Advances in chemistry research volume 8

ADVANCES IN CHEMISTRY RESEARCH

ADVANCES IN CHEMISTRY RESEARCH
VOLUME 8
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ADVANCES IN CHEMISTRY RESEARCH

ADVANCES IN CHEMISTRY RESEARCH
VOLUME 8

JAMES C. TAYLOR
EDITOR

Nova Science Publishers, Inc.
New York

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CONTENTS
Preface

vii 

Chapter 1

Association Nature of Dyes Chromaticity
Yu. A. Mikheev, L. N. Guseva, Yu. A. Ershov
andG. E. Zaikov 

Chapter 2

Thermal Bhaviour and Enthalpy Relaxation in Aromatic
Polycarbonate and Syndiotactic Poly(Methyl-Methacrylate)
Maurizio Penco, Stefania Della Sciucca,
Gloria Spagnoli and Luca Di Landro 

Chapter 3

Chapter 4

About Geometrical and Electronic of the Structure

of Molecular Insectitsid DDT (Nobel Award 1948, P. Muller)
V. A. Babkin, V. U. Dmitriev and G. E. Zaikov 
Parameters of the Combustion of Differential Propellant
in Mixture of Oxidants: Molecular Oxygen-Ozone
V. A. Babkin, K. V. Sergeeva, E. S. Titova
and G. E. Zaikov 

Chapter 5

Cobaloximes with Functionalized Ligands
Alexei A. Gridnev, Dmitry B. Gorbunov
and Gregory A. Nikiforov 

Chapter 6

The Tacticity Governed Stereomicrostructure
in Poly(Methyl Methacrylate) (PMMA) as a Way
to Explain its Physical Properties
N. Guarrotxena 

Chapter 7

The Modeling of Transition Metal Complex Catalysts
in the Selective Alkylarens Oxidations with Dioxygen:
The Role of Hydrogen – Bonding Interactions
L. I. Matienko, L. A. Mosolova and G. E. Zaikov

1 

29 

47 

51 

55 

67 

75 


vi
Chapter 8

Chapter 9

Chapter 10

Chapter 11

Index

Contents
New Carbofunctional Oligoisiloxanes for the Substrates
of Antibiocorrosive Covers
N. Lekishvili, Sh. Samakashvili, G. Lekishvili
and Z. Pachulia 
Performance, Stability and Qualification
of Developed Multifunctional Materials

Jon Meegan, Mogon Patel, Anthony C. Swain,
Jenny L. Cunningham, Paul R. Morrell
and Julian J. Murphy

115 

129 

Molybdenum-Initiated Ring Opening Metathesis
Polymerization of Noborn-5-ene-2-yl Acetate
Solmaz Karabulut

145 

The Co-Occurrence of Carrageenan and Agaran
Structures in Red Seaweeds
Marina Ciancia and Alberto S. Cerezo

155 
193 


PREFACE
This book presents original research results on the leading edge of chemistry research.
Each article has been carefully selected in an attempt to present substantial research results
across a broad spectrum. Topics discussed include thermal behaviour and enthalpy relaxation
in aromatic polycarbonate; cobalozimes with functionalized ligands; parameters of the
combustion of differential propellant in mixture of oxidants and the modeling of transition
metal complex catalysts.
Chapter 1 - In the range of waves lengths 200-800 nm are studied absorption electronic

spectra of individual molecules of triphenilmethane, xanthene and thiazene dyes. In
triphenilmethane a number are studied the malachite green, crystal violet, diamond green and
methyl violet. In xanthene number are studied rodamine B and rodamine G; in thiazene a
number - methylene blue. Molecular solutions of dyes prepared by heptane extraction from
commercial powders, and also by thermal processing of triacetate cellulose and the
cellophane films, painted by these dyes. It is established, that individual molecules of dyes do
not absorb light in visible range of a spectrum, i.e. have no chromogene groups. From here
follows, that usually observable chromaticity of dyes is caused by supramolecular structures dimers and larger dyes molecules associates at mutual orientation favorable for molecular
interaction. From here follows, that existing quantum-chemical theories of chromaticity of the
studied dyes classes are incorrect and demand revision.
Chapter 2 - The structural relaxation of polymers depends on the kinetic character of the
glass-transition phenomenon: amorphous polymers below their Tg are not at equilibrium and
their structures continuously relax in attempt to reach the equilibrium state. Several
phenomenological and molecular approaches have been proposed to describe the structural
relaxation but a universal model is still lacking. The enthalpy relaxation of glasses is usually
described with models developed on the basis of Tool-Narayanaswamy-Moynihan (TNM)
theory [1,2]: it is assumed that the instantaneous relaxation time(s) (τ) for enthalpy relaxation
depends on both the temperature (T) and the structure of the glass, identified by its fictive
temperature (Tf). This approach is able to describe the enthalpy relaxation in low-molecularweight glass-forming system fairly well [3,4], but discrepancies have been observed in
several polymeric systems [5,6]. One of these discrepancies concerns the overestimation of
enthalpy lost on aging the samples for long periods of time. Hodge [7], Gomez Ribellez [8]
and Cowie [9] ascribed this features in polymers to the effect of topological constraints, such
as chain entanglements, which are completely ignored in the TNM-based models.


viii

James C. Taylor

In this work, the enthalpy relaxation of aromatic polycarbonates and of syndiotactic

poly(methyl methacrylate)s (PMMA) are investigated performing DSC experiments with the
intention of characterize the effect of the composition and of the molar mass in aromatic
polycarbonates and the relaxation dynamic as a function of the molecular mass and to
highlight the effect of PMMA entanglement mass (Me) in syndiotactic poly(methyl
methacrylate)s (PMMA).
Chapter 3 - Quantum-chemical calculation of molecular of insectitsid DDT was done by
method AB INITIO in base 6-311G**. Optimized by all parameters geometric and electronic
structures of these compound was received. The universal factor of acidity was calculated
(pKa=26.5). Molecular of insectitsid DDT pertain to class of very weak Н-acids (рКа>14).
Chapter 4 - Calculation of the mixture of oxidants of differential propellant (molecular
oxygen – ozone) was made by classical quantum-chemical semitheoretical method CNDO/2
in parametrization of Santri-Poppl-Segal. Optimized geometric and electronic structure of the
combination of these oxidants was received. Parameters of the combustion of this mixture
were evaluated. Parameters of the combustion of mixture of oxidants (O2+O3) practically do
not differ from parameter of the combustion of the molecular oxygen.
Chapter 5 - Cobaloximes, alkylcobaloximes and borofluoride adducts on the basis of
asymmetric functionalized ligandes have been synthesized. These cobaloxime systems form
geometric isomers. The presence of chiral center in axial ligand gives rise to the appearance
of diastereotopics effect.
Chapter 6 - Three industrial samples of Poly(methyl methacrylate) (PMMA), prepared
under different conditions, have been extensively analyzed by means of 1H-NMR
spectroscopy. Starting from the mm, rr and mrandrm triad contents, as given by the spectra,
the type of tacticity statistics distribution has been deduced. Sample X appears to be
completely Bernoullian, while samples Y and Z deviate somewhat from this behaviour
exhibiting a tiny trend towards Markovian statistics. The fraction of mmrm and rrrm pentads
and that of pure heterotactic and atactic triad moieties has been calculated by assuming either
a Markovian statistics for samples Y and Z or a Bernoullian statistics for all the samples. On
the other hand, the fraction of the same pentads has been determined by deconvoluting the
overall triad signals of the spectra into the corresponding pentad signals. An appreciably good
agreement with the values obtained assuming Bernoullian statistics for all the samples

appears evident. As a result, the evolution of every pentad content from sample X to Sample
Z could be stated. Thus the samples prove to be appropriate models to study the relationship
between any physical property and the stereomicrostructure of PMMA as was done
previously for Poly(vinyl chloride) (PVC) and Polypropylene (PP).
Chapter 7 - The different methods of improvement of catalytic activity of transition metal
complexes in the oxidations of alkylarens with molecular oxygen are stated briefly. The
offered at first by authors and developed in their works the method of control of catalyst
activity of transition metal complexes with additives of electron-donor mono- or multidentate
exo ligands L2 in the oxidations of alkylarens (ethylbenzene, cumene) with molecular oxygen
into corresponding hydroperoxides is presented. The modeling of catalytic nickel and iron
complexes with use of ammonium quaternary salts and macro-cycle polyethers as exo
ligands-modifiers is described in detail. The role of the Hydrogen–Bonding interactions in
mechanisms of homogeneous catalysis is discussed. The modeling of catalyst activity of
complexes Fe(II,III)(acac)n with R4NBr (or 18-crown-6) (18C6) in the ethylbenzene oxidation
in the presence of small amounts additives of water (~10-3 mol/l) is analyzed. The role of


Preface

ix

micro steps of the chain initiation (O2 activation), and propagation in the presence of catalyst
(Cat + RO2•→) in the mechanism of nickel- and iron-catalyzed oxidation of ethylbenzene is
evaluated.
Chapter 8 - New carbofunctional oligoisiloxanes containing trifluorinepropil and
methacrylic groups at silicon atoms have been synthesized and studied. On the basis of the
data of IR and NMR spectral analysis the process of hydrosilylatrion, composition and
structure of synthesized compounds have been investigated. By using of diferential-thermal
and thermogravimetric analisis method the thermal stability of sintesized oligomers have been
studied. By the diferential-scanning calomerty method the phase transition temperatures of

synthesized oligomers were determined. It was established that synthesized oligomers are
amorphic one-phase systems.
The preliminary ivestigation showd that the sybthesized carbofunctional oligomers in
combination with polyepoxides and non-volatile bioactive organo-ellement arsenic complex
compounds new composite materials of multifunctional application for individual and environmental protection of various materials may be created.
Chapter 9 - In this article we will review the design, formulation and development of
materials exhibiting simplified structure / property relationships, reversible cure mechanisms,
increased resistance to physical property changes over time and stress sensitive behaviours.
These properties are discussed within the context of the external literature. The article also
provides a brief overview of the processes employed by AWE to qualify materials and further
understand their storage, ageing and compatibility properties.
Chapter 10 - MoCl5-e−-Al-CH2Cl2 catalyst system can efficiently polymerize noborn-5ene-2-yl acetate in moderate yields and in relatively high molecular weights. The analyses of
the product by FTIR, 1H NMR and 13C NMR spectra give the verification of metathetical
polymers. The polymer shows narrow molecular weight distribution and good solubility in
common organic solvents.
Chapter 11 - In the last seventeen years it has been shown that red seaweeds classified as
“carrageenophytes” also biosynthesize agaran structures, while certain “agarophytes” produce
small amounts carrageenan structures. No neat separation of these carrageenan/agaran
systems was obtained, leading to the idea of “hybrid” molecules, called DL-hybrid galactans.
Several points concerning these polysaccharide systems have been addressed:
1. Description of the systems of galactans, in which carrageenan and agaran
structures were found (DL-galactan systems), as well as the methodology
necessary for their detection.
2. Isolation of “pure” carrageenans or agarans from these systems using nondegrading conditions and the consequent new hypothesis of the formation of
molecular complexes.
3. Evidences favoring each hypothesis, namely, the existence of hybrid molecules
versus molecular complexes formation.
Versions of these chapters were also published in Polymers Research Journal, Volume 3,
Numbers 1-4, edited by Frank Columbus, published by Nova Science Publishers, Inc. They
were submitted for appropriate modifications in an effort to encourage wider dissemination of

research.



In: Advances in Chemistry Research. Volume 8
Editor: James C. Taylor

ISBN 978-1-61209-089-4
©2011 Nova Science Publishers, Inc.

Chapter 1

ASSOCIATION NATUREOF DYES CHROMATICITY
Yu. A. Mikheev1, L. N. Guseva1, Yu. A. Ershov2 and G. E. Zaikov*
1

N.M. Emanuel Institute of Biochemical Physics,
Russian Academy of Sciences, 4 Kosygin str., 119334 Moscow, Russia
2
N.E. Bauman Moscow State Technical University, 2-rd Baumanskaya str. 5, 105005
Moscow, Russia

ABSTRACT
In the range of waves lengths 200-800 nm are studied absorption electronic spectra
of individual molecules of triphenilmethane, xanthene and thiazene dyes. In
triphenilmethane a number are studied the malachite green, crystal violet, diamond green
and methyl violet. In xanthene number are studied rodamine B and rodamine G; in
thiazene a number - methylene blue. Molecular solutions of dyes prepared by heptane
extraction from commercial powders, and also by thermal processing of triacetate
cellulose and the cellophane films, painted by these dyes. It is established, that individual

molecules of dyes do not absorb light in visible range of a spectrum, i.e. have no
chromogene groups. From here follows, that usually observable chromaticity of dyes is
caused by supramolecular structures - dimers and larger dyes molecules associates at
mutual orientation favorable for molecular interaction. From here follows, that existing
quantum-chemical theories of chromaticity of the studied dyes classes are incorrect and
demand revision.

Keywords: nature of dyes, electronic spectra, supramolecular structures, quantumchemical calculations, chromaticity.

*

E-mail:


2

Yu. A. Mikheev, L. N. Guseva, Yu. A. Ershov et al.

The big number of the works devoted to the nature of organic compounds chromaticity is
published. Interest to a chromaticity problem is connected with requirements of development
of technology of dyeing, and also with problems of photochemistry and sciences about
photoconductivity and transformation of a solar energy to electricity [1-9].
All works devoted to the nature of organic compounds chromaticity, are based till now on
achievements of quantum chemistry of individual molecules (see [1-4] and Internet search
systems sites, for example, www.scirus.com). Thus the term «chromogene», used for a
designation of the molecular structure which are giving rise to coloring, connect exclusively
with the individual molecules. These possessing enough developed conjugated π-bonds
system, and the term «chromophore» designates various chemical groups which are under
construction chromogene [4].
However, in works [10, 11] at copper phtalocyanine research (a pigment of dark blue

color) the important fact has been established, that chromogene of this dye are individual
molecules, but supramolecular dimers and larger molecular associates are not. In these works
applied extraction molecules of dye from powders by means of polymeric films
(polyethylene, cellulose triacetate) and heptane. This method allows separating single
molecules from pigment particles. It is established, that commercial copper phtalocyanine
powders contain a cmall amount of an amorphous phase, heptane soluble. As a result did
received solutions of individual molecules possess a characteristic spectrum with the
developed system of electronic-oscillatory bands. These bands are in ultra-violet area, i.e.
individual molecules do not absorb visible light and do not form the painted solutions. From
here follows, that color of the given dye arises only as a result of compound of molecules in
supramolecular dimers and larger associates.
In the given work individual molecules of cation triphenilmethane, xanthene and thiazene
classes dyes are releaseed by extraction and thermal processing. It has appeared, that, as well
as in a case copper phtalocyanine, chromogenes of this dyes type are not individual
molecules, and their supramolecular dimers and larger associates are chromogene. From the
received results the urgency of working out of quantum chemistry methods follows with
reference to supramolecular structures of dyes.

EXPERIMENTAL
In this work used commercial powders of triphenilmethane (TPMD), xanthene (XD) and
thiazene (TD) dyes (Shostkinsky chemical reactants plant). Are studied TPMD - malachite
green (MG), crystal violet (CV), methyl violet (MV) and diamond green (DG) (in the form of
1% spirit solution). Are studied also XD – rodamins B and G, and representative of–
methylene blue (MB).
Molecules of the listed dyes contain developed positively charged π-systems and oxalateor chlorine anions.
Extraction of MG, CV and MV molecules from powders carried out by spectroscopic
pure heptane on a water bath. Extraction of DG and rodamine B molecules carried out from
their spirit solutions at 25º C. To notice, that chromogene molecular associates of the studied
dyes not soluted in heptane.

Association Nature of Dyes Chromaticity

3

For preparation of a rodamine B heptane molecular solution ~1mg dye sample dissolved
in ethanol (2 ml), added heptane (4 ml). Then the received mix diluted with water. Water
action consists, first, in heptane miscibility decrease with spirit, secondly, in heptane
extraction strengthening of dye molecules from an aqueous-alcoholic layer.
Heptane processing of rodamins and MG powders does not lead to formation of
molecular solutions. Thus rodamine and the MG molecules was not possible extract as well
from their specially prepared spirit solutions. Extraction subjected also solutions of
immonium hydroxides TPMD which prepared, mixing powders or their spirit solutions with
water solutions of alkali KOH (2-5%).
Used also release ion of molecular fractions of dyes by absorption from aqueousalcoholic solutions of dyes by triacetate cellulose (TAC) films. Solutions of dyes for
extraction prepared, mixing their spirit solutions (~10 mg in 10 ml of ethanol) with the
distilled water (~10 ml).
Influence of heating on electronic spectra of TAC and the cellophane films, containing
XD and MG is studied.
XD entered into TAC films (20 microns) from solutions in the mixed solvent (9 parts of
chloroform on one part of ethanol), evaporating solvent in Petri dishes. XD and MG entered
also into cellophane films (a thickness 40 microns) by absorption from aqueous-alcoholic
solutions. For this purpose mixed solutions of dye of 3 mg in 1 ml of ethanol about 20 ml of
the distilled water. As a result dyes concentration in films exceeded concentration in water
approximately in 100 times.
Solutions and films spectra registered on “Specord UV-VIS” and “Shimadzu UVmini1240” spectrophotometers.

DISCUSSION OF RESULTS
Spectral Properties of Individual and Aggregated Cationic
Triphenilmethane Dyes (TPMD)

The Chromogene Nature of the Malachite Green
TPMD molecules studied comprise grouping with developed π-system and a fragment
with the chinoid structure bearing a positive charge on atom of nitrogen (immonium cation).
Consider [1-4] what exactly such molecular structure serves as the reason of occurrence of
coloring, i.e. is chromogene.
The immonium cation structural formula of TPMD looks like:


4

Yu. A. Mikheev,
M
L. N.
N Guseva, Yuu. A. Ershov ett al.

Here R = СН
С 3 and R ' = H (MG); R = СН3 and R ' = N (CH3) 2 (C
CV);
R = С2H5 and
a R ' = H (D
DG); R = CH3 and R ' =NH (CH
( 3) (MV).
TPMD anions are Cl - inn molecules CV
C and MV, and
a oxalate-annions Ox- in MG
M and DG
m
molecules.
Thu
us MG and DG

D moleculess include two organic imm
monium cationns and two
am
mmonium catiions [12].
For example, MG formuula looks like
(Ox–N+H(C
CH3)2–Рh'–С(Р
Рh)=Рħ=N+–OCO–)
O
2,
where Ox - oxaalate-anion, Рhh and Рh' - phenyl and phennylene radicals, Рħ - a cycloohexadiene
w
frragment of a chinoid radicall.
The optical spectrum off a MG - oxalaate ethanol solution (1 molee/l) is resultedd on Figure
1аа, a curve 1. Maxima
M
spectrral positions (νν, cm-1 (λ, nm
m)): 16 200 (617); 23 500 (4225 nm) and
31 600 (316 nm
m) of absorptiion band of a MG oxalate ethanol
e
solutioon correspondd to literary
V
of the seeeming extinction coefficiennt, calculated for the main absorption
daata [1, 13]. Value
baand (617 nm) of MG chrom
mogene particlees dissolved inn ethanol counnting on conceentration of
inndividual arom
matic fragmentts (Ar) makes ε617 = 4.4×104 l / (mole.cm)).

(a)
Fiigure 1. Continu
ued on next pagge.


Association Nature of Dyes Chromaticity

5

(b)
Figure 1. Changes of optical spectra ethanol (a) and heptane (b) solutions of commercial MG oxalate in
the presence of KOH (a) and ethanol (b). Explanatory in the text.

On Figure 1а curves 2-4 represent transformation of a spectrum 1 in a MG carbinol
leycoform spectrum at addition of alkali KOH in a solution. Curves 2 and 3 characterize
change of a spectrum 1 in time (through 40 and 80 mines accordingly) at very low
concentration KOH - 8·10-5 mole/l, and 4 - at 3·10-3 mole/l.
It is necessary to underline, that for lack of alkali in a MG oxalate ethanol solution
(Figure 1а, the curve 1) in a spectrum is not found out any signs of increase in time of an
intensive carbinol leycoform band at frequency ν =38000 cm-1. It testifies to stability MG
oxalate in ethanol solution.
In alkaline environment MG oxalate is hydrolyzed finally with carbinol formation. It is
necessary to notice, that MG and CV carbinols for the first time are received in work [14] by
processing of these dyes chlorides by weak water solutions of alkalis. Thus MG and CV
carbinols were released in the form of deposits, slightly solved in water. Pure carbinols
received by recrystallization from heptane or ether, are steady and, contrary to representations
of authors of work [13], do not dissociate in ethanol solutions on Ar-cations and hydroxylions [14, 15].
Observed on Figure 1а character of spectral transformation of MG solution under the
influence of alkali finds out the step nature of this process. So, already at very low
concentration of alkali there is an intensity decrease chromogene bands νmax = 16200 cm-1 of

dye to simultaneous increase of a wide band νmax = 38 000 cm-1. Thus on curves 1-3 (Figure
1а) is available an isobiestic point at ν = 35 500 cm-1. From here follows, that at an
intermediate stage of hydrolysis intermediate products with identical spectroscopic properties
are formed which, however, are not carbinol. For reception of carbinol it is required to
increase concentration of alkali. So, at increase in concentration KOH to 3×10-3 mole/l the
isobiestic point disappears, and the UV-band arising thus (Figure 1а, a curve 4) an endproduct - carbinol keeps the form of a band of predecessors, but has higher intensity.
It is necessary to notice, that at the first stage of MG oxalate-ions hydrolysis are replaced
with hydroxide-ions with formation immonium-basis. I.e. immonium cations remain. At very
low alkali concentration disappearance of dye band (Figure 1, curves 1-3) is accompanied by


6

Yu. A. Mikheev, L. N. Guseva, Yu. A. Ershov et al.

simultaneous growth of an ultra-violet band (38 000 cm-1) which position in accuracy
corresponds to the carbinol UV-band. At such low KOH concentration reaction stops at
presence isobiestic point on a spectrum. Thus dye transforms in immonium hydroxide,
carbinol precursor. The solution becomes colorless, that is rather essential. It testifies that in
itself individual MG cations are not chromogenes.
The MG oxalate hydrolysis end-product - leycocarbinol is formed at increase in alkali
concentration with isobiestics infringement in a spectrum.
Leycocarbinol has two alkilaniline groups absorbing UV-light at 38 000 cm-1 (263 nm)
[13, 16]. Therefore its UV-band is more intensive in comparison with MG immonium cations,
having one alkilaniline group. Received for carbinol value of extinction coefficient ε263 =
2.8×104 l/ (mole.cm), calculated on a spectrum 4 (Figure 1а), practically coincides with
resulted in [15]. The same size turns out from parity D617/D263 = ε617 / ε 263, that corresponds
to practically full transform of arils MG Ar-fragments in carbinol. On a low-frequency slope
of a band of 38 000 cm-1 the excess in the range of 33 000 cm-1 (~ 300 nm) where according
to [13, 15] there is a weak additional carbinol absorption band is observed.

Simultaneously with carbinol UV- bands in a spectrum 4 (Figure 1а) is observed a weak
band at 28 000 cm-1. It belongs not MG cations, but to by-product Х which is formed at MG
synthesis. This collateral Х, too, as well as MG, is in an initial preparation of dye in oxalate
form. That a band ~ 28 000 cm-1 in its spectrum appear at big enough maintenance of alkali
(Figure 1а testifies to it, a curve 4) in that interval of frequencies, where a spectral curve of
dye (Figure 1а, the curve 1) has a minimum. Oxalate product Х the group eliminates not only
under the influence of alkali does not possess high firmness, and oxalate, but also at heating
in heptaneе.
On Figure 1б represented the spectrum (a curve 1) of compounds, heptane extracted
(volume of 10 ml) from initial MG sample (~ 100 mg) at ~ 100 ºС. The received extract has
been filtered through the paper filter and diluted in 2.5 times. In this spectrum the UV-band
νmax = 30 300 cm-1 (~ 330 nm) of compounds Х have big enough intensity and is batohrome
displaced to 28 000 cm-1 at replacement heptane by ethanol (Figure 1б, a curve 3). The
maximum of the same band in heptane, saturated with ethanol, is located at 30 000 cm-1, and
in the ethanol saturated heptane at 28 250 cm-1 (350 nm) (Figure 1б, a curve 2). (Heptane and
ethanol limited mix up with each other, forming two layers).
It is necessary to notice, that the compounds of type Х having the UV-bands with similar
properties are found out in all investigated dyes. It testifies that admixture compounds
molecules in them have identical chromophore groups. It is essential, that in spectra of
solutions (Figure 1б, curves 1 - 3), received heptane extraction, are absent signs of bands of
absorption of initial dye which practically we will not dissolve in heptane. There are no also
band signs MG carbinol forms (38 000 cm-1, see Figure 1а, a curve 4).
On Figure 1б the spectrum 3 characterizes ethanol solution received after heptane
evaporation from heptane extract and the subsequent dissolution of the dry rest in ethanol. It
is visible, that after transition in ethanol, the UV-band extracted compounds Х tests
batohrome displacement concerning a heptane solution band. However, the characteristic
band of carbinol MG forms at 33 000 cm-1 here is absent. This band appears only in the
presence of alkali. For example, the spectrum 2 (Figure 1б) is transformed to a spectrum 4
(Figure 1б) at addition in a solution of 20 mg KOH. Alkali entering, apparently, is not
reflected in the form and intensity of the UV-band at 28 250 cm-1, belonging to compound Х,

however, thus there is characteristic for carbinol UV-band at 33 000 cm-1.


Association Nature of Dyes Chromaticity

7

It is necessary to notice, that the spectrum 4 (Figure 1б) UV-light absorption is a little
deformed in area ν>33 000 cm-1 by spectrum imposing turbidness from light-scattering KOH
colloid particles. Light scattering deformed the widened band at 40 000 cm-1 represents the
sum of bands from formed carbinol and, probably, high-frequency band of compound Х.
It is necessary to pay attention also that in a spectrum heptane extract 1 (Figure 1б) the
UV-band with νmax = 41 200 cm-1 (243 nm) is clear expressed. The considerable contribution
to this band absorption not having bands in visible area of a spectrum bring passed in heptane
individual MG molecules, including immonium cations, but. That fact testifies to presence of
individual MG molecules in heptane extract, that band of 33 000 cm-1 arises under the
influence of alkali (Figure 1б, a spectrum 4) at absence in the extract chromogene associates
of MG molecules. Individual MG molecules can be a unique source of carbinol in this case
only.
Considering absence of visible bands of absorption of light at individual MG molecules,
it is necessary to assume, that formation dye chromogene associates from nonchromogene
(colorless) molecules take place probably in this case by self-assemblage of these associates.
Such conclusion proves to be true that at evaporation colorless heptane solutions with a
spectrum 1 (Figure 1б) on glass surfaces of vessels blue-green layers of dye are formed.
Formation chromogene MG crystals from colorless MG molecules can be observed also
by means of a band chromatographic paper absorbing heptane solution and painted during
movement on it and evaporation of solvent.
As MG chromogenes can act not only MG oxalate crystal particles, but also dimers,
formed of nonchromogene individual MG molecules at the expense of enough strong
intermolecular interactions.

The proof of that a band with λmax = 617 nm belong dimers molecules of MG oxalate, is
change of intensity of this band, observed at mixture of two parts spirit solution MG with one
part of ice acetic acid. Value ε617 MG spirit solutions = 4.4×104 l / (mole.cm). In the mixed
solution ε617 = 5.5·104 l / (mole.cm). Despite such increase, absorption coefficient oxalate MG
in a mix of spirit with acetic acid approximately in 2 times it is less, than at chloride MG in
98 % acetic acid (ε617=1.04·105 l/mole·cm) [4]. The observable divergence of characteristics
caused by distinction of the nature of solvents, is rather great. Such influence should be
expected at enough cmall size molecular associates, such as dimers.

Heptane Extracts Spectra of Products of Malachite Green Hydrolysis
Independent evidence is received in experiences with heptane extracts of products of
water-alkaline hydrolysis initial MG oxalate that individual MG cations do not possess
chromogene property. It is obvious, that thus chromogenes particles are formed only as a
result of association of the molecules bearing on compensated electric charges of ionic pairs.
As it was already marked, MG oxalate alkaline hydrolysis finds out, at least, two
macroscopical kinetic stages clear observed on UV-spectra. From the kinetic point of view
hydrolysis reaction proceeds through three consecutive stages [12].
The first stages of MG oxalate alkaline hydrolysis - fast reaction of an exchange of
oxalate ions on HO- anions going from cmall energy of activation:
(Ox–N+H(CH3)2–Ph'–С(Ph)=Pħ=N+–OCO–)2 + 2 HO– →

(I)


8

Yu. A. Mikheev, L. N. Guseva, Yu. A. Ershov et al.
2 Ox–N+H(CH3)2–Ph'–C(Ph)=Pħ=N+(CH3)2–OH + –OCOCOO– ,

(II)

After this the stage of neutralization of ammonium ions proceeds
HO– + II → H2O + Ox– + N(CH3)2Ph'–C(Ph)=Pħ=N+(CH3)2–OH,

(III)

In it the saltless form of hydroxide immonium is formed.
The final, third stage of process is carried out, most likely, by reaction hydroxydeа
immonium with HO- anion, attacking the central atom of carbon:
HO - + III → N (CH3) 2Ph '-C (OH) (Ph)-Ph '-N (CH3) 2 (carbinol) +-OH.
Molecules II and III bear on one dimetilaniline group, whereas a carbinol molecule - two
such groups. According to it, intensity of a band of UV-absorption at a carbinol molecule
should be twice more in the event that quinoid groups of compounds II and III do not bring
the considerable contribution to the given UV-band. Such situation it is possible to explain ν
= 38 000 cm-1 band strengthening in the conditions of the step hydrolysis, observed on spectra
Figure 1а at transition from curves 1-3 (with isobiestic point) to a curve 4. (That quinoid
groups in II and III have rather weak absorption in the range of frequencies 32 000 - 42 000
cm-1, proves to be true properties of compound X which will be considered later.)
UV-bands in the range of 33 000 cm-1 belonging immoniumе hydroxide (II, III) and
carbinol, too differ on the intensity. The spectra presented on Figure 2а proof to it. So, the
heptane extract spectrum in which forms immonium hydroxides II and III prevail, is
presented on Figure 2а, a curve 1. The given solution has been prepared by heptane extraction
(~ 10 ml) of the compounds formed at once after mixture spirit of a MG oxalate solution (~
50 mg in 20 ml of ethanol) with a water solution of alkali (to a consistence of 4 % KOH) and
then diluted in 100 times. At this spectrum there is implicitly expressed band at 33 000 cm-1.
The subsequent extraction the compounds collecting in the same alkaline solution, has
allowed to establish, that the band of 33000 cm-1 becomes more intensive during solution
ageing.

Similarly Rise in Temperature Operates Also at Extraction

On Figure 2а 2 and 3 spectra are presented of heptane extract received by heating (20
min) sample 54 mg MG oxalate to 10 ml of water alkali (5 %) at stirring about 10 ml heptane
and filtering (dilution in 40 times and 320 times accordingly). In both spectra the clear
maximum is observed at 33 200 cm-1, characteristic for a low-frequency band MG carbinol.
Mixture heptane extract with ethanol leads to formation of two layers, one of which
represents the spirit heptane saturated. The spectrum of such layer is presented on Figure 2а, a
curve 4. In this spectrum the carbinol band at 33 000 cm-1 is washed away, losing a maximum
and taking the form of a shoulder, practically repeating the form of the spectrum resulted in
[13]. We will notice also, that present at spectra 1-3 (Figure 2а) heptane solutions in the form
of an excess at 30 000 cm-1 the weak band of compound X, batochrome shift is in a spectrum
spirit a solution heptane saturated, receiving clear expressed maximum at 28 000 cm-1 (350
nm).


Association Nature of Dyes Chromaticity

9

There is one more important feature: freshly prepared heptane extracts colored by alkali
MG oxalate form dye layers on glass ampoules and spectroscopic a ditch. During ageing of
water-alkaline solutions of compound II and III gradually turn in carbinole, and received of
them heptane extracts give ever less a dye deposit. In itself carbinole does not form the
painted deposits.
Formation of the painted deposits from molecules II and III proceeds with the big ease on
the glass ampoules surface as adsorption of individual molecules gives them favourable
mutual orientation. Thus it is possible to use and chromatographic papers bands, immersing
them in heptane solution containing compounds II and III. Formed on a paper band during
movement and evaporation heptane dye is easily washed off by spirit.
The spectrum of eluate from a chromatographic papers band is presented on Figure 2б, a
curve 1. It has not only a band of dye of 16 100 cm-1 (621 nm), but also rather intensive

carbinol band at 37 900 cm-1 (264 nm) which too has been absorbed by chromatographic
paper. Formation of dye particles at adsorption goes in a competition to carbinol formation,
and easily proceeds also on a powder not polar polyethylene oxide, not soluble neither in
heptaneе, nor in spirit.

(a)
Figure 2. Continued on next page.


10

Yu. A. Mikheev, L. N. Guseva, Yu. A. Ershov et al.

(b)
Figure 2. Optical spectra гептановых extracts of products of alkaline hydrolysis оксалата МЗ (a) and
spirit eluates (b) of the compounds formed at adsorption of colourless products of MG hydrolysis on a
filtering paper and polyethylene oxide particles. Explanatory in the text.

On Figure 2б spectra of 2-4 heptane extract from the concentrated water-alkaline solution
MG oxalate, after its mixture with ethanol (in the ratio 1:1) and entering into a mix of 2 mg
polyethylene oxide powder are resulted. Long-wave absorption bands of the spectra 2-4,
observed right after mixing and through 4 and 26 ч accordingly, practically do not differ by
the spectral position from bands MG oxalate in spectra spirit solutions and MG cations in 98
% acetic acid [4].

Spectra of Solutions and Extracts of the Crystal Violet
Spirit solution of CV sample spectrum, presented on Figure 3а (the curve 1), has a visible
light absorption band at 17 380 cm-1 (575 nm), ε575 = 9.5×104 l / (mole.cm). We will notice,
that in extinction coefficient calculations considered presence crystallization waters in CV
powder: 18 molecules of water on 2 CV molecules [1, p.191]. In CV water solution (Figure

3а, the curve 2) a band maximum of dye is at 17 000 cm-1 (588 nm), ε588 = 8.8×104 l /
(mole.cm), that will be co-coordinated with data [1, 17]. On spectra 1, 2 (Figure 3а) is present
also a band not marked in the literature at 29 000 cm-1, belonging to admixture compound
XCV which molecules have chromophore group of type X.
Spectral CV bands are stable enough in time both in spirit, and in water solutions,
however, their intensity decreases at hit in solutions even rather low quantities of alkali.
Entering KOH to concentration of 10-3 mole/l in spirit solution with a spectrum 1 (Figure 3а)
causes its decoloration during 1 – 2 sec. Simultaneously there is a band at 38 000 cm-1 with
low intensive shoulder at 33 000 cm-1 (Figure 3а, a curve 3). The given transformation


Association Nature of Dyes Chromaticity

11

reflects formation carbinol CV forms and actually repeats a situation with formation MG
carbinol (Figure 1, a curve 4).
Observed in spirit a solution at 28 000 cm-1 a band (Figure 3а, the curve 1), belonging to
compound XCV, does not change in the presence of alkali. Dilution spirit heptaneом (spirit
have evaporated to 0.3 ml and then have added heptane to 3 ml) has caused гипсохромное
displacement of the given band to 29 000 cm-1 (Figure 3а, a curve 4).
Initial samples CV contain an impurity not only XCV, but also the rests not reacted
leycobase (triphenilmethane derivative), used for CV synthesis. Both compounds heptane
extracted at heating on a water bath, however residual triphenilmethane it is dissolved at 25
ºС in heptaneе better, than XCV. The spectrum of freshly prepared heptane extract of both
compounds is presented on Figure 3б, a curve 1. Curves 2, 3 (Figure 3б) represent spectra of
heptane solution received after loss from it (through 20) a colorless XCV deposit (spectra
wrote down after filtering and разбавления initial heptane extract accordingly in 140 (1), 100
(2) and 280 times (3).)
Observed during ageing heptane extract spectral transformation testifies, that in a deposit

passes mainly compound XCV (its band in heptaneе has νmax = 30 100 cm-1 (333) nm) whereas
in a solution remains triphenilmethane with an intensive band at νmax = 37 800 cm-1 (264.5
nm) and a weak band at 32 600 cm-1 (306 nm).
Repeated keeping in heptaneе parts of the deposit which has dropped out at 25 ºС, has
given the solution of compound XCV close to saturation, with a spectrum 4 (Figure 3б) and
νmax = 30 100 cm-1. Dissolution of other part of a deposit in spirit has given a spectrum 5
(Figure 3б) with a band displaced to 27 200 cm-1 (367 nm). In both cases practically there are
no triphenilmethane absorption bands (with νmax = 37 800 and 32 600 cm-1) which has
appeared will be better dissolved in heptaneе at 25 ºС, than XCV. It is necessary to notice, that
the UV-absorption spectrum of heptane solution triphenilmethane is very similar to a
spectrum of absorption of spirit solution CV carbinol [13]. However, as is known, carbinol is
badly dissolved in heptaneе at 25 ºС [14, 15].

(a)
Figure 3. Continued on next page.


12

Yu. A. Mikheev, L. N. Guseva, Yu. A. Ershov et al.

(b)
Figure 3. Optical spectra of crystal violet solutions in various mediums (a) both extract
triphenilmethane residual and by-product XCF of synthesis of dye (b). Explanatory in the text.

Good solubility in heptane compounds with νmax = 37 800 and 32 600 cm-1 allows to
identify it with triphenilmethane. Additional acknowledgment of that the given impurity is
not carbinol, serves that processing spirit a solution (a spectrum 5, Figure 3б) chloride
hydrogen does not lead to occurrence of spectral bands of dye - a reaction product carbinols
with HCl. Meanwhile, at processing of the same solution weak сернокислым a dichromate

solution калия it gets color, characteristic for CV, that corresponds to the mechanicm of
synthesis of the given dye [3, 4, 6,].
Let's notice, that in heptane extracts of CV powders, as well as in a case with extracts of
powders MG, are present nonchromogene molecules CV which band of absorption masks
absorption initial triphenilmethane and compounds XCV. A presence nonchromogene
molecule CV in heptane extracts is fixed on gradual release from heptane violet deposits on
walls spectroscopic a ditch. Similar process as it was marked, proceeds and in initially
colorless heptane solutions nonchromogene molecules MG oxalate. The painted layers
especially quickly cover the ampoules glasses containing such extracts, in the conditions of
heating on a water bath when molecules CV and MG have an opportunity to evaporate
together with heptane and then are adsorbed on glasses. Presence nonchromogene molecules
CV in heptane is easily defined the same as and in a case with MG, by means of a band
chromatographic paper shipped in a colorless extract, on occurrence of violet coloring during
moving of a solution and heptane evaporation.

Properties of Alkaline Solutions of the Crystal Violet
The spectral picture of interaction CV with alkali qualitatively reproduces a situation with
MG. So, an end-product of CV alkaline hydrolysis is corresponding carbinol, and formed at
intermediate stages of hydrolysis individual molecules CV hydroxide immonium (type II and


Association Nature of Dyes Chromaticity

13

III) it is possible extract by heptane. As it has appeared, heptane extracts in itself are
colorless, however, being in them hydroxide immoniumя can, as well as in a case with MG,
competely with carbinol formation to turn in supramolecularе dimers and larger units of
violet color. Unlike immonium hydroxide, colorless CV carbinol, as well as MG carbinol,
does not give the painted products without special acid processing.

Formation of layers of dye, as well as in a case with MG, easily proceeds at adsorption of
molecules CV immonium hydroxide on glass ampoules, especially at their evaporation
simultaneously with heptane. Are evident as well experiences with a chromatographic paper
band absorbing heptane extract immonium hydroxide.
Let's notice, that considerable similarity of CV and MG hydroxides immonium spectra
with spectra corresponding carbinols and their ability to form painted dimers, have served as
the reason of occurrence of idea about carbinols dissociation on cation dyes and anions HO- at
carbinol adsorption on firm surfaces [1, 13]. It was supposed [1], that such dissociation
especially easily proceeds at presence on ionized centers of firm surfaces. Meanwhile, results
of the present work proof, first, that cation dyes are not chromogene, secondly, that process of
formation of layers of dyes does not depend on presence ionized centers on adsorbents
surfaces. Really, the surface chromatographic papers contains only the HO- groups which
polarity not bigger polarity of HO- groups of ethanol, and in ethanol CV and MG carbinols do
not form chromogene structures in itself, without influence of acids. At the same time
immonium hydroxides easily form layers of paints even on a surface of particles not polar
polyethyleneoxyde, and especially quickly if particle preliminary to moisten with ethanol for
the purpose of plasticification and increase in molecular-segmental mobility.
It is necessary to notice, that all described above property are characteristic as well for
heptane extracts and for studied by us samples of diamond green (a spirit medical
preparation) and methyl violet, spectra of which spirit solutions qualitatively coincide with
MG and CV spirit solutions spectra.

Spectra and Properties of Compounds with Quinoid Structure of Molecules
As it was marked, all commercial dyes studied in the present work contain heptane
extracted impurity, whose molecules possess chromophore groups responsible for occurrence
in heptane solutions of similar UV-absorption bands in the range of 30000 - 31 000 cm-1 (333
- 320 nm). These bands are equally displaced at replacement heptane on ethanol to 28 000
cm-1 (357 nm). Batohrome displacement of UV-bands at carrying over of the molecules
possessing conjugated π-electronic system, from the hydrocarbonic environment in hydroxyl
one, as is known, stimulates to increase in polarity of molecules at electronic excitation and

accordingly about increase in energy of interaction with environment in comparison with not
exitated molecules [1].
Cmall amount admixture of molecules with similar spectra in all studied samples of dyes
it is possible to explain, proposing the mechanicm applied in manufacture of dyes. This
processing include oxidizing of triphenilmethane in case of MG, DG, CV and oxidizing of
initial compound - dimetilaniline in case of MV [3, 6, 18].
Oxidation triphenilmethane (general formula PhH1 (Ph2) CH-Ph'-N (CH3)2, here Ph1 and
Ph2 - phenyl groups having in para-position substitutants of corresponding dyes) - initiated


14

Yu. A. Mikheev, L. N. Guseva, Yu. A. Ershov et al.

chain free radical process (the initiator - usually lead dioxide) which end-product is carbinol
(Cb):
Ph1 (Ph2) CH-Ph'-N (CH3) 2 + r• → Ph1 (Ph2) C•-Ph'-N (CH3) 2 (R•) + rH,
R• + O2 → ROO•, ROO• + Ph1 (Ph2) CH-Ph'-N (CH3) 2 → ROOH + R•,
ROOH → RO• + HO•, RO• + Ph1 (Ph2) CH-Ph'-N (CH3) 2 → Cb + R•;
HO• + Ph1 (Ph2) CH-Ph'-N (CH3) 2 → H2O + R•;
2 ROO• → breakage,
Here r• - a radical of the initiator.
In parallel with carbinol formation chains of oxidation of CH3- (CH3CH2-) groups
proceed:
Ph1 (Ph2) CH-Ph'-N (CH3)2 + r• → rH + Ph1 (Ph2) CH-Ph'-N (CH3) CH2•, (R1•)
R1• + O2 → R1OO•, R1OO• + Ph1 (Ph2) CH-Ph'-N (CH3) 2 →
Ph1 (Ph2) CH-Ph'-N (CH3) CH2OOH + R1•,
Ph1 (Ph2) CH-Ph '-N (CH3) CH2OOH → Ph1 (Ph2) CH-Ph'-N (CH3) CH2O• + HO•,
HO• + Ph1 (Ph2) CH-Ph'-N (CH3)2 → H2O + R1•,
Ph1 (Ph2) CH-Ph'-N (CH3) CH2O• → CH2O + Ph1 (Ph2) CH-Ph'-N• (CH3) (R2•).

Formed nitric radical R2• enters disproportion reaction with ROO• with formation quinoid
compounds
ROO• (R1OO•) + R2• → ROOH (R1OOH) + Ph1(Ph 2) С=Pħ = NCH3 (X).
In technological synthesis of MV dye use oxidation dimetilaniline PhN(CH3)2 in which in
system formaldehyde is formed. Then consecutive condensation reactions of formaldehyde
with molecules initial dimetilaniline and formed monometilaniline proceed. For
monometilaniline formation in system enter phenol PhOH [18] which serves as the donor of
hydrogen for the nitric radical formed during oxidation, differing low reaction ability
PhN (CH3) 2 + r • → PhN (CH3) CH2 ,
PhN (CH3) CH2• + O2 → PhN (CH3) CH2OO•,
PhN (CH3) CH2OO• + PhN (CH3) 2 → PhN (CH3) CH2OOH + PhN (CH3) CH2•,
PhN(CH3)CH2OOH → PhN(CH3) CH2O• + HO•,
HO• + PhN (CH3) 2 → H2O + PhN (CH3) CH2•,
PhN (CH3) CH2O• → CH2O + PhN• (CH3),
PhN• (CH3) + HOPh → PhNH (CH3) + •OPh,
2•OPh → breakage.
As a result of condensation of formaldehyde with initial dimetilaniline and formed
monometilaniline there is a mix carbinol with different number methyl groups in aniline
fragments of molecules [3, 18]. At this mix inevitably there are by-products of oxidation with
quinoidной structure of molecules. The subsequent carbinole chloride hydrogen or oxalate
acid processing leads to formation of dyes with an impurity of corresponding salts of
compounds X, for example,