HOC2H4N (CH3)3+Cl-), Fig.
(3.41), show the υ (O-H) band at (3340.48) cm-1, υ (C-H) aliphatic at
(3008-2815.88) cm-1, υ (C-O) at (1265) and the other stretching band at
(1481) cm-1 assigned to the υ (C-N) (82,83)
. .
.
82
3.3.1. B. The infrared spectra of tartaric acid:

The infrared spectra of this compound ([CHOHCOOH]2), Fig.(3.42),
shows a sharp band appeared at (3409-3340) cm-1 assigned to the υ (O-H)
group, υ (C=O) at (1743.53) cm-1, υ (C-O) at (≈1251) cm-1.
And the other stretching band at (2900.74-2839.02) cm-1 assigned to the υ
(C-H) aliphatic (82,83). .
.
3.3.1. C. The infrared spectra of choline chloride/ tartaric acid
ionic liquid:
The infrared spectrum of this solvent choline chloride/tartaric acid
Fig.(3.43), show the presence of hydrogen bond (H···O-H) indicated by
the broad band, of υ (O-H), centered at (3340.48) cm-1 which could be
attributed to the polymeric hydrogen bonding. This might be responsible
for the viscose nature of the ionic liquid·. The band of υ (C-H) aliphatic
appeared at (2923.88) cm-1, the band of υ (C=O) found in tartaric acid
appeared at (1735.81) cm-1, also the band of υ (C-O) found in tartaric acid
appeared at (≈1250) cm-1 and the other stretching band of υ (C-N) at
(1481) cm-1 (82,83). .
3.3.2. The infrared spectra of {Cr (III), Fe(III), Co(II), Ni(II)

and Cu(II) chlorides} in choline chloride/ tartaric acid ionic
liquid: .
Infrared investigation of ionic liquid solvent suggested a structural
interaction between choline chloride and tartaric acid, the constituents of
the solvent. The liquid nature of this solvent was characterized by the
formation of hydrogen bonding that might cause the viscous nature
characterized by this solvent. .
83
In addition, the infrared spectra of all metal ions in this ionic liquid
did not show the characteristic covalent bonds between the metal and the
constituent ions of ionic liquid such as O2-, Cl¯ and N which was
attributed to the strong vibration of this ionic liquid in the low energy
range of the spectra where the bands are expected to be observed.
Therefore, the infrared investigation of Cr3+, Fe3+, Co2+, Ni2+ and
Cu2+ chlorides in pure ionic liquid Fig.(3.44-3.48) did not show a
significant changes in comparison with the vibration spectra of the ionic
liquid Fig.(3.43). However, the expected coordination of metal with the
expected donating atoms of oxygen, chloride or nitrogen expected to have
a low energy. .
84
Chapter three
85
Result and Discussion
Fig. (3.41): F.T.IR spectrum of choline chloride

Chapter three
86
Fig. (3.42): F.T.IR spectrum of tartaric acid

Chapter three
87
Fig. (3.43): F.T.IR spectrum of choline chloride/ tartaric acid ionic liquid
Chapter three
88
Fig. (3.44): F.T.IR spectrum of chromium (III) chloride

Chapter three
89
Fig. (3.45): F.T.IR spectrum of iron (III) chloride

Chapter three
90
Fig. (3.46): F.T.IR spectrum of cobalt (II) chloride

Chapter three
91
Fig. (3.47): F.T.IR spectrum of nickel (II) chloride

Chapter three
92
Fig. (3.48): F.T.IR spectrum of copper (II) chloride

3.4. Conclusion:
1- Metal chlorides in choline chlorides / tartaric acid ionic liquid at
room temperature were investigated.
2- Ionic liquid with viscous nature when metal chlorides alone or with
added oxalic acid or EDTA salt were added remained viscous.
3- The geometry of the metal cations were of different shape according
to the type of metal cations, regardless of their oxidation states.
4- The arrangements of the attached ligand strength could be put in the
following order:- Ionic liquid < oxalic acid < EDTA salt
5- The calculated ligand field shows different strength (according to the
10 Dq value), different Racah parameter (B`) and different electron
repulsion parameter (β), which refers to different ionic character
between the metal and the donor atoms of the ligands.
6- Formation of polymeric hydrogen bonding in the melt caused the
viscous nature.
7- Infrared spectra of dissolved metal compound to the melt can hardly
be evaluated due to the high vibration spectra of melt compounds.
8- As the solvent was of ionic nature, hence conductivity changes of
added metal compounds did not show a significant change at room
temperature.
93
3.5. Suggestion for future work:

The following suggestions can be postulated to ensure completion of the
study in this work:
1- Investigating the solubility and coordination of another set of

transition metal complexes using other transition metal ions such as
second or third rows of transition metal using the same ionic liquid.
2- Is to determine a suitable method to isolate the formed complexes

of transition metal ions from their ionic liquid solution and
carrying a more suitable method of identifications such as infrared
spectroscopy, magnetic susceptibility measurements and x-ray
diffraction.
94
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Republic of Iraq

Ministry of Higher Education

Coordination of some transition metal ion

September 2008 Ramadhan 1429

I certify that this thesis was prepared under my supervision at the

In view of the available recommendation, I forward this thesis for debate

Name: Assist. Prof. Dr. Salman A. Ahmed

Member Supervisor / Member

Approved for the council of the College of Science.

I wish to express my deepest gratitude and great appreciation

Sincere thanks are due to the Chemistry department, Al-

My deepest thanks and appreciation are also due to my lovely

Finally, sincere thanks and deep respect go to all my teachers,

Farah Awad Ahmed

Some transition metal chlorides, CrCl3.6H2O, FeCl3.4H2O,

3.1.1.2. Substitution Reaction with Oxalic acid. 44

NO. Figures Page

3.5 tartaric acid ionic liquid (0.096 M) (curve A) and in aqueous 41

3.10 chloride/tartaric acid ionic liquid with addition of EDTA 48

The UV-Vis. spectra of pale yellow solution of FeCl3.4H2O

3.17 Suggested structure for iron (III) in choline chloride / tartaric 55

3.26 liquid at room temperature curve (A), with addition of oxalic 65

Suggested structure for nickel (II) chloride in choline

3.31 chloride/ tartaric acid ionic liquid with addition of oxalic 70

3.39 tartaric acid ionic liquid at room temperature with addition 80

3.41 F.T.IR spectrum of choline chloride. 85

3.47 F.T.IR spectrum of nickel (II) chloride. 91

3.48 F.T.IR spectrum of cupper (II) chloride. 92

NO. Tables Page

2.2 tartaric acid ionic liquid with added number of moles of 29

2.3 Splitting of terms for dn configuration. 33

1.1. Molten salts and Room Temperature Ionic Liquids

Some ionic liquids, such as ethyl ammonium nitrate, are in a

1.2. Ionic liquids, literature review:

1.3. Green chemistry and green solvents:

Alternative promising areas of research in the replacement of the use

1.4. Some Physical properties of ionic liquids:

2-Viscosity: Generally, ionic liquids are more viscous than common

4-Conductivity: Ionic liquids have reasonably good ionic conductivities

5-Thermal stability: Ionic liquids can be thermally stable up to

6-Electrochemical window: By definition, the electrochemical window

1.5. Advantages of ionic liquids:

1.6. Applications of ionic liquids:

They can be designed specifically for every type of application since

1.7. Ionic liquid of choline chloride:

1.8. The chemistry of the first transition metal elements:

[CrX6] 3- (X=halide, CN, SCN, N3, H2O, NH3).

The hexaaqua ion [Cr(H2O)6]3+, which is regular octahedral, occurs

The magnetic properties of the octahedral Cr (III) complexes are

1.8.2. Iron (III), (d5):

The various hydroxo species, such as [Fe(OH)(H2O)5]2+, are yellow

1.8.3. Cobalt (II), (d7):

The aqua ion [Co(H2O)6]2+ is the simplest complex of cobalt (II). In

Addition of chloride caused a shift of the absorption maximum of

1.8.4. Nickel (II), (d8):

The coordination number of Ni (II) rarely exceeds 6 and its principal

Fig. (1.1):- Spectra of NiCl2, (curve A) c = 0.046 mol dm-3 in acetamide-potassium

1.8.5 Copper (II), (d9):

The aqueous solutions are prone to slight hydrolysis and, unless

The T ground term of the tetrahedrally coordinated ion implies an

1.9. Interaction of the ligands with the metal ions:

Stability of these complexes may be summarized as follows (61,63):

Tendency of ligands to complex with Tendency of ligands to complex