CHAPTER ONE

1.0 INTRODUCTION

Dyes are colors that bind chemically with fibers becoming a part of the materials on which it is
applied in place, a dye consist of colors producing structure the chromogen (electron acceptor)
and a part to regulate the solubility and dyeing properties the auxochrome (electron donor). The
chromogen is an aromatic body containing a color giving commonly called the chromophore, the

chemosphere group causes color by alternating absorption bands in the visible structure, the
auxochromes causes the dye to adhere to the material which it colors (usually textiles),
auxochromes group is responsible for dye fiber reaction (Noah, 1995).

Dyes are organic color substance which when applied to substrate, impact color to material by a
process which at least temporary destroys any crystalline structure of the colored substance
(Verssiom et al; 1991), Dyes are generally applied in an aqueous solution and may require a
mordant to improve the fastness of the dye on the fiber. Dyes are usually soluble in water where
as pigments are insoluble some dyes can be rendered insoluble with the addition of salt to a lake
pigment (Abrahant, 1997). A dye may also be a colorant that is induced by reactants. The
substrate is usually textile fiber but can also be paper, leather, hair, plastic material, foodstuff,
drugs and so forth (Ogunmakin, 1992). Dyes are colored substances because they absorb lights
of a wave within the visible spectrum, these characteristics is promoted by the existence in the
molecule of an organic group of atoms which are called chromophores. When these
chromophores are into organic compounds they absorb light only in the visible region, this
brings about absorption at lower frequencies and new compounds are colored for instance,
anthracene is colorless but anthraquinone is a pale yellow compound (Ogunmakin, 1992).

O
Figure 1.1: Anthraquinone

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 Figure 1.2: Anthracene

The wavelength of light absorbed is affected by constituent on the dye molecule, both through
their electron withdrawing ability or electron donating groups and also through the position they
occupy. Every dye or pigment exhibits a characteristic color arising from its chemical structure.
If a substance absorbs all visible light except one band which it reflects the substance will have
the color of that reflected band. Thus a substance can appear blue because it absorbs the yellow
portion of the spectrum only or because it absorbs the entire visible spectrum except blue, the
shades however will be different, apparently no dye gives a pure shade. Many substance which
appear to be colorless have absorption spectra but in these cases absorption takes place in the
infrared or ultra-violet are not in the region of visible spectrum therefore absorption spectrum
depends on chemical structure of dye (Vogel, 1998)

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The table below shows the pair of colors seen for a given colored at substances particular
wavelength within visible structure (Graham, 1972).

Table 1.1 Absorbed and reflected colors (Graham, 1972)

Wave Length (NM) Color Absorbed Color reflected

400 – 435 Violet Yellow – Green

435 – 480 Blue Yellow

480 – 490 Greenish-blue Orange

490 – 500 Bluish-green Red

500 – 560 Green Purple

0560 – 580 Yellow-green Violet

580 – 595 Yellow Blue

595 – 605 Orange Green-blue

605 – 750 Red Blue-green

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Bright colors are the result of narrow absorption bands with sharp peaks. Non-spectral colors
such as brown are absorption spread fairly evenly over a wide wavelength range and black is the
result of absorption throughout the visible region of the spectrum (Gregory et al.,2005)

1.1 Azo Dyes

Azo dyes can be classified under synthetic dyes. These are organic compounds bearing the
functional groups (- N=N-), among the synthetic dyes, azo dyes are one of the most
representative and large classes, they are usually strongly colored compounds which can be
intensely yellow, red, orange, blue or even green depending on the exact structure of the
molecule and as a result of their color, azo compounds are of tremendous importance as dyes in
industry today (Ebenso, et al., 2008).The structural features in organic compounds that usually
produce color are >C=C<, -N=O, - N=N, aromatic ring >C=O and –NO 2 but mostly the groups
that invariably confirm colors are the azo (-N=N-) and nitroso (-N=O) while other groups
actually do so under circumstances(Kirkan and Gup, 2008). Furthermore, azo dyes have been
studied widely because of their excellence thermal and optical properties in application such as
optical recording medium, toner ink jet printing (Gregory, 1990) and food chemistry. One of the
most investigated complexes reported in the recent years are related to copper coordinated
compound due to their ease of prepared structural flexibility, better resistance of the dye after
washing and applicability to biological system (Gregory et al., 2005)

1.2 Statement of Research Problem

Azo acid dyes are mostly used in leather industries but they are imported from overseas.
Government spend relatively a large amount of money on the importation of azo acid dyes which
is used on chrome tanned leather. Dyes used on chrome tanned leather has low penetrability, so
just small amount of dyes is absorbed by the chrome tanned leather, leading to a notable waste of
dyes in leather industries. Therefore, by synthesizing a low molecular weight azo acid dye
derived from 2-napthol-3, 6-disulphonic acid as the coupling component will produce dyes with
good exhaustion, better light fastness and good penetrability in the chrome tanned fiber.

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1.3 Justification

The use of azo acid dyes in the component of chrome tanned leather cannot be reduced due to its
contribution on dyeing textile fiber, dyes used on textile fiber are considered to be easy to use,
relatively cheap, and provide clear strong colors, about 50% of all dyestuff used in the leather
industry are azo dyes. Dyes which are used in food and textile industries consists of 60-70% of
azo acid dyes they are synthetic colors and most of them contain only one azo acid group which
will eventually provide a good substantively and better life fastness dyes for textile fiber.
Therefore, it is hoped that by synthesizing a low molecular weight azo acid dye derived from 2-
napthol -3,6-disulphonic acid as the coupling component will give better exhaustion and good
fastness properties on chrome tanned leather.

1.4 Aim and Objectives

1.4.1 Aim

The aim of this research is to synthesize and characterize azo acid dyes derived from 2-napthol-
3, 6-disulphonic acid as the coupling components and to study their application on chrome
tanned leather.

1.4.2 Objectives

The specific objectives of this research work are:

1. To synthesize azo acid dyes based on 2-napthol -3, 6-disulphonic acid as the coupling
component with 1-aminoanthraquione,3-aminobenzoic, sulphanilic acid and 4-chloroanaline
as the diazo components.
2. To characterize the synthesized dyes via melting point, UV-Visible spectroscopy, FT-IR
spectroscopy and solubility test.
3. To apply the synthesized dye on chrome tanned leather.
4. To investigate the fastness properties of the dyed chrome tanned leather to the external
agencies such as washing, and light fastness.

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CHAPTER TWO
2.0 LITERATURE REVEIW

2.1 Historical Review of Dyes

Dyeing of textiles has been practiced for thousands of years with the first written record of these
dyestuff dated at 2600 BC. In 1856 William Henry Perkin, while searching for a cure for
malaria, discovered the first synthetic dye, Mauve. The mauve dye was a brilliant fuchsia color,
but faded easily since that time, a great number of synthetic dyes have been manufactured and
their resistance to running and fading has been almost eliminated. Almost all garments purchased
today are dyed with synthetic dyes (Wiley, 2003).

Dyes used for fabric such as cotton, wool, and silk are complex organic molecules that contain
what is known as a chromophore group that is, they contain some type of conjugated alternating
double and single bonds in part of the molecule. These molecules can absorb certain wavelengths
of visible light and reflect the remaining light and thus give a fabric its color. Not only do the
dyes have polar or ionic groups, but fabrics such as cotton and wool also contain polar groups
such as –OH (hydroxyl) and –NH (amide) which help the dye attach to the fabric.
Sometimes chemical bonds are formed between the dye and the fabric molecules which hold the
two together (Peters, 1991).

Another process involves the use of a-mordant, which serves as sort of an intermediary that
bonds the dye and the fabric. If the dye molecules attach firmly to the fabric the color will be
"fast that is, it does not run when wet or washed after the initial rinsing of excess dye (Peter,
1991).

The use of colorants by mankind for painting and dyeing of their surroundings, their skin and
clothes dates back to the dawn of civilization until the middle of the 19 th century, all colorants
applied were from natural origin. For example, inorganic pigments such as soot, manganese
oxide, hematite and ochre have been utilized within living memory; organic natural colorant
have also a timeless history of application, especially as textile dye. These dyes are aromatic
compounds originating from plants but also from insects, fungi and lichens.

Synthetic dyes manufacturing started in 1856, when the English chemist W.H. Perkins in an
attempt to synthesize quinine, obtained instead a bluish substance with excellent dyeing
properties that latter known as aniline purple, Tyrian purple or mauveine. Perkin planted his
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invention and setup a production line. This concept of research and development was strongly
stimulated by Kekule’s discovery of the molecular structure of benzene in 1865. In the beginning
of the 20th century, synthetic dyestuffs had almost completely supplanted natural dyes (Vogel,
1998).

2.2 Development of Synthetic Dyes

The year 1856 witnessed an event which was to bring about a fundamental change in the whole
field of the chemistry industry. Although the distinction of being the first synthetic organic dye
belong to picric acid which is the simplest dye known. Picric acid was a bright greenish yellow
dye which belongs the acid class. But synthesis and manufacture of a purple dye by W. H.
Perkins in 1856 is rightly regarded as the beginning of the synthetic dye era In thus year, William
H. Perkins the son of the builder was sent to the city of London school where he showed aptitude
for chemistry which was under the guidance of Hoffman, the celebrated German chemist
(Garfield, 2001).

Perkins at the age of eighteen was attempting to synthesize Anti-malaria drug quinine by
oxidizing aniline with acidified potassium dichromate. He obtained a black precipitate and
observed that if these were extracted with naphthla and then with ethyl alcohol a brilliant purple
solution was obtained. Further work on this experiment led him to conclude that they had
produced useful dyestuff. Perkins work was of a profound significant because this was the first
time a chemist had created a dye from simple organic molecules. More importantly this product
was made from what was virtually a waste product in the destructive distillation of coal in the
gas works, and the discovery opened up an entirely new scene in the chemistry industry.

Perkins sent a sample of his dye to pillars of Perth, who tired it out in their dyeing works and
gave it favorable report. Perkins therefore at eighteen, assisted by his father and brother, built a
factory at Greenford near London. He then devised and erected plant for benzene; he further
pioneered the large scale reduction of nitrobezene to aniline, and worked out a means of
oxidizing the aniline and extracting the dyestuff (Gardon and Gregory, 1993). Aniline was a
basic dye and Perkins had to develop methods of applying his products and demonstrate them to
potential customers, thus starting the marketing concept of technical service which became a
standard feature of all the dyestuff manufacturers in our modern age (Noah, 1995).

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The birth of synthetic organic dyestuff industry in 1856 was followed by a total dependence on
colorant as a source of aromatic for virtually the first 100 years. Since 1905s petroleum
compounds, prior to Kekule’s structural explanation of benzene, the early dyes discovered were
purely based on empirical experiments and were all derivatives of benzene. Another important
discovery in the history of synthetic dyes which have profound influence on the dyestuff and
related industries was the air oxidation of naphthalene to phthalicpentoxide as catalyst by Gibbs
in 1927 (Nunn, 1990).

Human's love of color reaches back almost to prehistoric times, yet it is not actually until the
modern era that the full range of the rainbow has been accessible to the majority of people in
their clothes and other textiles. Ancient or medieval times have often been described as being
quite splendid with their “Tyrian Purple” and medwieval scarlet, but closer examination shows
that some of these colors were quite dull by today standards. The history of dyeing can be
divided into two great periods, the “pre-aniline,” extending to 1856 and the “post-aniline” period.
The former was characterized by a rather limited range of colors that were based on dye-
producing animals and plants. The main vegetable dyes available were extracted from madder
root (Asia and Europe), producing a brilliant red and leaves of the indigo plant (India), yielding
the blue dye still used to day in jeans. Among the most important animal based dyes is the
famous and expensive “Tyrian Purple” which was obtained from the small shellfish nurez. We
have the ancients’ word that this dye was unbelievably beautiful, but evidence taken from
ancient samples prove that it ranges through a rather uninspiring series of reds and purples. After
seeing it, we wish that Homer had written about some of today's inexpensive coal-tar purples and
reds. A far more beautiful natural color was introduced to Europe from Mexico in 1518, the
brilliant scarlet dye cochineal, which had been produced from tiny lice which infest certain types
of cactus.

Aniline (CH6-NH2) became available from coal tar in the 19th century and in 1856, William
Henry Perkin at the age of 17 used it in the synthesis of Mauveine. The era of synthetic dye was
born. Soon thereafter, the main component of the dye in the madder root, Alizarin, was isolated
by Carl Graebe and Carl Liebermann, prepared in the lab and the process commercialized.
Starting in 1865, recognizing the potential of synthetic dyes, Adolph von Baeyer researched the
synthesis of indigo and determined its structure and first synthesis in 1870. The structure of

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Indigo was established in 1897 and the large scale industrial synthesis of indigo started and
rapidly reached 10,000 tons a year, completely replacing the agricultural production. Azo acid
dyes they are straightforward to make and of industrial importance. Azo acid dyes are prepared
in a two-step reaction (Gung and Taylor, 2004).

2.3 Synthesis of Azo Dyes

Azo dyes synthesis involves two main steps; diazotization and coupling.

2.3.1 Diazotization

The formation of diazonium salt was discovered by Peter Cinese in 1869. Diazotization is (in an
ice bath) using mineral acid (NaNO2 and HCl). The diazonium salt formed is very reactive
reaction explosively with most reagent cannot be kept for long (Wiley, 2003).

Step 1: Generation of Nitronium ion

H2SO4→2HaNO2→NaSO4+H2O+NO+NO2

HCl +NaNO2→NaCl+H2O+NO

Scheme 2.1: The generation of Nitronium ion (the active electrophile specie.)

Step 2: Electrophilic attack on nitrogen of NH 2 followed by elimination of water molecules from

the intermediate resulting in the formation of the diazo compound.

2.3.2 Coupling Reaction

A coupling reaction in organic chemistry is a general term for variety of reaction where two
hydrogen fragment are coupled with the acid of metal catalyst. In one important reaction type a
main group of organo metallic compound of RM (R=organic fragment, M=main group center)
reacts with an organic halide of the type RX formation of a new carbon-carbon bond in the
repetitive product R-R (Kvavades et al., 2009)

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2.4 Classification of Dyes

There are different ways which dyes are classified some of them include;
2.4.1 Classification of dyes based on their chemical composition
2.4.1.2 Azo dyes

Azo dyes are organic compound bearing the functional group R-N=R1, in which R and R1 are
usually aryl. That are a commercially important family of azo compound, i.e. compounds
containing the linkage C-N=N-C. Azo dyes perllasivey used to treat textile, leather, articles and
foods chemically related azo dyes and azo pigment which are insoluble in water and other
solvents. Azo components or dyes are characterized by the presence of azo moiety (N=N-) in
their identical, mono or polycyclic aromatic or hetero aromatic system (Barder, 2010)
Synthesis of most azo compounds involve diazotization of a primary aromatic amine, followed
by coupling with one or more nucleophiles, thus benzoic phenolic, saucyclic and naphtolic
compound undergo diazotization reaction. Few times azo compound is often described as a
chromogene in the literature, the amino and hydroxyl group are commonly used coupling
compound (Barder, 2010). Furthermore, azo compounds also have many applications in photo
industry such as photodynamic therapy, photographic system and are dominant organic
photoconductive.

Azo dyes account for 60% of the total dyes known to the manufacture. They are characterized by
the presence of one or more azo chromophoric group and dye molecule which form bridge
between organic residues of which is usually an aromatic nucleus.

Figure 2.1: Azo colorant

Azo dyes are prepared by diazotizing primary aromatic amine followed by coupling to suitable
coupling component and active methylene compounds. Another method id the oxidative

2.4.1.2 Nitro Dyes

A group of dyes whose color result from the presence of nitro groups, (NO 2) and hydroxyl and
amino groups (OH and NHR). They may also contain CL, SO 2H and COOH substituent. Nitro

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dyes containing are more stable for example, disperse fast yellow is of practical importance for
dyeing a number of fibers.

Figure 2.2: Disperse Yellow 3

It is produced by reaction of 2,4dinotrochrolo benzene with p-aminophenol, Napthol yellow II is

used in a number of countries as a food dye. It is produced by nitration of product.

2.4.3 Nitroso Dyes

A group of dyes of aromatic compounds containing a nitroso group, (NO) in the ortho-position to
an OH group, the most important nitroso dyes in industry is derivatives of 1-nitroso-2-napthol.
Nitroso dyes are produced by the actin of sodium nitrate on aromatic hydroxyl compounds in
acid medium types which is green mordent dye, which is the product of the addition of sodium
bisulfite (NaHSO3), to 1-nitoso-2-napthol, the complex of this dye with divalent iron is a green
pigment in the production of wallpaper and pencil. The green pigment obtained directly on
cotton fibers from B green mordent dye, green mordent gives insufficient stable colors.

N=O N-H
OH O

Figure 2.3: Nitroso Dye

2.4.2. Classification Based on Method of Application
2.4.2.1 Acid dyes

Acid dyes are water soluble anionic dyes that are applied on fibers such as a nylon and modified
acrylic fibers using neutral to acid dye bath attachment to the fiber to attribute to least partly, to
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salt formation between anionic groups in the dye and cathonic groups with fiber. Acid dyes are
not substantive to cellulose fiber. Acid dyes are acidified basic dyes intended for use on protein
fiber but can be used on nylon. They have a fair light fastness but poor wash fastness.

Figure 2.4: Acid yellow 36

2.4.2.2Basic dyes

Basic dyes are water soluble cationic dyes that are mainly applied to acrlyic fibers. The colors
are very bright but not very fast to light washing and fastness is impured after treatment or
steaming. For example Rench silk are basic dyes and should be steamed to fix. They also find
some use of wool and silk. Usually, acetic acid is added to the dye bath to help the uptake of the
dye unto the fiber. Basic dy+es are also used in the coloration of paper ( Gergory, et al 1990).

Figure 2.5: Basic dyes

2.4.2.3 Azoic dye

Azoic dyes contains at least one azo group (-N=N) attached to one or often two aromatic rings.
They produce non textile fiber usually cotton ray and polyester by diazotization of a primary
aromatic amine followed by coupling of the resulting diazonium salt with an electron rich
nucleophile (azo coupling). The product of bluish red azoic dye from the following two
component is an example of azoic dye.

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Figure 2.6: Bluish red azoic dye

2.4.2.4 Vat dyes

Vat dyes are essentially insoluble in water and capable of dyeing fiber directly. However,
reduction in alkaline liquor produces the water soluble alkali metal salt of the dye. Which is
leuco form, has an affinity of textile fiber. Subsequent oxidation reforms the original vat dyes.
They are the fastest for cellulose fibers and made soluble with alkali, put in a vat with a reducing
agent, using sodium hydrosulphate, which removes all oxygen from the liquid and fabric is dyed
then oxidized in the air to archive the true color (Graham, 1972).

Figure 2.7 Vat Blue

2.4.2.5 Direct dye

Direct dyes are used on cotton, leather, wool, silk and indicators as a biological stain. Direct dye
is a dye that adheres to its substrate, a textile by non-ionic force. The amount of this attraction is
known as substansitivity, the higher the substansitivity, and the greater the attraction of the dye
to the fibers. The development of substantive dyes help make mordant dye obsolete, they are set
in slightly basic or neutral environment at high temperature close to boiling point. Dyes are set
by formation of aggregate of dyes with interstice of the fibers (Graham, 1972).

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Figure 2.8: Direct orange dye

2.4.2.6 Reactive dyes

Reactive dyes are the most recent dyes. They are popular in the present world fabric artist and
used at first only by surface designer. The dyes reacts with the fiber molecule to form the color
as a result, extremely fast to both light and washing. Reactive dyes are also suited to screen
painting, fabric painting and piece dyeing.

Figure 2.9: Reactive blue 5

2.4.2.7 Mordant dyes

Mordant dyes are class of dyes used on fabric by forming of a co-ordinate complex which
attached to fabric. It may also be used by dyeing stains in cells and tissues preparation to make it
prominent (Gerald, 1988).

Figure 2.10: Mordant red 11

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2.4.2.8 Disperse dyes

Disperse dye is a class of dye slightly water insoluble introduced for dyeing acetate and usually
applied from fine aqueous suspension. Disperse dye are widely used for dyeing most of the
manufactured fibers. The term disperse dye have been applied to the origin coloring substance
which are free from ionizing group and are low water solubility suitable for dyeing hydropholic
fibers. Disperse dye have substantively for one or more hydropholic fibers examples are nylon,
polyester and synthetic fibers. The negative charge on the surface of hydropholic fibers like
polyester cannot be reduced by any means, so non-ionic dyes like disperse dye are used which
are influenced by the surface charge (Graham, 1972).

Figure 2.11: Maritus Yellow

2.5.3 Classification of Dyes Based on their Origin

2.5.3.1 Natural dye

The dyes used earlier were natural dyestuff (saffron, henna and logwood) derived from plants
and animals. Most natural dyes are of mordant types that requires a fixating agent. With the
advent of synthetic dyes which are far more varied in shades and properties and generally more
brilliant, the production of natural colors has been decreased to a very small portion of the
market. Their greatest use is in the dyeing of leather. Many thousands of dyes which have been
synthesized in the laboratories, about 3500 have had commercial use. These have been induced
in several complications. The societies of dyes and colorist England and American association of
chemist and colorist gave each dye an individual 5-digit number as identification regardless of
the dyes which have common names with general assuage, commercial dyes were sold under
large number of names, many of which relate to some material (Ramassami, 2001).

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2.5.3.2 Synthetic dyes

Synthetic dyes which are obtained by mixing up chemical to give colouring materal which are

capable of impacting colors to materials. They are man-made dyes which are from petroleum,

sometimes in combination with minerals derived component. It has an origin in London (Nunn,

1990).The first human made organic dye, mauveine was discovered by Williams Henry Perkins

in 1856, the result of failed attempt at the total synthesis of quinine. Other aniline dyes followed

such as fushine, safranine and induline. Many thousands of synthetic dyes have since been

prepared (Venkataraman, 1978).

2.6 Properties of Dyes

Dyes are used for the coloration of various substrate including paper, hair, food plastic and
textile. For dye to be suitable for any application, it must meet some certain requirement
depending on the type of substrate (Wiley-VCH, 2003).

1. Water solubility during dyeing or either permanently.

2. Ability to be absorbed and retained by the fiber or to be chemically attached to it.
3. It must have an intense color i.e. it must possess functional strength or color power.
4. Dyes should not be toxic (non-toxic) and used in its purest form.
5. Its colors substance should not change or vary with light source.
6. It should be safe and economical for manufacturing substrate like food, hair, drugs, and
cosmetics.

2.7 Textile Fiber

Textile fiber is a material made from natural or synthetic source. This this material can be
converted into making of textile yarn, fabric woven and knitted. It may be in a form of a pliable
hair like strand or as the smallest visible unit of textile production (Ramassani, 2001).

2.8 Classification of Textile Fiber

Since from the past, there are many types of textile industry such as cloth, rope and yarn. They
are classified into two type base on their source (Billie, 2001).

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2.8.1 Natural Fiber

Natural fiber is a material made from an originated natural source. There are three main source
that natural fiber can be obtained which are; cellulosic fiber from plant; protein in fibers from
animals; mineral fiber can only produce a staple yarn in terms of fiber and would be hairiness
surface because of their origin. Each kind of them has their own characteristics and end-use
demand (Billie, 2001). The various source of natural fibers are:

1 Protein fiber are obtained from hair, wool and filament.

2 Cellulosic fiber is obtained from seed and leaf.
3 Unlike the other two source, mineral fiber is obtained from varieties of rock source which
is also called asbesto fiber. It is a fibrous form of silicate made of magnesium and calcium.
2.8.2 Synthetic Fiber

Synthetic fiber refers to materials that is not originated from natural source but are developed by
human by using chemical and mechanical process. There are basically two types of man-made
fiber that has been widely used by textile industry which are;

1. Synthetic Base: Which refers to a fiber that has been made totally by man-made process
using chemical substance source. Example are polyamides, polyester and acrylic.
2. Natural Polymer: It is a manufactured fiber that is derived from natural cellulosic source
such as wood pulp. The composition of these cellulosic will be treated or alter with
polymerized technique to regenerate into a new form of fiber (Chandru; et al, 2018)

2.9 Fiber Structure in Relations to Dyeing

Textile fibers, whether natural or synthetic consist of polymer molecules as their fundamental
units. The functional groups within the polymers retain their chemical properties and determine
the types of dyestuff for which the fiber have affinity for. In fact, fibers having many polar
functional groups (hydrophilic fiber) will have greater affinity for the ionic dyestuff.
Crystallinity tends to impart hydrophobicity on fibers even when they have polar functional
groups. This is due to the screening off of polar functional groups with possible intermolecular
hydrogen bonds. Also, the close arrangement of polyester molecule leaves little or no space for
molecules to penetrate into it from the dyeing bath (Ingamells, 1973).

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2.10 Force of Attraction between Dyes and Fiber

2.10.1 Ionic Bond

This is the mutual attraction between positive Centre in fiber and negative center in a dye
molecules and between negative fiber sites and positive center in a dye molecule. This is the case
when an atom transfer its electron to another atom, the one that the electron becoming positively
charged while the atom that received the electron will become negatively charged.

These type of forces play a large part in dyeing of protein fiber with acid and direct nylon with
acid dyes and polyacrylics with basic dyes (Ingamells, 1973).

2.10.2 Hydrogen bonding

This result from the acceptance by a covalently bound hydrogen atom of a lone pair of electron
donor atom. Hydrogen bonding can act in different ways as follows;

1. Intermolecularly extending over many molecules.

2. Intermolecularly joining two molecules together.
3. Intermolecularly where the electron donating is by double bond linkage.
4. Intermolecularly forming a chelate ring.
5. Intermolecularly as ion in hydrogen fluoride.

2.10.3 Covalent bonding

These are chemical bonds between dyes and substrate molecules. They are chemical reaction
between reaction dye molecules and the substrate molecules example hydroxyl group of a cotton
fiber, in fact covalent bonding has to do with primary valence bonding where each of the
participating atoms has to donate one electron to the common linkage. This is the strongest of all
dye fiber bonds. They have the highest energy of about 84kkj/mol. Covalent bonding is the
bonding is he bond responsible in reactive dye bond on leather, wool, polyester and nylon.

2.10.4 Van Der Waals Force

These are forces existing between atoms and molecules of all molecules of all substance and are
small compound with the other inter atomic forces present in the dyeing process. They are the
result of second order wave mechanical interaction of the X-orbit of dye and fiber molecules.

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These forces are especially effective when the dye molecules are linear, i.e. long and flat which
can approach closer enough to the fiber molecules

2.11 Hides and Skin

Hides and skins are end product of animal production. As an end product – although more
correctly they are a by-product – they are an important and valuable resource. In the developing
world they are almost never exploited to anything like their full potential. Hides and skins are
often thought of as intrinsically unclean and end up being discarded or wasted because of
ignorance or misinformation. Others are processed improperly which greatly reduces their
potential value. Hides and skins are a renewable resource of national and international
significance. They provide scope for exploitation on a sustainable long-term basis. More
particularly, production and marketing of hides and skins provide opportunities to support and
sustain livelihoods especially in rural areas. As a resource, hides and skins are the raw materials
for various types of businesses – such as collecting, processing and distributing – which provide
many service jobs in countries where livestock are produced (Heidemann, 1992).

2.12 Functions of Hides and Skin

A hide or skin is an animal skin tanned or dried for human use. The term hide applies to all
leather, with and without the animal hair on the surface. The term hide sometimes includes furs,
which are harvested from various species with soft hair. There is a distinction between skin and
hide in the English-speaking countries. It`s not always clear when which of the two terms should
be used. Experts designate all small skins as skin. But also all hides of hoofed animals. Pig
leather is also referred to as skin and the hides of young animals. Only the skins of animals with
a shoulder height of more than one meter are called hides. It is unclear with the kangaroo.
Through the upright walk the shoulders are high, but by the physique the hides are not always
very large depending, on the type (Jae-Hong-Cho et al, 2008).

1. Skin is the outer covering of humans and animals and has various functions: it affects the
body temperature; it is a sense organ for heat, cold, touch and pain; and it protects against
injuries, bacteria and the sun.
2. The skin of mammals consists of 98% protein, fat, water and minerals. It is divided into
three layers: epidermis (about 1% of the thickness), dermis (about 85%) and hypodermis
(about 15%). The dermis is the layer used in leather production.

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3. All mammals and races have different types of skin. The skin varies according to age,
gender, nutrition and climate.
4. A leather skin also contains different leather fiber structures. All this must be considered by
the tanner when selecting the raw material, and in the production process, in order to provide
leather of good quality.
5. The tanned leather skins, which have not yet been cut to size, are called hides. The hair of
the animal can be removed or still be present on hides. Hides with very soft hair are called
furs. Presently, hides are mainly used for footwear, upholstery, leather goods; skins are used
for clothing, particularly as coats, gloves, leather goods and footwear. It is also used for
bookbinding.
6. Many traditional drum, especially hand drums like the pandeiro, continue to be made using
natural skins. The alligator drum was formerly important in Chinese music. Banjo was
originally made from skins but is now often synthetic. Hides is used as a slang term to refer
to a drum set (Cunningham,1996).

2.13 Tanning

Tanning is the process of treating skins and hides of animals to produce leather. A tannery is the
place where the skins are processed. Tanning hide into leather involves a process which
permanently alters the protein structure of skin, making it more durable and less susceptible to
decomposition, and also possibly coloring it. Before tanning, the skins are unhaired, degreased,
desalted and soaked in water over a period of 6 hours to 2 days. Historically this process was
considered a noxious or "odoriferous trade" and relegated to the outskirts of town.

Traditionally, tanning used tannin, an acidic chemical compound from which the tanning process
draws its name (tannin is in turn named after an old German word for oak or fir trees, from
which the compound was derived). The use of a chromium (III) solution was adopted by tanners
in the Industrial Revolution (Cunningham, 1996).

The English word for tanning is from Medieval Latin tannāre, derivative of tannum (oak bark),
from French tan (tanbark), from old-Cornish tann (red oak). These terms are related to the
hypothetical Proto-Indo-European meaning 'fir tree'. (The same word is source for Old High
German tanna meaning 'fir', related to modern Tannenbaum). Despite the linguistic confusion
between quite different conifers and oaks, the word tan referring to dyes and types of hide
preservation is from the Gaulic use referencing the bark of oaks (the original source of tannin),
20
and not fir trees Ancient civilizations used leather for water skins, bags, harnesses and tack,
boats, armor, quivers , scabbards, boots, and sandals . Tanning was being carried out by the
inhabitants of Mehrgarh in Pakistan between 7000 and 3300 BC. Around 2500 BC, the
Sumerians began using leather, affixed by copper studs, onchariot wheels.

Formerly, tanning was considered a noxious or "odoriferous trade" and relegated to the outskirts
of town, amongst the poor. Indeed, tanning by ancient methods is so foul smelling, tanneries are
still isolated from those towns today where the old methods are used. Skins typically arrived at
the tannery dried stiff and dirty with soil and gore. First, the ancient tanners would soak the skins
in water to clean and soften them. Then they would pound and scour the skin to remove any
remaining flesh and fat. Next, the tanner needed to remove the hair from the skin. This was done
by either soaking the skin in Urine, painting it with an alkaline lime mixture, or simply allowing
the skin to putrefy for several months then dipping it in a salt solution. After the hairs were
loosened, the tanners scraped them off with a knife. Once the hair was removed, the tanners
would "bate" (soften) the material by pounding dung into the skin, or soaking the skin in a
solution of animal brains. Bating was a fermentative process which relied on enzymes produced
by bacteria found in the dung. Among the kinds of dung commonly used were those of dogs or
pigeons (Cunningham, 1996).

Historically, the actual tanning process used vegetable tanning. In some variations of the process,
cedar oil, alum, or tannin were applied to the skin as a tanning agent. As the skin was stretched,
it would lose moisture and absorb the agent (Nuremberg, 1609). Following the adoption in
medicine of soaking gut sutures in a chromium (III) solution after 1840, it was discovered that
this method could also be used with leather and thus was adopted by tanners (Cunningham,
1996).

2.14 Tanning Procedure

The tanning process begins with obtaining an animal skin. When an animal skin is to be tanned,
the animal is killed and skinned before the body heat leaves the tissues. This can be done by the
tanner, or by obtaining a skin at a slaughter house, farm, or local fur trader. Preparing hides
begins by curing them with salt. Curing is employed to prevent putrefaction of the protein
substance (collagen) from bacterial growth during the time lag from procuring the hide to when
it is processed. Curing removes water from the hides and skins using a difference in osmotic
pressure. The moisture content of hides and skins is greatly reduced, and osmotic pressure
21
increased, to the point that bacteria are unable to grow. In wet-salting, the hides are heavily
salted, then pressed into packs for about 30 days. In brine -curing, the hides are agitated in a salt
water bath for about 16 hours. Curing can also be accomplished by preserving the hides and
skins at very low temperatures (Li-Y et al, 2006).

2.14.1 Beam House Operations

The steps in the production of leather between curing and tanning are collectively referred to as
sbeam house operations. They include, in order, soaking, liming, removal of extraneous tissues
(unhairing, scudding and fleshing), deliming, bating or puering, drenching, and pickling.

1. Soaking
In soaking, the hides are soaked in clean water to remove the salt left over from curing
and increase the moisture so that the hide or skin can be further treated. To prevent
damage of the skin by bacterial growth during the soaking period, biocides, typically
dithiocarbamates, may be used. Fungicides such as 2-thiocyanomethylthiobenzothiazole
may also be added later in the process, to protect wet leathers from mold growth. After
1980, the use of pentachlorophenol and mercury -based biocides and their derivatives
was forbidden.
2. Liming (leather processing)
After soaking, the hides and skins are taken for liming: treatment with milk of lime (a
basic agent) that may involve the addition of "sharpening agents" (disulfide reducing
agents) such as sodium sulfide, cyanides, amines, etc. The objectives of this operation are
mainly to:
 Remove the hair and other keratinous matter
 Remove some of the interfibrillary soluble proteins such as mucins
 Swell up and split up the fibres to the desired extent
 Remove the natural grease and fats to some extent
 Bring the collagen in the hide to a proper condition for satisfactory tannage
 The weakening of hair is dependent on the breakdown of the disulfide link of the
amino acid cystine, which is the characteristic of the keratin class of proteins that
gives strength to hair and wools (keratin typically makes up 90% of the dry weight
of hair). The hydrogen atoms supplied by the sharpening agent weaken the cysteine
molecular link whereby the covalent disulfide bond links are ultimately ruptured,
22
 weakening the keratin. To some extent, sharpening also contributes to unhairing, as
it tends to break down the hair proteins.
 The isoelectric point of the collagen in the hide (this is a tissue-strengthening
protein unrelated to keratin) is also shifted to around pH 4.7 due to liming.
3. Unhairing and scudding
Peeling hemlock bark for the tannery in Prattsville, New York, during the 1840s, when it
was the largest in the world. Unhairing agents used at this time include; Sodium sulfide,
sodium hydroxide, sodium hydrosulfite, calcium hydrosulfide, dimethyl amine, and
sodium sulfhydrate. The majority of hair is then removed mechanically, initially with a
machine and then by hand using a dull knife, a process known as scudding.
4. Deliming and bating
The pH of the collagen is brought down to a lower level so the enzymes may act on it, in
a process known as deliming. Depending on the end use of the leather, hides may be
treated with enzymes to soften them, a process called bating. In modern tanning, these
enzymes are purified agents, and the process no longer requires bacterial fermentation (as
from dung-water soaking) to produce them.
5. Pickling
Once bating is complete, the hides and skins are treated first with common salt (sodium
chloride) and then with sulfuric acid, in case a mineral tanning is to be done. This is done
to bring down the pH of collagen to a very low level so as to facilitate the penetration of
mineral tanning agent into the substance. This process is known as pickling. The salt
penetrates the hide twice as fast as the acid and checks the ill effect of sudden drop of pH
(Li-Y et al, 2006).

2.15 Mineral Tanning (Chrome tanning)

Chromium (III) sulfate has long been regarded as the most efficient and effective tanning agent.
Chromiumn (III) compounds of the sort used in tanning are significantly less toxic than
hexavalent chromium, although the latter arises in inadequate waste treatment. Chromium (III)
sulfate dissolves to give the hexaaquachromium (III) cation, [Cr (H 2O)6]3+, which at higher pH
undergoes processes called olation to give polychromium (III) compounds that are active in
tanning, being the cross-linking of the collagen subunits. The chemistry of [Cr (H 2O) 6]3+ is more

23
complex in the tanning bath rather than in water due to the presence of a variety of ligands. Some
ligands include the sulfate anion, the collagen's carboxyl groups, amine groups from the side
chains of the amino acids, and masking agents. Masking agents are carboxylic acids such as
acetic acid, used to suppress formation of polychromium (III) chains. Masking agents allow the
tanner to further increase the pH to increase collagen's reactivity without inhibiting the
penetration of the chromium (III) complexes (Cunningham, 1996). Collagen is characterized by a
high content of glycine, proline, and hydroxyproline, usually in the repeat -gly-pro-hypro-
gly-.These residues give rise to collagen's helical structure. Collagen's high content of
hydroxyproline allows for significant cross-linking by hydrogen bonding within the helical
structure. Ionized carboxyl groups (RCO2−) are formed by hydrolysis of the collagen by the
action of hydroxide. This conversion occurs during the liming process, before introduction of the
tanning agent (chromium salts). The ionized carboxyl groups coordinate as ligands to the
chromium (III) centers of the oxo-hydroxide clusters (Etherington, 2011)

Tanning increases, the spacing between protein chains in collagen from 10 to 17 Å. The
difference is consistent with cross-linking by polychromium species, of the sort arising from
olation and oxolation. Prior to the introduction of the basic chromium species in tanning, several
steps are required to produce a tannable hide (Christie,2001).The pH must be very acidic when
the chromium is introduced to ensure that the chromium complexes are small enough to fit in
between the fibers and residues of the collagen. Once the desired level of penetration of chrome
into the substance is achieved, the pH of the material is raised again to facilitate the process. This
step is known as basification. In the raw state, chrome-tanned skins are greyish-blue, so are
referred to as wet blue. Chrome tanning is faster than vegetable tanning (less than a day for this
part of the process) and produces a stretchable leather which is excellent for use in handbags and
garments. Subsequent to application of the chromium agent, the bath is treated with sodium
bicarbonate to increase the pH to 4.0–4.3, which induces cross-linking between the chromium
and the collagen. The pH increase is normally accompanied by a gradual temperature increase up
to 40°C. Chromium's ability to form such stable bridged bonds explains why it is considered one
of the most efficient tanning compounds. Chromium-tanned leather can contain between 4 and
5% of chromium. This efficiency is characterized by its increased hydrothermal stability of the
skin, and its resistance to shrinkage in heated water (Li-Y et al, 2006).

24
2.16 Vegetable Tanning

Vegetable tanning uses tannins (a class of polyphenol astringent chemicals), which occur
naturally in the bark and leaves of many plants. Tannins bind to the collagen proteins in the hide
and coat them, causing them to become less water-soluble and more resistant to bacterial attack.
The process also causes the hide to become more flexible. The primary barks processed in bark
mills and used in modern times are chestnut, oak, redoul, tanoak, Hemlock, quebracho,
mangrove, wattle and myrobalans from Terminalia spp., such as Terminalia chebula. Hides are
stretched on frames and immersed for several weeks in vats of increasing concentrations of
tannin. Vegetable-tanned hide is not very flexible and is used for luggage, furniture, footwear,
belts, and other clothing accessories. Wet white is a term used for leathers produced using
alternative tanning methods that produce an off-white colored leather. Like wet blue, wet white
is also a semi-finished stage. Wet white can be produced using aldehydes, aluminum, zirconium,
titanium, or iron salts, or a combination thereof. Concerns with the toxicity and environmental
impact of any chromium (VI) that may form during the tanning process have led to increased
research into more efficient wet white methods (Li-Y et al, 2006).

2.17 Dyestuff available for Leather Industries

Leather dyeing is a transition process between tanning and finishing. Some kinds of leathers
require penetration of dyestuff into collagen network while certain kinds of leather need not be
dyed through, it is enough to dye them on the surface. This decreases consumption of dyestuff,
which is an expensive material. It is important to know how penetration of dyestuff proceeds.
The processes done affect the chemical properties of leather. The result of dyeing is not only
dependent on tanning agent and method used, reactions of fat, surfactant and water should also
be taken into consideration. Collagen contains functional groups, part of them bound in the
tanning process, and tanning agents which may possibly react with dyestuffs: in a vegetable
leather these may be sugars and phenols and in mineral tanned leather these may be complexes
of chromium or other metals as well as fats, surfactants or proteins. Isoelectric point of collagen
lies in the range of pH 7-7.8 that of chrome tanned collagen pH 6.5, of vegetable tanned one pH
3.5, aldehyde, Quinone and oil tanned about pH 4.5. It is essential to choose dyestuffs so as to
ensure opposite charges on both substances. In conventional dyeing process the dye is dissolved
in water, and the leather is treated with this solution. During dyeing the color fixes chemically to
the leather, leaving the water colorless. Under ideal conditions all the dye offered is fixed to the

25
leather, and subsequent washing of the dyed leather with water should not wash off any color.
The dyeing is then said to be 100% wash fastness.

Manufacture of dyestuffs is an old branch of industry which is based or synthetic organic

chemistry. Various intermediates need to be prepared using typical reactions such as nitration,
sulphonatin, caustic fusion, halogenation, reduction and oxidation. Also some specialized
techniques are necessary. Because aniline was prominent as an intermediate in the early days of
the industry, synthetic dyestuffs are still sometimes referred to as aniline dyes but this practice
has been incorrect for many years. A very important publication in the field of dyestuffs is the
Color Index (Lan et al., 2000).

Modern dyestuffs contain the benzene ring in their molecular structure. The significance of this
is that the orbital arrangement of the electrons is sensitive to light. Starting with relatively simple
organic molecules, colored compounds are made by joining these together by such processes as
diazotization and coupling, etc. Very large complex molecules are made where the electronic
orbits are sensitive to light of specific wavelengths (certain colors). Functional groups on the
aromatic ring are of chromophore character. These groups are shifting pi electrons in the rings
thus forming some negatively or positively charged centers in an aromatic molecule. A simple
orange dyestuff made from aniline, diazotized and coupled with napthol would be insoluble in
water. It is sulphonated to introduce strongly ionizing groups with high water stability. The
means employed to make leather dyestuffs water soluble is of particular importance, carboxylic,
sulfonic amino or hydroxylic groups are introduced to increase water solubility (Lan et al, 2000).

(A) Anionic Dyes:

In the case of the orange dye the dye is referred as an anionic dye, it has a negative charge. It will
tend to precipitate or “fix” on to cationic colloids which have a positive charge. The skin leathers
come into this category under acid conditions (i.e. if pH is below their isoelectric point).
Consequently anionic dyes “fix” on the leather under acid conditions by ionic forces. These are
powerful forces and the reaction or fixation can vary rapid particularly at higher temperatures.
Such rapid fixation can lead to unleveled dyeing of leather. This is even more important if one
wishes the dye to penetrate through the thickness of the leather. If the fixation is rapid then the
bulk of the dye will fix on the outer surfaces and the solution which eventually diffuses into the
skin center will be denuded of color. These factors may be controlled by control of pH of the
dyeing system. To obtain high degree of penetration it is usual to start the process under non-acid
26
conditions, drumming or paddling until penetration is obtained, at the end, acid is added to cause
fixation. Dyes of anionic type are often termed “acid” dyes which refer to the desirability of
using acid to fix them. There is a very wide range of colors available. However, the individuals
dyes may have vastly different structure and have different degrees of resistance (fastness), to
light (fading in sunlight), water washing, soap washing, dry rubbing (marking off), or dry
cleaning solvents. These properties are usually evaluated by the dyestuff supplier and graded in
pattern books as specifications often by a system in which 5 means excellent properties and 0
means very bad. Generally acid dyes have good average properties, i.e. are reasonably fast and
water resistant. But there are outstanding exceptions. These “fastness” properties are not entirely
functions of the ionic charge on the dyestuff. The dyestuff molecules are large complexes and
can exhibit high secondary valence forces due to dipole moment or H-bonding which play a
significant role once the dye molecule is drawn into close proximity of the fiber by ionic forces.
This accounts for the phenomenon that whilst the dye may be fixed by acid, if subsequently the
acid is neutralized with alkali (e.g. Ammonia) the dye is not entirely “unfixed” or stripped from
the leather. Dyes which have strong secondary valence forces often aggregate in strong-
concentrated solutions (Li et al., 2006).

Temperature Effects: The normal method of dissolving acid dyestuff is to paste the powder with
a little cold water until thoroughly wetted and then add boiling water to an amount 20 times the
weight of dyestuff. Secondary forces are weakened by the rise of temperature and large molecule
aggregates are broken down to give good solution. Thus the higher the temperature of dyeing,
the smaller the dye molecules, the better penetration and distribution on the leather and the less
fixation due to these forces. However, the ionic forces which are pH dependent increase with
temperature, giving more rapid fixation and less penetration or levelness the higher the
temperature. Temperature rise has an opposite effect on these two types of force. To get good
penetration the dyes would choose a “penetrating dyestuff” (i.e. probably low secondary valence
forces), adjust the pH of leather and dye bath to a point of minimum acidity by neutralizing or
ammonia addition, e.g. pH 6.0 thus reducing ionic fixation, dye warm (40-60 C) and later acidify
to pH 3.7 (Christie, 2001).

Effect of Concentration: Given a known quantity of dye and leather, the less water used the
stronger the surface shade obtained will be. However, if one is drum dyeing, the less the amount
of water used the much greater will be the mechanical action, giving rapid diffusion of the dye.

27
Such penetration would reduce the accumulation of dye on the surface and give paler shades
(Venkataraman, 1978).

Effect of Tannages: Acid dyes being anions will combine ionically with the cationic basic amino
groups of the skin and also by secondary forces (Venkataraman, 1978).

Other types of Anionic dyes:

Direct or Cotton or Substantive Dyestuffs so-called because they can give direct dyeing on
cotton (without any mordant pre-treatment). Fundamentally they are made similarly to acid
dyestuffs with sulfonic groups to give water solubility. However, the molecule is so built that it
has very large secondary valence potential and the minimum degree of sulphonation and hence
of ionic affinity. The expression substantive refers to the dyes’ ability to fix on cotton which
contains no ionic groups and hence refers to secondary valence bonds, e.g. H-bonds or dipole
fixation. The expression “acid-substantive” dye refers to one which has approximate equal
bonding by these forces and ionic forces. They are used exactly the same way as acid dyestuffs.
On chrome leather, they can give very strong surface shades of little penetration without acid
exhaustion at pH 4-5. This is due to strong secondary valence forces on chrome tanned fiber.
They have similar behavior on Zn and Al tanned leathers. On vegetable tanned leathers they
behave in a similar way to acid dyes (Vogel, 1998).

(B) Cationic Dyes-Basic Dyes

These were the original “aniline” dyestuffs and are made from tar distillation products by similar
methods to those used for acid dyestuffs, except that the sulphonation processes are omitted.
Water solubility is conferred by the presence of amine groups which form strongly ionizing salts
with acids. The colloidal dye ion carries a positive charge. Consequently there is a strong ionic
attraction between these cations and colloidal anions. Basic dyes give strong surface shades, no
penetration and often unlevel dyeings on vegetable/syntan tanned leathers. In a similar way they
will give a strong surface shade on leather previously dyed with anionic dyes. This fixation is
rapid hot or cold and is relatively independent of pH between 3 -9. Conversely cationic dyes
have very little affinity on cationic chrome leather, giving only the faintest tints. However, if the
chrome leather have been heavily masked, dried out and vegetable retanned or syntan
mordanted, and fat liquored with highly sulphated or sulphited oils, or is anionic dyed, these
anions may increase the affinity for basic dyestuffs. Basic dyestuffs give a range of strong
brilliant shades of yellow, orange, red, blue, violet and brown. Rich blacks are made from a
28
 mixture of these. Unfortunately they fade badly in sunlight, although some may be better. Some
improvement can be made by an after-treatment with salts of phosphomolybdo-tungstic acids.
Basic dyes tend to be soluble in some oils, greases, waxes and solvents. The free bases or their
oleates are very soluble and are used for coloring oils, waxes, etc (eg. Boot polishes, carbon
paper, typewriter ribbons, etc.). This property is associated with their properties of “marking off”
i.e. by simple contact, color may be transferred to another surface. This must be avoided on
many clothing leathers, etc. Their solubility in non-aqueous solvents may cause trouble in dry
cleaning or where a leather finish contains such solvents. The free base obtained under alkaline
conditions is of poor water solubility. Hard water or alkaline conditions may cause precipitation.
Basic dyestuffs are often dissolved by pasting with a little acetic acid, before adding boiling
water to avoid this happening (Vogel, 1998)
(C) Nonionic dyestuffs
(E.g. azoic ones) require longer dyeing times. Binding occurs at very broad pH Nonionic
dyestuffs are resistant to washing and abrasion. However surfactants of glycols of polyether type
remove them, probably due to formation of new hydrogen bonds. These dyestuffs may be
completely washed out from pelt by acetone; in chrome-tanned leather, however, 1/3 of them
will remain. One may conclude that in the binding of dyestuffs to chromium complexes strong
bonds participate. Behavior of dyestuff in solution depends primarily on dissociation of its
functional groups being responsible of its solubility. The effect of individual substituents on the
pH has been known for long. The following are some rules worth mentioning:
1. Sulfonic group is strongly dissociated when attached to an aromatic ring or in the presence of
amino groups; its pH is 0.5.
2. Carboxylic group is more dissociated when attached to benzene ring, than when linked to an
aliphatic chain. Attachment of other groups to the ring changes the degree of dissociation of the
group itself; direction of this change depends on the kind of group and on its position; nitro
group in ortho position increases dissociation the strongest.
3. Hydroxylic group is affected by other groups; nitro groups and halogens in phenols increase
significantly the degree of dissociation.
4. Amino groups dissociate to a small extent, other groups influence it like, e.g. and hydroxyl. Two
groups of dyestuffs of very specific way of action have gained importance recently: metal
reactive dyestuffs (Vogel, 1998).

29
2.18 Dyeing of Leather

2.18.1 Vegetable Tannages and Syntannages

Vegetable Tannages and syntannage are also anionic and in such leathers the cationic groups will

be largely blocked by their presence, thus reducing the number of sites on the leather molecule to

which the acid dye can fix. Consequently, acid dyes on these tannages show a lower rate of

fixation which gives good penetration and level dyeing, but paler shades result and it is

impossible to get strong shades. Auxiliary type of syntans will block these amino groups to a

greater degree than most vegetable tans and therefore give paler shades. They are often used as

“level dyeing” assistants. Acid addition will increase fixation, but lower pH are needed than on

other tannages to get equivalent fixation (usually pH 3.2-3.7). Usually penetration is easily

obtained at pH 4.0-4.5. One should be careful in adding ammonia to higher pH to obtain

penetration, for it will tend to strip the anionic vegetable tannage from the fiber. Vegetable

tanned leather may be quoted as having a shrinkage temperature of 62 0C by lab test but it will

not stand this temperature under drum dyeing conditions of an hour or more, when the normal

safe maximum is 45 0C. Vegetable tanned leather has a pale brown color, and with the

transparent color of dyestuffs this is an important factor because the color of dyed leather will be

a mixture of pale brown and that of dyestuff used. This pale brown tends to dull, or darken green

and blue shades in particular. Vegetable tannages do not have good “light fastness”, on exposure

to light they become a darker brown. In many cases their light fastness is much worse than that

of dyestuffs used. This can give rise to peculiar effects. Dyestuffs fade on exposure to light. Thus

a brown dyed vegetable tan leather may appear to have good light fastness, because although the

brown dye fades, the brown of the vegetable tan darkens. With an equivalent blue on the same

leather, the light effect would be most marked, I.e. the blue color would disappear to be replaced

by the darkening brown of the vegetable tan. Vegetable tannages do not have very good

30
resistance to water or soap washing and are not used for leathers requiring these properties

(Traubel and Eitel, 1977).

2.18.2 Chrome Tannage

Chromium salts fix to the acid carboxyl groups of the skin protein and consequently tend to

increase the cationic charge of the skin. Further, chromium salts hydrolyze giving acids which

also increase the acidity of the leather. The combination of both factors make chrome tanned

leather very cationic giving rapid surface fixation with acid dyes. This strong surface dyeing is

usually coupled with unleveled dyeing and poor penetration. Increase in temperature increase

these effects. Chrome tannages vary in this respect. Masked tannages are less cationic and give

more level dyeing, penetration and paler shades. Chrome leather that has been dried out and then

wetted back also should show loss of cationic charge and give less rapid dye fixation. Levelling

or penetrating agents usually consist of anionic syntans applied before or in the dyebath to

reduce the affinity for anionic dyestuffs. Many acid dyestuffs contain chemical groups which can

coordinate with the chrome complex, in a similar way to “masking” salts. Loosely defined as

“chrome mordant” dyes they give impoverished wash and water fastness (Traubel and Eitel,

1977).

2.18.3 Zirconium and aluminum tannage:

The Zirconium and aluminum salts used for tannage hydrolyze to a greater extent than the

corresponding chrome salts and thus give more highly cationic or more acid leathers. They also

give co-ordinated complexes with many dyes which can be of high colour value. Normally the

give strong surface shades of poor penetration and a tendency to unlevel dyeing. They are white

tannages, of good light fastness and can give very clean brilliant shades. Wash and solvent

fastness we usually improved. Alum tannage can raise particular problems, if the alum is not

31
well fixed, and tends to wash out in the dye bath. Traditionally alum tanages were dyed with dye

woods or vegetable extracts (Traubel and Eitel, 1977).

32
CHAPTER THREE

3.0 MATERIALS AND METHODS

3.1 Materials

These includes; sodium nitrite, dimethylformamide (DMF), dimethylsulphoxide (DMSO), 3-

aminobenzoic acid, urea, Sulphanilic acid,1-aminoanthraquione,4-chloroanaline 2-naphthol-3,6-

disulfonic acid (R-Acid), Conc. Hydrochloric acid, sodium hydroxide, copper sulphate, sodium

nitrite, ethanol, acetone, chrome tanned leather.

3.2 Apparatus and Equipment

Thermometer, pH meter, heating mantle, magnetic stirrer, eletronic balance, Gallenkamp melting

point apparatus, Agilent CARY 300 UV-visible spectrophotometer, Agilent CARY 630 FT-IR,

Electric Oven, beakers, round bottom flask, 250ml volumetric flasks, Buchner flask, hot plate,

steam bath, sample bottles.

3.3 Methodology
3.4 Procedure for Diazotization and Coupling

3.4.1 Diazotization of 1-aminoanthraquionone

The amine 1-aminoanthraquinone (2.5 g of 0.02 M) was weighed and dissolved in 30 ml of 2 M

sodium hydroxide. The temperature of the mixture was cooled to 0-5 oC in an ice bath. Cold

solution of sodium nitrate (50 ml of 1 M) and dilute sulpuric acid was added drop wise to the

mixture with constant stirring for 30 minutes to form the diazonium salt. Urea (0.5g) was then

added to the mixture and stirred continuously for another 10 minutes to achieve complete

diazotization. The reaction scheme is as given below;

33
Scheme3.1: Diazotization of 1-aminoanthraquinone acid

3.4.2 Diazotization of 3-aminobenzoic acid

The amine 3-aminobenzoic acid (2.5 g of 0.02 M) was weighed and dissolved in 30 ml of 2 M

sodium hydroxide. The temperature of the mixture was cooled to 0-5 oC in an ice bath. Cold

solution of sodium nitrate (50 ml of 1 M) and dilute hydrochloric acid was added drop wise to

the mixture with constant stirring for 30 minutes to form the diazonium salt. Urea (0.5g) was

then added to the mixture and stirred continuously for another 10 minutes to achieve complete

diazotization. The reaction scheme is as given below;

Scheme3.2: Diazotization of 3-Aminobenzoic acid

Where R = represent the coupling component (i.e. 2-naphthol-3, 6-disulfonic acid)

3.4.3 Diazotization of sulphanilic acid

Sulphanilic acid (3.5 g of 0.02 mol) was dissolved in 30 ml of 2 M solution of NaOH. The

solution will be cooled in an ice bath. A solution of sodium nitrite (50 ml of 1 M) and 10 ml cold

solution of Conc. HCl was added drop-wise with continuous stirring for 30 min to form the

34
diazonium salt solution. Urea (0.5g) was then added to the mixture and stirred continuously for

another 10 minutes to achieve complete diazotization. The reaction scheme is as given below;

Scheme 3.3: Diazotization of Sulphanilic acid

3.4.4 Diazotization of 4-Chloroanaline

4-Chloroanaline (3.5 g of 0.02 mol) was dissolved in 30 ml of 2 M solution of NaOH. The

solution will be cooled in an ice bath. A solution of sodium nitrite (50 ml of 1 M) and 10 ml cold

solution of Conc. HCl was added drop-wise with continuous stirring for 30 min to form the

diazonium salt solution. Urea (0.5g) was then added to the mixture and stirred continuously for

another 10 minutes to achieve complete diazotization. The reaction scheme is as given below;

Scheme 3.4: Diazotization of 4-Chloroanaline

3.4.5 Coupling reaction

The coupling component (i.e. 2-naphthol-3, 6-disulfonic acid) was dissolved in acetic acid and

cooled to 00C, by adding ice. The diazonium salt solution of 1-aminoanthraquinone previously

prepared will be added over 30-40 minutes with vigorous stirring. The mixture was stirred for
35
further 30 min, under the temperature of 0-5 oC and the pH of the solution was adjusted to 4-5

using 10 % sodium hydroxide solution. The resulting product was then collected by filtration.

The crude product obtained will be purified by recrystallizing it from ethanol to obtain dye 1.

The above procedure was repeated by coupling the solution of 2-naphthol -3, 6-disulfonic acid

with the diazonium salt solution of 3-Aminobenzoic acid to obtain dye 2, Sulphanilic acid to

obtain dye 3, 4-chloroanaline to obtain dye 4.

The proposed structure of the synthesized dyes is as shown in figures 3.1 below;

Figure3.1: Dye 1

Figure 3.2: Dye 2

36
Figure3.3 Dye 3

Figure3.4 Dye 4
3.5 Characterization of the synthesized dyes and intermediates.

The synthesized dyes was characterized via analytical techniques such as melting point, Fourier

transform infra-red spectroscopy (FT-IR), UV-visible spectroscopy and solubility test.

3.5.1 Melting point determination

The melting points of each dye was determined by using Gallenkamp melting point apparatus.

Small amount of each dye was filled into a capillary tube and placed into the apparatus; the

melting point of each sample was obtained by consistently focussing on the apparatus as the

apparatus gradually heat the samples in order to determine the purity of the dyes.

37
3.5.2 Determination of visible absorption spectra

The visible absorption spectra of the dyes was recorded on an Agilent CARY 300 UV-VISIBLE

spectrophotometer from dye solutions in DMSO and methanol at a concentration of 1.5×10 -5

mol/l as described by Yuh and Wei (2006).

3.5.3 FT-IR determination

FT-IR spectra of the synthesized dyes was recorded on Agilent CARY 630 FT-IR

spectrophotometer, in other to obtain the functional group present in the synthesized dye.

3.5.4 Solubility test

The solubility test of the synthesized dyes was determined by using both polar and non-polar

solvents.

3.6 Application of Dyes

3.6.1 Preparation of dye stock solution

Exactly 1 % stock solution of each dye was prepared, a liquor ratio of 50:1 was used, 2 % shade

on weight of fabric (O.W.F) and 1 g of chrome tanned leather. The volume required from each

stock solution was calculated based on the formula;

V=

Where:

P = percentage shade

W = weight of fabric

38
C = percentage concentration of stock solution.

3.6.2 Dyeing of leather

The synthesized dyes was used in dyeing of chrome tanned leather. The standard method of

dyeing leather was followed using the recipes below:

For neutralisation of chrome tanned leather:

I. 100 % water

II. 1 % sodium bicarbonate

III. Run for 15 minutes

For dyeing of chrome tanned leather:

i. 120 % of water (60 oC)

ii. 1 % of dye

iii. Run for 45 minutes

For dye fixation:

I. 0.1 % of formic acid

II. Run for 15 minutes

The pH of the chrome tanned leather was adjusted to 5.5 using 1 % sodium bicarbonate to

neutralize the leather and thereafter wash thoroughly with distilled water. A solution of the dye

sample (1 %) was made with distilled water using heating mantle and the temperature of the

medium was raised to 60 oC, the leather sample was then introduced into the dye bath solution

and run for 45 minutes. Thereafter, 0.1 % of the formic acid was added to the dye bath and

further run for 15 minutes in order to fix the dye on the substrate. The dyed leather was then

39
removed from the bath and rinse severally under running tap water and dried. This procedure

was repeated for the second synthesized dye on chromed tanned leather (Traubel and Eitel,

1977).

3.7 Assessment of Fastness Properties

3.7.1 Wash fastness test

The dyed chrome tanned leather was subjected to I.S.O.3 wash fastness test by the following

procedures: The specimens was prepared by cutting the dyed leather into 5 cm x 2 cm

dimensions; they were made into composites by stitching the test specimen made of the dyed

sample placed in between white cotton of dimensions 10 cm x 4 cm. The composite was agitated

in the solution made up of the following (Nkeonye, 1987):

Soap solution 5 g/l

Sodium carbonate 2 g/l

Liquor ratio 50:1

The washing was maintained at 50 °C for 45 minutes with continuous agitation. At the end of the

washing test the composite specimen will be removed, rinsed in cold water and the components

separated and dried at room temperature. The change in colour of the dyed leather and the

staining of adjacent undyed cloths was assessed using the appropriate grey scale.

3.7.2 Light fastness test (Using 8-Blue Wool Standard)

The dyed chrome tanned leather samples and blue wools standard was exposed facing due south

and inclined at an angle to the horizontal approximately equal to the latitude of the place where

the exposure is being made. Adequate ventilation of the samples during exposure was ensured.

The partly covered samples was exposed to UV radiation. As exposure proceeded for 3 days, the

samples under test and the blue wool standards was examined at intervals and the change in

colour of the samples was compared visually with the changes that occur in the standards. The
40
light fastness of the sample is the number of the standard that shows a similar visual contrast

between the exposed and unexposed part of the samples. The exposure was determined when the

blue wool standard 7 fades or when fully exposed and non-exposed test samples is equivalent to

grade 3 on the grey scale (Nunn, 1990).

Light fastness values for the dyed chrome tanned leather was obtained by comparing the degree

of fading with that observed with Blue wool standard. Rating was given according to the Wool

standard with which the dyed material fading is comparable.

41
 CHAPTER FOUR

4.0 RESULTS

4.1 Physical Properties of Synthesized Dyes

The physical properties of synthesized dyes are shown in Table 4.1 below;

Table 4.1: Physical Properties of Synthesized Dyes

S/N Sample Melting point (°C) % Yield Appearance

1 Dye 1 253-255 75 Deep brown

2 Dye 2 178-180 60 Light brown

3 Dye 3 288 -270 70 Brownish black

4 Dye 4 290-295 80 Black

Where: Dye 1 is dye from 1-aminoanthraquinone

Dye 2 is dye from 3-aminobenzoic acid

Dye 3 is dye from sulphanilic acid

Dye 4 is dye from 4- chloroaniline

42
4.2 Solubility Test

The solubility test of synthesized dyes was carried out in five (5) different solvent, based on their
polarities from Table 4.2 below;

Table 4.2: Solubility Test of Synthesized Dye

S/N Solvent Dye 1 Dye 2 Dye 3 Dye 4

1 Water Soluble Soluble Soluble Soluble

2 DMSO Soluble Soluble Soluble Soluble

3 Ethanol Partially Soluble Insoluble Insoluble Soluble

4 Methanol Partially Soluble Insoluble Insoluble Soluble

5 Acetone Soluble Soluble Insoluble Soluble

43
4.3 Visible Absorption Spectroscopy of Dye

The visible absorption spectroscopy of the dyes in water were measured in DMSO and Ethanol
as shown in table 4.3

Table 4.3 Visible Absorption Spectroscopy of Dye

Dye No. DMSO ETHANOL

1 483.00 479.00

2 485.00 489.00

3 493.00 4800

4 487.00 486.00

44
4.4 Infra-Red Spectra of the Dye

The FT-IR perks observed with the corresponding groups present for the dye as shown is
presented in Table 4.4 below

Table 4.4: Infra-Red Spectra of the Dyes

Dyes Vibration Frequencies (cm-1)

Dye 1 3470.2, 3302.4, 3418.0 (N-H /O-H

Stretch), 1673.6(C=O Stretch), 3019.1 (H-C-H
Stretch), 1587.8, 1543.1, 1453.7(-N=N- Stretch).

Dye 2 3425.4, (O-H/N-H Stretch), 3058.4 (C=C-H Stretch)

1982.9 (C=C Stretch), 1558.0, (-N=N Strech).

Dye 3 3451.5 (O-H /N-H Stretch), 3063.9 (C=C-H

Stretch), 2922.2 (H-C-H Stretch), 1595.3(C=C

Stretch), 1558.0, 1446.2, 1505.8(-N=N- Stretch).

Dye 4 3403.1(O-H /N-H Stretch), 3056.4(C=C-H

Stretch), 2687.4(C-H Stretch), 1554.3(-N=N-
Stretch)

45
4.5 Assessment of Fastness Properties to Wash and Light

The resistance of dyed material to laundry treatment such as washing is referred to as washing
fastness. The washing fastness test is considered very useful since dyed fabrics are subjected to
various washing conditions during use. The procedure recommended by International Standard
Organization, number 3 (ISO 3) for washing and 8-Blue wool standard for light fastness were
adopted and the results shown in Table 4.5-4.6 below.

Table 4.5: Wash Fastness of the Synthesized Dye on Chrome tanned Leather Using IOS 3
Standards.

Dye Sample Change in Color of Chrome Staining of Color on Chrome Tanned

Tanned Leather Adjacent Leather Leather
Dye 1 5 4/5 Dark brown

Dye 2 4 3/4 Light-brown

Dye 3 4 4 Brownish-black

Dye 4 5 5 Black

Change in shade staining

5= Excellent 5= No staining

4= Very good 4= Very slight staining

3= Good 3= moderate staining

02= Fair 2= Significant staining

1= Poor 1= Deep staining

46
Table 4.6: Light Fastness of the Dyes on Chrome Tanned Leather Using 8-Blue Wool
Standard

The light fastness test results obtained using 8 blue wool standard for the dyed substrate is
presented table 4.6 below:

Dye Samples Chrome Tanned Leather

Dye 1 6

Dye 2 5

Dye 3 4

Dye 4 6

Fastness grade Degree of fading Fastness grade Degree of fading

8 none 4 appreciable

7 very slight 3 significant

6 slight 2 extensive

5 moderate 1 very extensive

47
 CHAPTER FIVE

5.0 DISCUSSSION, CONCLUSION, AND RECOMMENDATION

5.1 DISCUSSSION

5.1.1 Physical Properties of the Synthesized Dyes

The melting point, percentage yield and the appearance of the synthesized dyes are present in
Table 4.1. The color of the synthesized then purified dye ranges from brown to black. The
synthesized Dye 1 from (1-aminoanthraquinone) gave a deep brown\black appearance due to its
stronger solubilizing group than the synthesized Dye 2 from (3-aminobenzoic acid) and Dye 3
from (sulphanilic acid) which gives a light brown\brownish brown appearance.

All dyes exhibited well defined melting point which ranges from the highest 178-295°C, Dye 1
had a melting point of 253-255°C, and Dye 2 has a melting point of 178-180°C, Dye 3 has a
melting point of 288-270°C, Dye 4 has a melting point of 290-295°C.

The percentage yield of the dyes ranges from 60-80% .Thus Dye 1 percentage yield was 75%,
Dye 2 percentage yield was 60%, Dye 3 percentage yield was 70 and Dye 4 percentage yield was
80% which gave the highest percentage yield and gave an excellent affinity of the dyes on
chrome tanned leather.

5.1.2 Solubility Test

The solubility test of the synthesized dyes were carried out in different solvents. In Table 4.2 it
was observed that all the synthesized dyes were soluble in water and DMSO. Dye 4 was also
observed to be soluble in all solvents used while some of the synthesized dyes were partially
soluble or insoluble in ethanol, methanol and acetone. The extent of the solubility of these dyes
may be due to the strength of the polarities of the solvent used and thus, the dyes tend to dissolve
more in highly polar solvents such as DMSO

48
5.1.3Visible Absorption Spectroscopy of Dye

Table 4.3 shows λmax (Wavelength of maximum absorption) of the dyes obtained in different
solvents. All the dyes shows strong and broad absorption in visible region, which indicates the
presence of color imparting chromophores which are responsible for the hues. Hues is the
predominant colors transmitted by an organic compound when the complementary colors
contained in the light passing it has been absorbed. The wavelength of the dyes ranges from 483
to 493 nm in DMSO, and 479 to 489 in ethanol. It can be observed that the UV-visible of the
dyes recorded in DMSO has the highest wavelength of maximum absorption which makes the
dyes to be more bathochromic, as compared to ethanol. This means that the higher the polarity of
the solvent, the more the bathochromic shift in the wavelength absorption (Yu and Wei 2006).

5.1.4 Infra-Red Spectra of Synthesized Dyes

The result of the infra-red analysis carried out on synthesized dye is shown in Table 4.4.
The synthesized Dye 1 (from 1-aminoanthraquinone) had a peak that appeared at a frequency
range of 3470.2cm-1 , 3302.4cm-1 and 3418.0Cm-1, indicating the presence of N-H stretch of
Amine compounds, the peak that appeared at a frequency range of 1988.7cm-1 indicating the
presence of C=C stretch of Alkane compounds, the peak that appeared at a frequency range of
1673.6cm-1 indicating the presence of (C=O)Stretch of carboxylic acid, the peak that appeared at
a frequency range of 3019.1cm-1 indicating the presence of (H-C-H) Stretch of Alkane
Compound, the peak that appeared at a frequency range of 1587.8cm1,1453.7cm1,1453.7cm-
1
indicating the presence of (-N=N-).

The synthesized Dye 2 ( from 3-aminobenzoic acid) had a peak that appeared at a frequency
range of 3425.4cm-1 indicating the presence of O-H/N-H Stretch of Hydroxyl ion, the peak that
appeared at a frequency range of 3058.4cm -1 indicating the presence of C=C-H stretch of Alkane
compounds, the peak that appeared at a frequency range of 1982.9cm -1 indicating the presence of
C=C stretch of Alkene compounds, the peak that appeared at a frequency range of 1558.0 cm-
1
,1505.8 cm-1,indicating the presence of (-N=N-) Stretch.

The synthesized Dye 3 ( from Sulphanilic acid) had a peak that appeared at a frequency range of
3451.5cm-1 indicating the presence of O-H/N-H stretch of Hydroxyl ion, the peak that appeared
at a frequency range of 3063.9cm-1 indicating the presence of C=C-H stretch of Alkene
49
compounds, the peak that had a frequency range of 2922.2cm -1 indicating the presence of H-C-H
stretch of Alkane compounds, the peak that appeared at a frequency range of 1595.3cm-
1
indicating the presence of C=C stretch of Alkene compound ,the peak that appeared at a
frequency range of 1558.0cm-1,1446.2cm-1,15058cm-1(-N=N-).

The synthesized Dye 4 ( from 4-chloroanaline) had a peak that appeared at a frequency range of
3403.1cm1indicating the presence of N-H stretch of Amine compound, the peak that had a
frequency range of 3036.4.cm-1 indicating the presence of C=C-H Stretch Alkene compounds,
the peak that had a frequency range of 2687.4cm -1 indicating the presence of C-H stretch of
Alkane compounds, the peak that had the frequency range of 1554.3cm- 1 indicating the presence
of (-N=N-)Stretch.

5.1.5 Assessment of Fastness Properties to Washing and Light

5.1.5.1 Wash Fastness of the Synthesized Dyes on Chrome Tanned Leather Using ISO 3
Standards.

The wash fastness of the dyed chrome tanned leather is presented in Table 4.5 and the result
comprises of the change in color on the chrome tanned leather and staining of the adjacent fabric.
The color of the dyes on the dyed substrate ranges from dark brown to black with a deeper
shades, high tectorial strength and excellent levelness on the chrome tanned leather. The
variation in the shade of the dyed chrome tanned leather may be as a results from the alteration in
the diazo components. Thus Dye 1 and 4 exhibited an excellent fastness to washing while Dye 2
and 3 exhibited very good fastness to washing on chrome tanned leather.

The remarkable degree of levelness and brightness after washing, indicates good penetration and
excellent affinity of the dyes to the chrome tanned leather. In addition, the results obtained
showed that the dyed chrome tanned leather with Dye 1 and 4 have excellent fastness level(scale
5)to washing as compared to Dye 2 and 3(scale 4), which may be due to the presence of
solubilizing group, which affects solubility and washing ability of the dye-out of the dyed
substrate.

5.1.5.2 Light Fastness of the Dyes on Chrome Tanned Using 8 Using Wool Standards.

The light fastness rating of the dyed chrome tanned leather is presented in Table 4.6 the results
indicated in Dye 1 and 4 shows slight light fastness, Dye 2 shows moderate light fastness, Dye 3
shows appreciable light fastness so it’s then observed that there’s absolute value for light fastness
50
of a dye. Light fastness is a property of a colorant such as dye or pigment that describe how
resistant to fading when exposed to light, the bleaching of the color is caused by the impact of
ultra violet radiation in the chemical structure of the molecule giving the color of the subject, the
part of the molecules responsible for the color is called chromophore. Light encountering a
painted surface can either alter or break the chemical bonds of the pigment, causing the colors to
bleach or change in a process known as photodegradation, materials this resist the effect are said
to be the light fast. The rating obtained for a given colorant for any fading test depends on many
factors most of which are: concentration and/or degree of aggregation of dye within the chrome
tanned leather. However, the light fastness observed for the dyes ranges from 4-6 which could be
ascribed to the coupling component used molecular structure of the dyes, planarity dyes and
substituents that provides shields from radiant energy on azo chromophores, and which conferred
good light fastness properties on dyed substrate.

51
 5.2 Conclusion

Four different Azo acid dyes were synthesized using 2-napthol -3, 6-disulphonic acid as the
coupling component along with 1-aminoanthraquionone, 3-aminobenzoic acid, sulphanilic acid
and 4-chloroanline as the diazo components. The dyes were mostly brown and black, the melting
point ranges from 178-2950C. The percentage yield of the synthesized dyes were also calculated
to be 60%-80%. The dyes absorption varies with their level of bathochromicity based on the
degree of polarity of the solvents used. From the UV-visible spectra in DMSO and ethanol,the
dyes with DMSO were more bathochromic as compared to ethanol.

The infra-red spectra of the synthesized dyes confirmed the presence of chromophores such as
C=O, N-H, C=C, and -N=N- respectively, which accounts for the colored nature of the
synthesized dyes.

5.3 Recommendation

1 Further application of the synthesized dyes in textile and leather industries.

2 Further Structural eluidication of the synthesized dyes should be carried out using
GCMS, NMR and high resolutions Mass Spectroscopy should be carried out.

3 Determination of the antimicrobial properties of these dyes on some pathogenic

microorganism.

52
 APPENDICES

APPENDIX I: UV-VISIBLE SPECTROSCOPY OF DYES

Wavelength (nm)

Uy-Visible Result of Dye 1 in DMSO

4
1.47

4
47900
,

3
3
2
Ab

2
s

1
1
0
0
40
40 50
50 60
60 70
70 80
80
0 0 0 0 0

Wavelength (nm)

Uv-Visible Result of Dye 1 in Ethanol

53
 1.503

485.00
,
3
Ab

2
s

0
400 500 600 700 800
Wavelength (nm)

Uv-Visible Result of Dye 2 in DMSO

Wavelength (nm)

UV-Visible Result of Dye 2 in Ethanol

54
 Wavelength (nm)

Uv-Visible Result Dye 3 in DMSO

4
0.987

487.00
,

3
Ab
s

0
400 500 600 700 800
Wavelength (nm)

Uv-Visible Result of Dye 3 in Ethanol

55
 Wavelength (nm)

Uv-Visible Result of Dye 4 in DMSO

Wavelength (nm)

Uv-Visible Result of Dye 4 in Ethanol

56
APPENDIX II: INFRA-RED SPECTRA OF THE DYE

FT-IR Result of Dye 1

FT-IR Result of Dye 2

57
 FT-IR Result of Dye 3

Chart of Dye 4

FT-IR Result of Dye 4

58
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