A-level Applied Science/Colour Chemistry/Dyes

< A-level Applied Science | Colour Chemistry

Dyes are soluble, coloured compounds.

Pigments are insoluble - see Dyes and pigments.
Chromogens are substances which are readily converted into dyes or pigments.
Contents
[hide]

1 Experiments

2 Basic dye

3 Vat dye

4 Acid dye
4.1 Structures

4.2 Classes of acid dyes

4.3 Health and safety

5 Fibre reactive dye

6 Direct dye

7 Disperse dye

8 Azo dye

9 Anthraquinones
o

9.1 Natural occurrences

9.2 Industrial applications

10 Sulphonic dye

11 Triaryl dye

12 Cationic dye

13 Anionic dye

14 Polyphenols

15 Halochromic dyes and Indicators

16 References

17 Sources

Experiments[edit]
Onion skin dye.

Basic dye[edit]
Basic dyes are water-soluble cationic dyes that are mainly applied to acrylic fibres, but find some
use for wool and silk. With cellulosic fibres an anionic tannic acid mordant is required. Usually
ethanoic ('acetic') acid is added to the dyebath to help the uptake of the dye onto the fibre. Basic
dyes are also used in the colouration of paper.
The first synthetic dyes, such as mauveine (developed in 1856), are basic. They have a wide colour
range, but a reputation for poor light fastness. Modern basic dyes are light fast, and if water can be
excluded from the chemical strucutres the lightfastness is further increased. They are fairly fast to
washing except on acrylics; however, the newer basic dyes are very fast on acrylics. They contain a
=NH2+ or a -NH3+ group, giving them a charge in solution of +1.

Vat dye[edit]
Vat dyes are an ancient class of dyes, based on the natural dye, indigo, which is now produced
synthetically. Modern vat dyes (1901) include anthraquinone derivatives, but indigo remains the
most important vat dye. They are useful mainly for cotton; but also for wool and other fibres.
The process "vat dyeing" refers to dyeing in a bucket or vat. It can be performed whenever a solid,
even shade over the entire garment is desired. Almost any dye can be used, including fiber reactive
dyes, direct dyes, and acid dyes. One alternative to vat dyeing is direct dye application, such as the
process used for tie dyeing. "Vat dyes" are a special class of dyes that work with a special chemistry.
Note that not all vat dyeing is done with vat dyes!
About Vat Dyes
Most vat dyes are less suitable than, say, fibre reactive dyes, for the home dyers, as they are difficult
to work with; they require a reducing agent to solubilise them. The dye is soluble only in its reduced
(oxygen-free) form. The fibre is immersed repeatedly in this oxygen-free dyebath, then exposed to
the air, whereupon the water-soluble reduced form changes colour as oxygen turns it to the waterinsoluble, oxidised form. Indigo is an example of this dye class; it changes from yellow, in the
dyebath, to green and then blue as the air hits it.
Instructions for dyeing with vat dyes
PRO Chemical & Dye, which sells some vat dyes, provides instructions online for Immersion Dyeing
using PRO Vat Dyes. The process requires the use of lye (sodium hydroxide), which must be used
with due care, including the use of safety goggles.
Indigo is subject to major crocking (rubbing off of the dye onto other items) unless it is applied
carefully. This means use a weaker dyebath, and dipping many times, rather than a single strong
dipping.
Light-oxidised Vat Dyes
Ink-o-dye is a type of vat dye which uses light rather than oxygen to 'fix' the dye, with an
inspirationally wide variety of possible effects. These dyes, which are chemically similar to vat dyes,
Inkodyes are developed by light instead of being applied in an oxygen-free bath and being
developed in the fabric by exposure to oxygen. Inkodyes are true dyes, not fabric paints. (A dye
actually itself attaches to the fabric; fabric paint includes a glue-like binder, which imparts a stiffer
feeling to the fabric.) The process is more difficult than the process of tie-dyeing with fiber reactive
dyes. One retail source of Inkodye is Dharma Trading Company.
Further Reading
Imagery on Fabric by Jean Ray Laury
The Chemistry of Vat Dyes by Dianne Epps

Acid dye[edit]
Acid dyes (developed in 1862) are water-soluble anionic dyes that are applied to fibres such
as silk, wool, nylon and modified acrylic fibers using neutral to acid dyebaths. Attachment to the fibre
is attributed, at least partly, to salt formation between anionic groups in the dyes and cationic groups
in the fibre.
Acid dyes are have good fastness if the appropariate dye is chosen; but in general they are not
substantive to cellulosic fibres. They have a good colour range.
Chemically they are carboxylic or sulphonic acid salts used in an acid dye bath. In the home or art
studio, the acid used in the dyebath is often vinegar ('acetic' or ethanoic acid) or citric acid. The dye
molecule forms an anion with a charge of -1 to -4, occasionally more.
In textiles, acid dyes are effective on protein fibers, i.e. animal hair fibres like wool, alpaca, mohair
and silk. They are effective in dyeing the synthetic fibre nylon but of minimal interest in dyeing any
other synthetic fibres.
Acid dyes are generally divided into three classes which depend on fastness requirements, level
dyeing properties and economy. The classes overlap and generally depend on type of fibre to be
coloured and also the process used.
Acid dyes are thought to fix to fibres by hydrogen bonding. They are normally sold as the sodium salt
therefore they are in solution anionic. Animal protein fibres and Nylon fibres contain many cationic
sites therefore there is an attraction of anionic dye molecule to a cationic site on the fibre. The
strength (fastness) of this bond is related to the desire/chemistry of the dye to remain dissolved in
water over fixation to the fiber.

Structures[edit]
The chemistry of acid dyes is quite complex. Dyes are normally very large aromatic molecules
consisting of many linked rings. Acid dyes usually have a sulphonyl or amino group on the molecule
making them soluble in water. Water is the medium in which dyeing takes place. Most acid dyes are
related in basic structure to the following:
Anthraquinone type:
Many acid dyes are synthesised from chemical intermediates which form anthraquinone-like
structures as their final state. Many blue dyes have this structure as their basic shape. The structure
predominates in the levelling class of acid dye.

Acid Blue 40 is an anthraqinone-based acid dye.

Azo dyes:

Although Azo dyes are a separate class of dyesuff mainly used in the dyeing of cotton (cellulose)
fibres many acid dyes have a similar structure, most are red in colour.

Acid Orange 7 an azo-based acid dye.

Triaryl type:

Acid Green 16 is a triaryl acid dye.

Triaryl acid dyes predominate in the milling class of dye.

Classes of acid dyes[edit]

Equalising/levelling acid dyes:
Highest level dyeing properties. Quite combinable in trichromatic shades. Relatively small molecule
therefore high migration before fixation. Low wet fastness therefore normally not suited for clothing.
Milling acid dyes:
Medium to high wet fastness. Some milling dyes have poor light fastness in pale shades. Generally
not combinable - used as self shades only.
Metal complex acid dyes:
More recent chemistry combined transition metals with dye precursors to produce metal complex
acid dyes with the highest light fastness and wet fastness. These dyes are also very economical.
They produce, however, duller shades.

Health and safety[edit]

Any dyes including acid dyes have the ability to induce sensitisation in humans due to their complex
molecular structure and the way in which they are metabolised in the body. This is extremely rare
nowadays as we have a much greater understanding through experience and knowledge of
dyestuffs themselves. Some acid dyes are used to colour food. We wear fabrics every day exposing
our skin to dyes.
The greatest risk of disease or injury due to dyes is by ingestion or exposure to dye dust. These
scenarios are normally confined to textile workers. Whereby the dye itself is normally non toxic, the
molecules are metabolised (usually in the liver) where they may be broken back down to the original
intermediates used in manufacture. Thus many intermediate chemicals used in dye manufacture

have been identified as toxic and their use retricted. There is a growing trend among governments to
ban the importation of dyes synthesised from restricted intermediates. For example: the dye CI Acid
red 128 is banned in Europe as it was found to metabolise in the body back to ortho-toluidine, one of
its chemical intermediates. Many intermediates used in dye manufacture such as o-toluidine,
benzidine etc. were found to be carcinogenic. All the major chemical companies have now ceased to
market these dyes. Some, however, are still produced but they are found to be totally safe when on
the fiber in its final state. The use of these dyes is declining rapidly as cheap and safer alternatives
are now easily available.
The incident concerning the dye Sudan 1 is an example of a suspected toxic dye finding its way into
the food chain. Such incidents are extremely rare.

Fibre reactive dye[edit]

Fibre reactive dyes utilise a chromophore containing a substituent that is capable, when activated,
of directly reacting with the fibre substrate. The covalent bonds that attach reactive dyes to the fibres'
amine or hydroxyl groups make them among the most permanent of dyes.
Reactive dyes first appeared commercially in 1956, after their invention in 1954 by Rattee and
Stephens at the ICI Dyestuffs Division site in Blackley, Manchester, UK. The dyes contain a reactive
group, either a halo-heterocycle or an activated double bond, that, when applied to a fibre in a
weakly alkaline dye bath, forms a chemical bond with a hydroxyl group on the cellulosic fibre.
Trichlorotriazine is a common reactive group:

Its three chlorine atoms can readily form HCl with a hydrogen from -OH or -NH2, leaving the O or N
attached to the triazine ring in place of the Cl.

Reactive Blue 4 is shown with amine groups it can react with on a protein chain. The chromophore is in blue, the
reactive halo-heterocycle in green and the protein in black.

"Cold" reactive dyes, such as Procion MX, Cibacron F, and Drimarene K, are very easy to use
because the dye can be applied at room temperature. Reactive dye is by far the best choice for
dyeing cotton and other cellulose fibres at home or in the art studio. Reactive dyeing is now the most
important method for the colouration of cellulose fibres. Reactive dyes can also be applied
on wool and nylon, in the latter case they are applied under weakly acidic conditions.
Reactive dyes are avaialble in a good range of colours.
For more info Fundamental Chemistry of reactive dyes
Other reactive dyes:

Carbene dyes

Direct dye[edit]
Direct or substantive dye molecules (developed 1884) are attracted by intermolecular forces to the
textile. The amount of this attraction is known as "substantivity": the higher the substantivity the
greater the attraction of the dye for the fibre. They are easy to apply (direct means without
mordant) and come in a wide range of colours.
Direct dyeing is normally carried out in a neutral or slightly alkaline dyebath, at or near boiling point,
with the addition of either sodium chloride (NaCl) or sodium sulphate (Na2SO4). Direct dyes are used
mainly on cotton and paper; but also with leather, wool, silk and nylon. Some are used as pH
indicators and as biological stains.
Direct dyes are fairly fast to washing, and this can be improved by after-treament. Some have high
light fastness. Chemically, the dyes contain the sulphonate group, essential for water-solubility. The
more groups, the more water-soluble. Usually 2-4, occasionally 1 or 5 groups. The chromophore is
usually azo type.

Disperse dye[edit]
Disperse dyes were originally developed (1923) for the dyeing of cellulose acetate, but can also be
used to dye nylon, triacetate and polyester fibres. They are fast if the correct dye is selected for the
fibre. Acrylics can be dyed with disperse dyes, but are only moderately fast and will not take intense
dyeing.
Chemically, disperse dyes are water-insoluble azo and anthraquinone dyes. The dyes are finely
ground in the presence of a dispersing agent and then sold as a paste, or spray-dried and sold as a
powder.
The dyes are applied as dispersions (emulsions). In some cases, a dyeing temperature of 130 C is
required, and a pressurised dyebath is used. The very fine particle size gives a large surface area
that aids dissolution to allow uptake by the fibre. The dyeing rate can be significantly influenced by
the choice of dispersing agent used during the grinding.

Disperse Yellow 7 is a diazo disperse dye. Note the lack of -NH (basic) or -SO3(acidic) groups.

Disperse dyes are available in a wide range of colours.

Azo dye[edit]
Azo dyeing is a technique in which an insoluble azo dye is produced directly onto or within the fibre.
This is achieved by treating a fibre with both diazoic and coupling components. With suitable
adjustment of dyebath conditions the two components react to produce the required insoluble azo
dye. This technique of dyeing is unique, in that the final colour is controlled by the choice of the
diazoic and coupling components.
Azo compounds generally have a molecular formula of the form R-N=N-R', in which R and R' can
be either aromatic or aliphatic. The N=N group is called an azo or diimidefunctional group. The
aromatic groups help to stabilise the N=N group by making it part of an extended delocalised
system. This also has the effect of making many azo compounds coloured, as delocalised
or conjugated systems often absorb visible frequencies of light.

A typical Azo compound, chrysoidine dye

Another typical Azo compound, 4-hydroxyphenylazobenzene, a.k.a. yellow azo dye

The name azo comes from azote, an old name of nitrogen that originates in French and is derived
from the Greek a (not) + zoe (to live). Aromatic azo compounds (R = R' = aromatic) are usually
stable and have vivid colors such as red, orange, and yellow. Therefore, they are used as dyes,
which are called azo dyes. Some azo compounds, e.g. Methyl orange, can also be used as acidbase indicators, due to their ability to function as weak acids, and the different colours of the acid
and salt forms. Azobenzene is another typical aromatic azo compound. Their colour originates from
absorbance in the visible region of the spectrum due to the delocalisation of electrons in the
benzene and azo groups forming a conjugated system, whereby the N=N group is the chromophore.
Aliphatic azo compounds (R and/or R' = aliphatic) are rather unstable. At an elevated temperature or
by irradiation, two carbon-nitrogen (R-N) bonds are cleaved simultaneously with the loss of nitrogen
gas to generate carbon-centered radicals.
Aromatic azo compounds can be synthesized by using an azocoupling reaction, that is, an
electrophilic substitution reaction on aromatic rings with diazonium salts. Diazonium salts
decompose at temperatures warmer than about 5 degrees Celsius, so the reaction must take place
in solution under freezing conditions:

Anthraquinones[edit]
Template:Chembox header| Anthraquinone

Chemical name

Anthraquinone

Chemical formula

C14H8O2

Molecular mass

208 g/mol

CAS number

[84-65-1]

Density

x.xxx g/cm

Melting point

286 C

Boiling point

379.8 C

SMILES

O=C2c1ccccc1 C(c3c2cccc3)=O

Template:Chembox header | Disclaimer and references

Anthraquinone (9,10-dioxoanthracene) is an aromatic organic compound. It is a derivative of

anthracene. It has the appearance of yellow or light grey to grey-green solid crystalline powder.
Its other names are 9,10-anthracenedione, anthradione, 9,10-anthrachinon, anthracene-9,10quinone, 9,10-dihydro-9,10-dioxoanthracene, and trade names Hoelite, Morkit, Corbit, and others.

Natural occurrences[edit]
Anthraquinone naturally occurs in some plants (e.g. aloe, senna, rhubarb, and Cascara buckthorn),
fungi, lichens, and insects, where it serves as a basic skeleton for their pigments. Natural
anthraquinone derivates tend to have laxative effects.

Industrial applications[edit]
Anthraquinone is used in production of dyes, such as alizarin. Many natural pigments are derivatives
of anthraquinone.

Alizarin is a typical anthraquinone dye. Formerly extracted from the madder plant, it is now synthesised.

Sulphonic dye[edit]
Direct dyes and acid dyes contain sodium sulphonate groups.

Triaryl dye[edit]

Triphenylmethane

Dyes having structures related to triphenylmethane are known as triaryl ('aryl' refers to the 'phenyl'
(benzene) rings).
There are many yellow and green dyes commercially applied to fibres that are related to
triphenylmethane.

Cationic dye[edit]
See Basic dye

Anionic dye[edit]
See Acid dye

Polyphenols[edit]
Many coloured plant compounds are classed as polyphenols as they contain multiple benzene rings
with multiple -OH groups attached. (A benzene ring with a single -OH group is called phenol.)

The structure of phenol can be shown in two ways. One emphasises the aromatic ring, the other shows the C=C
bonds which can conjugate.

The main active dye in turmeric is the polyphenol curcumin:

Demethoxycurcumin and bis-Demethoxycurcumin are also present, in smaller quantities. They lack
one or both methyl groups present in curcumin.
Flavonoids are polyphenols based on the flavone structure:

The yellow dye in onion skins is made a of mixture of flavonoids: quercetin, kaempferol and
quercetin-3-glucoside.[1]

Quercetin

Kaempferol

Quercetin-3-glucoside = Isoquercitin

Halochromic dyes and Indicators[edit]

A halochromic material is a material which changes colour when pH changes occur. The term
chromic is defined as materials that can change colour reversibly with the presence of a factor. In
this case, the factor is pH. pH indicators have this property.
Halochromic substances are suited for use in environments where pH changes occur frequently, or
places where changes in pH are extreme. Halochromic substances detect alterations in the acidity of
substances, such as detection of corrosion in metals.
Curcumin is a halochromic dye - at high pH its -OH groups become ionised to -O- and its colour
changes from red to yellow.
Redox indicators are not halochromic. These compounds change colour according to whether they
are oxidised or reduced.
Indigo (left) is blue and insoluble when oxidised, but is colourless and soluble when reduced (right).
In the reduced state it is known as leucoindigo.

Indigo

LeucoIndigo

Methylene blue is another example.

References[edit]

The Essential Chemical Industry (1985) Polytechnic of North

London.

Aspland, JR (1993) Chapter 12: The application of basic dye

cations to anionic fibers: Dyeing acrylic and other fibers with basic
dyes. Textile Chemist and Colorist Vol 25, No 6 June 1993 21-26

Aspland, JR (1991) Chapter 2/Part 2: Direct Dye Structure. Textile

Chemist and Colorist Vol 23, No 12 December 1991 30-32

StainsFile Dyes used in microbiology, with good details given.

1. Jump up Lokhande, HT & Dorugade, VA (1999) Dyeing Nylon

With Natural Dyes, American Dyestuff Reporter Feb. 1999 2934

Sources[edit]
w:Acid dye
w:Vat dye
w:Reactive dye
w:Azo compound
Category:

Technical Aspects of Azo Colorants

General chemistry
Azo colorants
Azo colorants encompass substances, which have one or more chromophoric groups
in their chemical structure and therefore are capable of colouring diverse substances
by selective reflection or by transmission of daylight. Azo colorants include both azo
dyes and azo pigments.
Azo colorants range in shade from greenish yellow to orange, red, violet and brown.
The colours depend largely on the chemical constitution, whereas different shades
rather depend on the physical properties. However, the important disadvantage
limiting their commercial application is that most of them are red and none are green.
Azo group
The part of an azo colorant molecule which produces colour, the chromophore group,
is a double bonded azo linkage. The chromophoric group of azo colorants alters
colour of a substrate, either by selective absorption or by scattering of visible light, i.e.
light with wavelengths of approximately 400-750 nm.
The azo linkage consists of two nitrogen atoms, which are also linked to carbon
atoms. At least one of these carbon atoms belongs to an aromatic carbocycle, an aryl
moiety, usually benzene or naphthalene derivatives or a heterocycle, e.g. pyrazolone,

thiazole. The second carbon adjoining the azo group may also be part of an aliphatic
derivative, e.g. acetoacetic acid.
In general, an azo colorant molecule can be summarised as follows:
aryl - N = N - R,
where R can be an aryl, heteroaryl or -CH = C(OH) - alkyl derivatives.
Stability of azo linkage
The azo linkage is considered the most labile portion of an azo dye. The linkage easily
undergoes enzymatic breakdown, but thermal or photochemical breakdown may also
take place. The breakdown results in cleavage of the molecule and in release of the
component amines. However, the azo linkage of azo pigments is, due to very low
solubility in water not available for intracellular enzymatic breakdown.
The component amines which may be released from azo dyes are mostly aromatic
amines (compounds where an amine group or amine-generating group(s) are
connected to an aryl moiety). In general, aromatic amines known as carcinogenic may
be grouped into five groups (Clayson & Garner, 1976).
Anilines, e.g. o-toluidine.
Extended anilines, e.g. benzidine.
Fused ring amines, e.g. 2-naphthylamine.
Aminoazo and other azo compounds, e.g. 4-(phenylazo)aniline.
Heterocyclic amines.

The aromatic amines containing moieties of anilines, extended anilines and fused ring
amines are components of the majority of the industrially important azo dyes.
Azo dyes
Azo dyes are, due to their relative simple synthesis and almost unlimited numbers of
substituents, the most numerous group of synthetic dyes. Azo dyes do not occur
naturally.
Azo dyes may have one or more azo groups. Azo dyes with one azo group are called
mono azo dyes, with two azo groups, diazo dyes, followed by triazo and polyazo dyes.

Azo dyes with more than three azo linkages are designated polyazo dyes. The most
commercial important are mono- and diazo dyes, triazo dyes, whereas polyazo are
much less important.
Nomenclature
Due to the complexity of the chemical names, azo colorants are only rarely referred to
using the IUPAC or CAS nomenclatures. Technical literature has adopted the
classification of azo colorants either by the chemical constitution or by the colour.
All commercial important azo colorants are identified by the Colour Index system.
Each colorant is given a generic name, e.g. Direct Brown, which briefly gives
information on application and colour. In addition to the generic name, a five-digit
number is allocated which unambiguously identifies the chemical structure of the
colorant.
In the Colour Index system, the azo colorants are provided with numbers ranging from
11,000 to 39,999 in correspondence with the Chemical Class shown in Table 3.1:
Table .1
Colour Index classification of azo colorants.
Klassificering af azofarvestoffer i henhold til Colour Index systemet.
Chemical Class

CI constitution no.

Mono azo

11,000-19,999

Diazo

20,000-29,999

Triazo

30,000-34,999

Polyazo

35,000-36,999

Azoic

37,000-39,999

Azo pigments
Azo pigments constitute the largest group of organic pigments due to the relatively
easy synthesis and the good technical performance.

In principle, the chemical structure of azo pigments is identical to the chemical

structure of azo dyes where the azo linkage is the chromophore group. The necessary
low solubility is achieved by avoiding solubilising groups or by incorporating groups
reducing solubility, e.g. amide groups, or by forming insoluble salts (lake formation)
of carboxylic or sulfonic acids.
Azo pigments are particulate solids, which are almost insoluble in water or other
media in which they may be dispersed for application. They colour other substances
by being physically attached to or incorporated into it. Furthermore, they are
physically and chemically unaffected by the substrates, which they are intended to
colour.
Technical properties of azo dyes
Azo dyes represent the largest, in number, group of synthetic dyes and the most
widely, in tonnage, manufactured. These dyes are, compared to natural dyes, better
capable of meeting requirements regarding technical properties, e.g. fastness to light.
The chemical diversity of azo dyes permits a wide spectrum of shades, mainly within
the scale of red. A disadvantage limiting their application is, however, that none of the
azo dyes are green.
The great majority of azo dyes are water soluble and they colour different substrates
by becoming physically attached. The attachment may be due to adsorption,
absorption or mechanical adherence.
Azo dyes have a broad industrial application field. They are used for colouring of
synthetic and natural textile fibres, plastics, leather, paper, mineral oils and waxes.
Their abilities of keeping an intense colour and fastness to light are quite good in most
cellulose fabrics but are relatively poor in colouring of cotton and wool.
A number of azo dyes are used as food colorants in cosmetics and as drugs for
treatment of bacterial infections.
Most of the commercial available azo dyes are in fact formulations of several
components in order to improve the technical properties of the dyeing process. The
content of a specific dye lies in the range of 10 to 98%.
The grouping of dyes, including azo dyes, often reflects a strict defined concept of
application. The majority of industrial important azo dyes belongs to the following
groups:

Acid dyes
Basic dyes
Direct dyes
Disperse dyes
Mordant dyes
Reactive dyes
Solvent dyes

The acid, basic, direct and reactive azo dyes are ionic, whereas disperse, mordant and
solvent azo dyes are non-ionic dyes.
Acid dyes
Acid dyes are the most widely used azo dye in Europe. The dyes are manufactured
and employed as water-soluble sodium salts of the sulfonic or carboxylic acid groups.
Acid dyes, which are anionic, are used in the textile industry for dyeing of all natural
fibres, e.g. wool, cotton, silk and synthetics, e.g. polyesters, acrylic and rayon. To a
less extent they are used in a variety of application fields such as in paints, inks,
plastics and leather.
Basic dyes
Basic dyes include water-soluble cationic azo dyes, characterised by positive
charge(s) introduced to the molecule.
Basic azo dyes belong to the oldest known class of synthetic dyes. Their first
application was in colouring of natural fibres, e.g. cotton, silk and wool. Later, they
were applied for the colouring of synthetics, like e.g. polyesters, acrylics and rayon.
Azo dyes with several cationic charges are important dyes for polyacrylonitril fibres.
Some of the basic azo dyes are used in medicine for treatment of bacterial infections.
Direct dyes
Direct dyes include water-soluble anionic azo dyes, which require the presence of
electrolytes for the dyeing process. Most of the direct dyes are benzidine-based. They
are classified as direct dyes, because they may be applied directly to celluloid fibres.

Furthermore, they are used for co- louring of rayon, paper, leather and to a less extent
nylon.
Disperse dyes
Disperse dyes encompass azo dyes, which are sparingly soluble in water and mainly
used for dyeing of synthetic (hydrophobic) fibres. The disperse dyes are clearly the
dominating group within azo dyes used world-wide. The fibres shall be in an organic
medium, in which the dye is more soluble than in water. The disperse dyes have been
used for cellulose acetate fibres, but now they are used in large quantities for dyeing
of polyester, polyamide and acrylic fibres.
Mordant dyes
Mordant dyes include azo dyes, which are converted into their final, insoluble form on
the fibres. A mordant is a metal, most commonly chromium, aluminium, copper or
iron. The dye forms together with a mordant, an insoluble metal-dye complex and
precipitates on the natural fibre. The application area is limited to the colouring of
wool, leather, furs and anodised aluminium.
Reactive dyes
Reactive dyes encompass azo dyes, which form covalent bonds with the fibres they
colour, e.g. cotton, rayon, cotton, wool silk and nylon. The dye molecule contains
specific functional groups, which can undergo addition or substitution reactions with
the -OH, -SH and -NH2groups present in the fibres. Due to very good fastness of the
substrate, the reactive dyes are one of the most important group of dyes for colouring
of textiles.
Solvent dyes are used on a large scale in many industrial sectors. They are dissoluted
in the substrate they colour. The small fastness to light of these dyes depends heavily
on the substrates being coloured. They are used for coloration of inks, plastics (mainly
for polystyrene and resins of polymethacrylate), wax and fat products and mineral oil
products (gasoline, fuels lubricants and greases).
Solvent dyes
Technical properties of azo pigments
Pigments are widely used. The most important area of use is in the graphic printing
inks, where approximately 50% of all pigments are used. 25% of the pigments are
used in paints and coatings and less than 20% in plastics and fibres. The remaining

application fields are e.g. textile printing, office articles, wood, paper, cosmetics and
food and feed colouring.
The industrial production and use of pigments, including azo pigments, are expanding
world-wide. Most probably 50% of the organic colorants applied within industrial
processes are today organic pigments (Ullmann, 5th Edition).
Physical properties like size and shape of pigment particles, crystal geometry and
presence of impurities are responsible for the efficacy of the colouring process. The
maximum particle size of most of the commercial pigments is less than 1 m and
often even smaller than 0.3 to 0.5 m. The smallest particles may be one to more than
two orders of magnitude smaller. The small particles tend to agglomerate and form
crystallites, and this tendency increases with decreasing particle size. Organic
pigments, as powders, will therefore comprise of a mixture of such crystallites and
single crystals.
Pigment particles may assume a variety of shapes, such as cubes, platelets and needles
as well as a number of irregular shapes in combination.
Commercial pigments are available as powdered crystalline solids or already
dispersed forms. Dispersion is performed by the manufacturer and may contain carrier
material and dispersing agent. The efficiency of dispersion is very important for the
process of colouring. After dispersion of the pigment, particles may be stabilised in
order to avoid flocculation. This is particularly important for the application of
pigments in thermoplastic materials, e.g. polyvinylchloride.
Technical properties of azo pigments always refer to the complete pigment system,
which beside a pigment constitutes of e.g. solvents and binders etc. Of particular
interest are migration, thermal stability, fastness to light and weather resistance. In
solvent-based printing inks, pigments must be extremely resistant to the solvent used
in the ink.
The rough grouping of azo pigments may be based on the numbers of azo groups
and/or the type of coupling component. Azo pigments may be allocated to the
following groups (Ullmann, 5th Edition):
Benzimidazolone pigments
Diazo pigments
Disazo condensation pigments

Monoazo Yellow and Orange pigments

Naphthol AS pigments
b -Naphthol pigments
Azo pigment lakes

Benzimidazolone pigments
Benzimidazolone pigments provide a range of colours ranging from greenish yellow
to orange, medium red to carmine, bordeaux and brown shades. The technical
performance is excellent. Benzimidazolone pigments are used for exterior-use paints
of a high quality, e.g. car finishes. Furthermore they are used for colour plastics and
for high grade printing inks.
Diazo pigments
Disazo pigments may be characterised by a double azo and/or by double coupling
components. Diazo pigments provide colours in the range from very greenish yellow
to reddish yellow and orange and red. In comparison with the yellow and orange
pigments of monoazo, the diazo pigments provide better solvent and migration
fastness, but poorer fastness to light and weather resistance. These pigments are
economically very important, particularly in the production of printing inks. The main
use encompasses printing inks and plastics.
Disazo condensation pigments
Condensation of two monoazo pigments provides a pigment "double in size". The
final colours range from greenish yellow to orange, red and brown. Due to their large
molecular size, they are of very good technical properties, particularly very good
migration fastness and thermal stability. These properties make disazo condensation
pigments suitable for colouring of plastics and paints.
Monoazo Yellow and
Orange pigments
Monoazo pigments provide a range of colours from yellow to orange. The yellow
pigments were introduced 80 years ago and they are relatively cheap and very light
fast. Therefore they are still very widely used, mainly in coating materials and
especially in air-drying and emulsion paints. They are also used in the printing
industry.

Naphthol AS pigments
Naphthol AS pigments, so-called naphthol reds, are all red, providing a range of
colours from yellowish and medium deeply red to brown and violet. The technical
properties vary. In general Naphthol AS pigments have a good fastness to light and
are weather resistant, but they tend to migrate. The main area of use is in printing inks
and interior paints.
b -Naphthol pigments
b -Naphthol pigments belong to the oldest known synthetic colorants. They are
characterised by good fastness to light and weather resistance. On the other hand they
have a poor migration fastness. Today only a few b -naphthol pigments are in use,
mainly for colouring of inexpensive coating materials.
Azo pigment lakes
Azo pigment lakes are synthesised from monoazo dyes, which are converted to an
insoluble form by formation of salt with metals. Azo pigment lakes provide colours
from yellow to red. The red pigments have a brilliant shade and are of great industrial
importance. The technical properties of azo pigment lakes vary, but they have a good
fastness to light, weather resistance and a high thermal stability, whereas some tend to
migrate. They are used in almost all printing sectors and for colouring of plastics.

REACTIONS OF DIAZONIUM SALTS

This page looks at some typical reactions of diazonium ions,
including examples of both substitution reactions and coupling
reactions. If you have come straight to this page from a search
engine and want to know about the preparation of the diazonium
ions, you will find a link at the bottom of the page.

Substitution reactions of diazonium ions

Diazonium ions are present in solutions such as
benzenediazonium chloride solution. They contain an -N2+group.
In the case of benzenediazonium chloride, this is attached to a

benzene ring.
Benzenediazonium chloride looks like this:

In this set of reactions of the diazonium ion, the -N2+ group is

replaced by something else. The nitrogen is released as
nitrogen gas.
Substitution by an -OH group
To get this reaction, all you need to do is warm the
benzenediazonium chloride solution. The diazonium ion reacts
with the water in the solution and phenol is formed - either in
solution or as a black oily liquid (depending on how much is
formed). Nitrogen gas is evolved.

This is the same reaction that you get if you react phenylamine
with nitrous acid in the warm. The diazonium ion is formed first
and then immediately reacts with the water in the solution to
give phenol.
Note: In this, and all the other reactions of diazonium ions on this
page, I am going to write the attached groups at the side of the
benzene ring rather than at the top. There's no very sophisticated
reason for this! When I write the equations for the coupling reactions
further down this page, that's the way I want to draw the structures,
because I think it makes them clearer. I am just trying to keep
everything else consistent with that.

Substitution by an iodine atom

This is a good example of the use of diazonium salts to

substitute things into a benzene ring which are otherwise quite

difficult to attach. (That's equally true of the previous reaction, by
the way.)
If you add potassium iodide solution to the benzenediazonium
chloride solution in the cold, nitrogen gas is given off, and you
get oily droplets of iodobenzene formed.
There is a simple reaction between the diazonium ions and the
iodide ions from the potassium iodide solution.

Coupling reactions of diazonium ions

In the substitution reactions above, the nitrogen in the diazonium
ion is lost. In the rest of the reactions on this page, the nitrogen
is retained and used to make a bridge between two benzene
rings.
The reaction with phenol
Phenol is dissolved in sodium hydroxide solution to give a
solution of sodium phenoxide.

The solution is cooled in ice, and cold benzenediazonium

chloride solution is added. There is a reaction between the
diazonium ion and the phenoxide ion and a yellow-orange
solution or precipitate is formed.
The product is one of the simplest of what are known as azo
compounds, in which two benzene rings are linked by a
nitrogen bridge.

Note: You might wonder where the hydrogen in the -OH group
comes from. It was pushed off that same ring when the nitrogen
became attached.
I have made a positive decision not to give names for the products of
these coupling reactions. The problem is that there are lots of
different variations on the names in common use. Almost every book
you look in calls them something different. One web source quoted 45
versions for the compound sometimes called "aniline yellow" (see
below). Admittedly, 29 of these were terms like "fast spirit yellow" and
"Sudan yellow R", but 16 were variations on chemical names.
Any name which I give is quite likely to conflict with one which you
have got from another source - teacher, lecturer or textbook. I'm not
going to add to your confusion! Learn the structures, and don't worry
too much about the names.

The reaction with naphthalen-2-ol

Naphthalen-2-ol is also known as 2-naphthol or beta-naphthol. It
contains an -OH group attached to a naphthalene molecule
rather than to a simple benzene ring. Naphthalene has two
benzene rings fused together.
The reaction is done under exactly the same conditions as with
phenol. The naphthalen-2-ol is dissolved in sodium hydroxide
solution to produce an ion just like the phenol one. This solution
is cooled and mixed with the benzenediazonium chloride
solution.
An intense orange-red precipitate is formed - another azo
compound.

The reaction with phenylamine (aniline)

Some liquid phenylamine is added to a cold solution of
benzenediazonium chloride, and the mixture is shaken

vigorously. A yellow solid is produced.

These strongly coloured azo compounds are frequently used as

dyes known as azo dyes. The one made from phenylamine
(aniline) is known as "aniline yellow" (amongst many other
things - see note above).
Azo compounds account for more than half of modern dyes.

The use of an azo dye as an indicator - methyl orange

Azo compounds contain a highly delocalised system of electrons
which takes in both benzene rings and the two nitrogen atoms
bridging the rings. The delocalisation can also extend to things
attached to the benzene rings as well.
If white light falls on one of these molecules, some wavelengths
are absorbed by these delocalised electrons. The colour you
see is the result of the non-absorbed wavelengths. The groups
which contribute to the delocalisation (and so to the absorption
of light) are known as a chromophore.
Note: A Canadian university site describes "chromophore" as "one of
those useful but sloppy words whose meaning depends somewhat on
the context."
Some sources take the chromophore as being the whole of the two
benzene rings and the nitrogen bridge. Others seem to take it as just
the -N=N- group.
I'm taking the line that it is the two benzene rings plus the -N=Ngroup. If your examiners take the more restricted meaning, obviously
you should go with what they want. The only way you will find that out
is to look at recent exam papers and mark schemes. If you are a UK
A level (or equivalent) student follow this link to the syllabuses page
to find out how to get hold of these if you haven't already got them.

Modifying the groups present in the molecule can have an effect

on the light absorbed, and so on the colour you see. You can

take advantage of this in indicators.

Methyl orange is an azo dye which exists in two forms
depending on the pH:

Note: You may find other structures for the red form (I use a variation
elsewhere in this site!) with different arrangements of the bonds
(although always with the hydrogen attached to that same nitrogen).
The truth is that there is delocalisation over much of the structure, and
no simple picture will show it properly. This case is discussed in detail
on a page in the analysis section of the site about UV-visible
spectroscopy. This is quite difficult stuff, and if you are coming at this
from scratch you will have to explore at least one other page before
you can make sense of what is on that page. There is a link to help
you to do that. Don't start this lightly!

As the hydrogen ion is lost or gained there is a shift in the exact

nature of the delocalisation in the molecule, and that causes a
shift in the wavelength of light absorbed. Obviously that means
that you see a different colour.
When you add acid to methyl orange, a hydrogen ion attaches
to give the red form. Methyl orange is red in acidic solutions (in
fact solutions of pH less than 3.1).
If you add an alkali, hydrogen ions are removed and you get the
yellow form. Methyl orange is yellow at pH's greater than 4.4.
In between, at some point there will be equal amounts of the red
and yellow forms and so methyl orange looks orange.
Note: You can find out much more about indicators in the physical
chemistry part of this site.