DYES AND ITS CLASSIFICATIONCOLOUR & CONSTITUTION Witt's Theory of Colour (1876) According to the Otto N. Witt calour theory a dye is made up of two essential kinds of parts, Chromophores and Auxachromes, He-designated a group that produces colour as a chromophore (Gr. chroma, colour + Phors, to carrier). Chromophores are unsaturated groups. Presence of at least one such group is essential to produce a colour in an organic compound and a molecule containing such a group is called as chromogen. Some most effective chromophores are > =e aes Thus for example nitrobenzene is pale-green, azobenzene is orange-red, p-quinones are yellow and O-quinones are orange or red, Certain other unsaturated groups produce colour only when several of them are present in a molecule and when they are conjugated. Thus though acetone is colourless, biacetyl_ yellow colour. certain groups, while not producing colour themselves, are able to intensify the colour when present in a molecule together with a chromophore, These are called auxochromes (Gr, Auxein = to increase). The most effective auxochromes are: -OH ,-OR , -NH2 ,-NHR & —NRe . Thus nitrophenots and nitroanitines are more intensely coloured than nitrobenzene and aniline and are deep yellow to orange. wTModern theory of colour When white light falls on a substance, the liglit may be completely reflected and in this case substance will appear white. If it is compietely absorbed, the substance will appear black. If a substance absorbs all visible light except that corresponding to e.g. yellow, it will transmit or reflect only yellow colour and will be seen as yellow. However, it is generally seen that, light of only one colour is absorbed in which case the substance will appear to have the complementary colour. Thus, if the light is absorbed from the violet region of spectrum, the substance will be seen as yellow. If light is absorbed from the red region, the substance will appear green read (Munsell Colour Wheel)Valence bond theory According to this theory, itis the resonance stabilization of excited states that is responsible for the absorption in the visible region. When ultraviolet or visible light is absorbed by a molecule, an electron is excited, that is, it is promoted to an orbital of higher energy. The wavelength of light absorbed depends on the energy difference between the excited and ground states of the molecule. The smaller difference between the two states, the longer is the wavelength of the light absorbed, The energy required to promote an electron depends upon the environment of the electron. Sigma (o) bond electrons are firmly held and very high energy (or shart wavelength) is necessary to promote electrons and may at times break the molecule and form free radical. Pi (n) electrons are less firmly held and require less energy (or longer wavelength) to excite, Electrons belonging to conjugated systems fequired even less energy (still longer length). Conjugation and resonance stabilize the excited state by sharing and delocalizing higher energy of the excited electron. s conjugation and resonance increases, the wavelength of light absorbed also increases and when the wavelength is long enough to be in the visible region, we observe colour. ond! Be O44 ad Cotourless Cotourtess inscorbe 1800 4 Ansorbs B170 A Absorbs S808 vas B-carotene ( Orange Xabsarbs at 4510 A, that is, in the visible region).Molecular orbital theory The electronic transitions can occur b ythe absorption of ultraviolet and visi ble radiation. Although transitions ar e possible; only the following ty pes are allowed: no" “nn anda + nt Ao —+ o* transition takes place when a bondin g @ -electron is excited to an antibonding « orbital, ie. 0”. This type of transition requires a. very large amount of energy as. o - electrons are very tightly bond. Hence the compounds like saturated hydrocarbons which do not have any n oro electrons may undergo ‘only a — a® transions, However, these tran sions do not take place by absorbing in the ord inary ultraviolet region, e.g,, ethane absorbs. at 135 mp. ‘Chan sowing molecu ort Athens thang aarp weeding 7 ewes, + sete, roDYE ~ Dyes are colored organic compounds that are used to impart color to various substrates, including paper, leather, fur, hair, drugs, cosmetics, waxes, greases, plastics and textile materials. » ADye isa colored compound, normally used in salution, which is capable of being fixed to a Oe een 1. Colour 2. Solubility in water 3. Ability to be absorbed and retained by fibre (substantivity) or to be chemically combined with it Kreactivity). 4, Ability to withstand washing, dry cleaning and exposure to light. + The dye has a colour due to the presence of chiomophore and its fixed property to the acid or basic groups such as OH.SO3H, NH2, NRz, etc. - The polar auxechrome makes the dye water-soluble and binds the dye to the fabric by interaction with ‘the oppositely changed groups of fabric structure. va}CLASSIFICATION OF DYES. A. Classification Based on the Source of Matetialgmon ciassification of the dyestuff is based on the source from which it is made. Accordingly ‘the classification could be: 1. Natural Dyes + Natural dyes are dyes or edlorants derived from plants, invertebrates. or minerals. he marae of natural dyes are vegetable dyes from plant sources. E.g. roots, berries, bark, leaves, and woot Other organic sources include fungi and lichens. 2. Synthetic Dyes Almost ail the colors that you see today are Synthetic dyes. Synthetic dyes are used everywhere in everything from clothes,to paper, from food to wood. This is because they are cheaper to produce, brighter, more color-fast, and easy to apply to fabric vas eg, Acid Dyes, Azo Dyes, Basic Dyes, Mordant Dyes, etcB. Classification Based on Chemical Structure 1. Nitro Dyes : Nitro dyes are polynitro derivatives of phenols containing at least ane nitro group ortho or para to the hydroxyl group, They are of little importance industrially because the colors are not very fast. A few examples are : H “oe “OG NO, Hs (Picriciaeid) (Naphthol yellow $) Naphthol yellow S can be used to dye wool, & is one of colors permitted in foods. ¢2. Azo Dyes The azo dyes are by far the most important class, accounting for over 50% of all commercial dyes, They are, characterized by the presence of one or more azo groups ( --N=N-), which from bridges between two or more aromatic rings. Preparation : Involves two steps - 1. Diazotation NaNO2 = + HCL ———+ HNOz + NaCl Cu) + HNO: + Ho OSC, eS tia + 2H:O (Nitrous acid) (A primary (Adlazonium aromatic amine) compound) 2. Coupling JOH(— NH2;- NR2) ae on or an (adye) raya. Aniline Yellow Cris + On tT: wer Benzenediazanium chloride Aniline yellow is used as a dye for oils & lacquers, & is also an intermediate for other dyes. b, Butter Yellow ¢. Chrysoidine © Chrysoidine is an orange: red dye . It is used for dyeing paper , leather .& jute. wer cr nvphenylediamine asld. Methyl Orange vs CH Diazatized sulfanilic acid NN-Dimetylaniline Helianthine Hic » fethyl_ Orany p Dienattantt ae RR inte Acid) Preparation- Methyl orange is prepared from Diazotized sulfanilic acid and N.N-dimethylaniline. The first product obtained from the coupling is the bright red acid form of methyl orange, called helianthine. In base, helianthine is converted to the orange sodium salt, called methyl orange. aslProperties- Methyl orange is a pH indicator and due to its clear color change it is very often used in titrations, Methyl orange changes color at the pH of a mid-strength acid and is usually used in titrations for acids. Unlike a so called universal indicator, methyl orange does not have a full spectrum of color change, but has 2 Spoce-filling model of methyl | Potaer of methyl orange Left: Methyl orange in an acidic range soluton ight: Methyl orange im an basic sohition Methyl orange is often used as an acid-base indicator. In sélutions that are more basic than pH 4.4, methyl orange exists almost entirely as the yellow negative ion, In solutions that are more acidic then pH 32, itis protonated to form a red-dipolar ion, ‘i = _ Ne ot pe KOM si methy! orany son [Her =D f } WY z 2 an wa of ne ne Soe = = read Rema ~ 5200e. Bismarck Brown ar Ny aes “cy rat Phenylenediamine Phenylenediamine Tetrazotized yy phenylenediamine HON NH CouplINE HN NH, N N Ne Sn Bismarck Brown It is also a diazo dye. Bismarck brown is obtained by coupling tetrazotised m-phenylenediamine ‘with two molecules of m-phenylenediamine. Bismarck brown is used for dyeing leather , wool, & cotton m3. Diphenylmethane Dyes Skeleton Of all diphenylmethane dyes is eg. Auramine O H.@-H ce Auramine O is used to dye wool, silk, nylon , rayon & paper, vay4. Triphenylmethane Dyes Central carbon atom is joined to two benzene rings & to a p-quinoid group. ‘Skeletal str. eg. CH, Orn. Malachite Green ‘Triphenylmethane dyes are not fast to light or washing , however , except when applied to acrylic fibers. They are used in large quantities fer coloring paper & type written ribbons where fatness to light is not so important. vay5. Xanthene Dyes Skeletal str. ©8- Fluorescein HO. 0. OH CT os OX 0 Fluorescein Uranine Fluorescein is of no value as a dye . It is a red powder, which is insoluble in water. The sodium ‘Salt of fluorescein is called Uranine . It is used to dye wool & silk, vay6. Phthaleins 8, Phenolphthalein Ho. os he. = . | oH Be cate cost | Phenoiphthalein 2 ‘Sodium salt (Red) ‘Trisodium salt ( Colorless ) Phenolphthalein is not a dye. It is-a colortess solid, mp 261 C & is insoluble in water , but dissolves in alkalis to form deep red solutions, Because of the color changes shawn above, phenolphthatein is used as an indicator in aci titrations, Phenolphthalein is an extremely powerful laxative , & this accounts for its widespread use as a denaturant for laboratory alcohol. Via} base7. Indigo Dyes Indigo dye is an organic compound with a distinctive blue color Historically, indigo was a natural dye extracted from plants. But today nearly all indigo dye is produced synthetically. It contains carbonyl chromophore. 9° q oO Indigo The primary use for indigo is as a dye for cotton yarn, which is mainly for the production of denim cloth for blue jeans Small amounts are used for dyeing wool and silk. asl8. Anthraquinone Dyes Anthraquinone dye, any of a group of organic dyes having molecular structures based upon that of anthraquinone. °o I or n eg. Alizarin oO On coo” QO Alizarin Alizarin is also used commercially as a red textile dye. vC. Classification Based on Methods of Application 1. Direct Dyes Carried out in a neutral or slightly alkaline dye solution. It contains acidic or basic auxechromes. Polar in nature: Used on cotton, paper, leather, wool, silk and nylon, OH NOz NO, Fiber-NHz + HO-Dye Martius yellow Fiber-NHB¥..... vad2. Mardant Dyes: This class of dyes requires a pretreatment of the fiber with a mordant material designed to bind the dye. ‘A mordant is any substance which can be fixed to fabric and reacts with the dye to produce Colour on Fabric. Actually the mordant forms an insoluble co-ordination compound between the fabric & the dye & bound the two. Metallic mordants like salt of alurninium , chromium , iron ,tin etc which are used with acidic dyes. eg, Alizarin is a classic mordant dye. It provides different colors depending on different mordant. It gives a red colar with aluminium & tin salt , brownish red colour with chromium mordant & black violet “ALL APE OP BOA are involved in the fundamental reaction betwe (Fabac] ena mordant dye and a mordant. One is a covalent bond with usu M ally hydroxyl oxygen and the metal atom. The other is a coordin eet ate bond with the metal with the double banded other oxygen Al aan on + Als 4 Fiber Coordination compound ef Alizarin Alizarin with Ab-3. Vat Dyes ‘These dyes are insoluble in water , but on reduction with sodium hydrosulfite yield alkali soluble forms leuco- compounds) which may be colorless, It is in this form they are introduced into the fabric. After the reduced dye has been absorbed in the fiber , the original insoluble colored dye is reformed by oxidation with air or chemicals Vat dyes are used to dye cotton, & are very fast because of their insolubiity in Water . Indigo is a good example of vat dye. CBiue, wane ok, Indizo-whies, Colourless ; water soluble4. Ingrain Dyes ‘These are also called developed dyes; these dyes are actually made inside the fibers of the fabric. The fabric is treated with the two components used to synthesize the dye. These precursor molecules are small enough to diffuse into the pours and spaces between the fibers in the fabric. They then react to form the dye which is trapped inside or “in the grain” of the fibers, because of the large size of the dye molecule. Azo dyes such as Parared are used as ingrain dyes for cotton, The fabric is soaked first in a solution of the coupling component f-naphthol and then ina solution of diazotized p-nitroaniline 5. Disperse Dyes ‘These dyes are insoluble in water, but are capable of dissolving certain synthetic fibers. Disperse dyes are usually applied in the form of a dispersion of finely divided dye in a soap solution in the presence of some solubilising agen such as phenol.cresol or benzoic acid. The absorption in to the fiber is carried out at high temperature and pressure. isperse dyes are used to dye avetate rayons.nylon and other synthetic fibers celliton fast pink B (I.umino-4hydroxy-anthraquinone) and cel aminoanthraquinone) are the examples of disperse dyes n fast blue B (1,4-N,N"-dimethyt ro2 y ; Hy? OH O HN Celliton Fast Pink B Celliton Fast Blue B ROPERTIES OF DISPERSE DYES: 1 Disperse dyes are readymade dyes and are insoluble in water or have very low water solubility. 2.They are organic colouring substances which are suitable for dyeing hydrophobic fibers 3.Disperse dyes are non-ionic dyes.so they are free from ionising group. A.Disperse dyes are used for dycing man made cellulose ester and synthetic fibres specially acetate and poly ester fibres and some times nylon and acryllic fibres S.currier for dispersing agents are required for dyeing with disperse dyes. 6.Disperse dyes have fair to good light fastness with rating about 4-5, Via!