UNIT-III DYES —— INTRODUCTION A dye is a coloured substance which when applied to the fibric imparts to it a permanent colour. ‘The colour imparted is resistant to the action of light, water and soap. ‘Some important characteristics of a dye are : (i) It should impart a suitable colour. (ii) It should be resistant to the action of water, soap and detergents. (iii) It should be capable of fixing itself to the material to be dyed. (iv) Tt should be fast to sunlight, heat and other normal atmospheric conditions. (v) It should be preferably soluble in water. It may be noted that all dyes are coloured but all coloured substances may not act as dyes. Essentials of a coloured substance to act as dye. Some essentials of a dye are : (i Presence of Chromophore. These are the groups which produce colour to a dye since they are capable of absorbing light inthe near ultra-violet region, ~ NO,, > C = O, (- CH= CH ~) etc, are some of the chromophores. The compounds in which chromophores are present are called chromogens. (ii) Presence of Auxochromes. A dye should be resistant to the action of light, soap and water. Clearly, it should attach to the fibres by means of stable chemical bonds. The group which forms stable chemical bonds are either acidic or basic in nature. Such groups are called auxochromes or colour enhancing groups. ~ OH, ~ SO3H, ~ NH, etc, are some of the auxochromes. A chromogen without an. auxochrome can never act as a dye.S ore 321 coLouR AND CONSTITUTION («) Colour. We know that when white ligh falls on a substance, three Processes (i) In case the light is totally reflected, the substance appears white, em (i) In case the light is totally absorbed, the substance appears black, (ii) In case, the light is partially absorbed and the re st is reflected, colour of the reflected light, then the substance has the Table 4.1 Wave lengths and Complementary colours Wavelength Colour Colour reflected (nm) absorbed (complementary colour) 400-435 Violet ‘Yellow-green 435-480 Blue Yellow 480-490 Green blue Orange 490-500 Blue-green Orange 500-560 Green Purple 560-580 Yellow-green Violet 580-595 Yellow Blue 595-605 Orange Green-blue 605-750 Red Blue-green Alsoif only a single band is absorbed, then the substance has complimentary colour of the absorbed band. For example, if a substance absorbs blue colour, then the reflected light will have yellow colour, ‘The reason is that yellow is the complimentory colour of blue ‘mn fact, no substance absorbs a single band, no dye has a pure shade. For example, Melachite ‘green predominantly reflects green light but also to small extent, it also reflects red, blue and violet colour, It may, however, be noted that substances which appear to be colourless also have absorption Spectra. In such cases, absorption takes place in the LR and UV regions but not in the visible region of tlectomagnetic spectrum. (©) Relationship between Colour and Constitution, Many theories have been put forward ‘ime to time to relate colour with the molecular structure of the compound. A few such theories are described below: rea, it’s ehromophore-auxochrome theory. Otto Witt (German-1876) put forward his theory " SNE colour and constitution, It is known as chromophore-auxochrome theory. The main points of his theory are as follows : ’ tragy Som PoUn Should essentially contain certain groups which are ale a ee eh ups on Mares. These groups generally contain double ot tiple bons ‘ompound, deeper is the colour. from eeMODERN COLLEGE CHEMISTRY (SEMESTER VI PAPER Xi! Ayp xIv) 322 Some important chromophores are : ° Z ii) SI iii) -N=N- 0% oe eet (eitro) (iv) >C =O (iv) >C=S (i) (( CH=CH -), sete. (Carbonyl) (thiocarbonyl) i) The compound which contains a chromophore is called chromogen. Niro group usually imparts yellow colour to the substance, In - CH = CH — compounds, intensity of colour increases if the number of double bonds in conjugation increase. (iii) There are certain groups which when present alongwith a chromophore deepens the colour, Such groups are called auxochromes. The auxochromes do not produce any colour in the absence of a chromophore. Auxochromes are essential groups for the chromogens to act as dyes. Some important auxochromes are : (a@)- OH (b) OR (c) - NH (d) - NHR etc. (iv) In CgHs(CH = CH),C¢Hs, as the number of conjugated dienes increases, the colour deepens, For example C,H; (CH = CH),C,H; CH, (CH = CH);CgHs Colourless Pale yellow Carotene (pigment present in carrots) has orange red colour due to the presence of eleven conjugated double bonds in it) ‘OH (auxochrome) a Sy NOz Oz (chromophare) | chromophore xy 2 NOz NO2 1,3-Dinitonaphthalene (Pale yellow) 2, 4-Dinitro-t-napththol (orange rec) Also consider the following compounds containing chromophores. Let us consider the following dyes: : -OH is auxochrome @ on—_\—v=n—_Y- OH colour is deep orange a = —NHe is auxochrome iy on n_S- NH Golour is Red-Yellow i ow Yn nt_S- N(CHg)2_ N(CHg)2 is auxochrome colour is Deep red oH OoN Noo Here Trintrobenzene is chromogen and -OH group is auxochrome No2\“ 323 ves . ‘i pathochromic effect. This effect is due to the groups which when introduced in a chromogen a apsorption (0 higher wavelength. Thus, these groups cause a red shift, ie., absorption shi ai “seed end. Such gr0US are auxochromes which help inthe deepening ofthe colour e : ; . pw i. sochromic effect. It is an effect by virtue of which the absorption is shifted towards shorter | ‘the absorption shift towards shorter wavelength is also called blue shift. cgvelengt. : row valence Bond Theory. According to the modem concept, valence bond theory expsins fly effect of SFOUPS in the absorption of colours. The electron pairs of a molecule in its ground state are teat of silation, When a molecule is placed ina beam of ight it absorbs photon of light. The poke getsexited. The energy absorbed is clearly the diference in energy between the two stats of ‘Smoke. Smaller the difference in ener, longer is the wavelength absorbed. It may be noted that. required to excite o-electrons, lesser energy for -lectrons and still lesser energy sasimam energy 18 : jsrequired (0 promote delocalised z-electrons. Clearly, the absorption in wavelength is raised, if : (there is greater conjugation in double bonds. (ii) there is greater delocalisation of z-electrons. We know that ethylene is colourless but polyene is coloured. Actually the intensity in colour ingeases with increase in the number of double bonds in conjugation. For example, Ethylene (one double bond) absorbs at 170 mue while butadiene absorbs at 217 mu. The bathochromic shift (shift to iongee wavelength) is more pronounced if double bonds are in conjugation as compared to isolated double bonds in which there is a litle interaction between them. In a compound of highly conjugated the p-orbitals of carbon atoms overlap and cause extensive delocalisation of the zt-electrons. system, nergy level of highest occupied orbital is raised and that of the lowest unoccupied ‘The net result is that the e1 antibonding orbital is lowered. Now this absorption corresponds to the transition of lower energy or higher wavelength (See Fig 4.1), a7 aa (Conjugates aan. (overlapping of p-orbitals) Fig. 4.1 Electronic transitions in conjugated dienes. (Highest occupied molecular Asthe et orbital) is lowered. Due i ital i raised 0 this Crease in. ; Shifteg 1545 yy in energy absorption, the wavelength is raised. The four, # towards higher wavelength in conjugated system as the electron density i ON atoms, . Ms. A highly conjugated system such as -carotene absorbs longer wavelengths lent of conjugation increases, the energy level of HOMO While the energy level of LUMO (Lowest unoccupied motecula absorption maximum is usually pread on whichMODERN COLLEGE CHEMISTRY (SEMESTER VI PAPER Xill AND XIV) 324 highly conjugated system and it appears orange fall in the range of the visible spectrum, f-carotene is a (visible region). -Carotene (orange) in conjugation, the energy I decrease in energy, shifts the V/-R effect extends evel of the excited state is lowered absorption to higher wavelengths. the conjugation system and thus As already stated, with the increase and that of the ground state is raised. This ‘The presence of auxochromes with +/4R or — shifts the absorption to the higher wavelength. 3, Molecular Orbital theory. According to this the light, one electron is promoted from a bonding or non ponding orbital toan antibonding orbital. Depending upon the types of electrons present in a molecule, different types of electronic transitions are possible. (i) The antibonding orbital which is ass with the excitation of a electron is called o* antibonding orbital. Sug too* transition takes when o (sigma) electron is promoted *) orbital. It is represented ory, when a substance absorbs a photon of sociated Toe place to antibonding (0" as 0 > o* transition nding (n) electron gets ding sigma orbital, then 7a ° osaF (i) When a non-bo promoted to antibon it represents n—> 0* transition. _—+ m* transition represents the f m-electron to an antibonding Fig, 4.2 Electronic excitation energies. Gii) Similarly promotion of orbital ie. 2* orbital. ‘Similarly, when electron is promoted to antibonding orbital, itrepresentsn—> 2° orbital. The energy required for various transitions obey the following order. o— ot > n— oF > > nT It may be noted that 7 —* z* and n—> 7* transitions lie in the ordinary ultraviolet region (200-400 nm). As the conjugation increases, absorption - (CHo=CHe CH= CHe fv, Ethylene due to 7 —> z* transitions shift to longer wavelengths and may reach visible region which is responsible for the es colour, When ethylene molecule gets excited, it gives ae ip — CH, diradical. The electron cloud is spread ; prea on. Eo Fig, 4.3 Molecular orbitals of carbon atoms and absorption occurs at 170 nm. Butadiene Buta-t, diene.pves. 325 ctiy= CH ~ CH = CH as two double bonds in eo (Cae savelength and it absorbs at 212 nm. The batho Jone ained as below : sexe! . ‘A double bond consists of two zt - MO, i. one bonding and one antibonding. But when two double bonds are in conjugation, four MO. result. ‘Two of these are zr; and 3 (bonding MO) and each cccupy @ Pai of electrons, The other two (i.e, zt3* and am4*) are antibonding MO. Asa result of increase in conjugation, the energy of the highest occupied molecular orbital (HOMO) increases and that of the lowest unoccupied molecular orbital (LUMO) decreases. Clearly, fag" transition occurs at lower energy or higher wavelength Alsoas the two molecular orbitals (77, and5*) come closer, the interaction between them increases nd due to this, absorption is intense i.e. f=, increases, Similarly, a molecule with three double bonds inconjugation absorb at still higher wavelength, It js found that a compound with more than six double tonds in conjugation start absorbing in blue region and the substance appeares yellow which is its complementary colour. -Carotene (orange) absorbs in the greenish blue region. Now let us consider benzene and polynuclear aromatic compounds. Benzene absorbs at 254 nm ue to - 27* transition. Naphthalene and anthracene with increased conjugation absorb at 225 nm and 315 nm respectively but still these are colourless compounds. Naphthacene is yellow at 474 nm and Pentacene is blue at 580 nm. OOOO OOODO Naphthacene Array 474 nm Pentacene, Aa 580 nm (yellow) (Blue) njugation. The conjugation shifts absorption to chromic sift (ie., shift to increased wavelength) Classification of Dyes Dyes can be classified in the following ways : 1. Mordant dyes and Chemistry of dyeing. These dyes require a mordant for dyeing animal (vegetable fibres. For an acidic dye, a basic mordant is used and vice [Link] acidic dyes, the Mordants are metallic hydroxides while for basic dyes, tannic acid is generally used.)For metal ‘ordanting, the fabric is dipped into a solution of the metallic salt and the padded fibre is then dipped ‘othe solution of the dye. This produces an insoluble coloured lake which is fast to washing. For in mordanting, the fibre is dipped into a tannin bath, but since the lakes are dull and tend to be ‘igtve, artaremetic is added to the tannin bath. This produces brighter and more insoluble lakes. a - ‘ai, <—— Mordant LN Oo oO ,OH OU —~ The coy ° ; 5 * chelate gat OF the lake depends on the metal such as iron, chromium, aluminium etc, Lakes Pounds formed between the metal and the dye. The majority of the mordant dyes3 26 MODERN COLLEGE CHEMISTRY (SEMESTER VI PAPER Xill AND XIV) owe their special properties to the presence of hydroxyl groups and it appears that dyes containing one hydroxyl group will be mordanted if this hydroxyl group is ortho to the carboxyl, nitro or azo group. These dyes are primarily used to dye wool. The cloth is Ast dipped in solution of a suitable fetal salt (mordant) and the soaked fabric is then dipped in the solution of the dye. Insoluble coloured complexes (lakes) are formed on the fabric. Metal ions first attack to the fabric and dye fwolecules then link to the metal ion Ly covalent co-ordinate bonds. For example, see the bonding of aluminium ions with alizarin. sons form brownish red and magnesium form violet colour. water but are reduced by sodium ‘AI ions form blue colour. Cr** 2. Vat dyes and Chemistry involved, These are insoluble in ily reoxidised to the dye. These reduced hyposulphite to alkali soluble compounds which are re’ compounds are often white or colourless and so are called leuco compounds. ly Grat dyes are mostly Dyes in the leuco condition dye both animal and vegetable fabric direct used on cotton) The fabric to be dyed is soaked in the vlkaline solution and then oxidised to the ‘air or by some oxidising agent such as perboric acid. An insoluble coloured form by exposure to important example of vat dye is Indigo. Reduction ‘Oxidation indigo {Leuco form) 3. Azodyes — their synthesis (@) Methyl orange. Synthesis. N-dimethyl aniline. roe yt prions O>-10 O)-w ety! oraned and applications. 11 is prepared by coupling diazotised sulphanitic acid with N, Mechanism. @ J H ° cut “ HO3S- =N Tico > H03S N=N N(CH3)2 p-N, N-dimethyllaminoazo benzene to them but the colour is not fast ~ “Applications. (i) It dyes wool and silk and imparts orange colour to light or washing. 4 (ii) his employed as an indicator in acid-base titrations. It gives yellow colour in alkali solution = oe ‘in the acid solution. The change in colour at the end point is due to the change in the structure 038: _ ft - + is {S11 One os KO XD 7 (Yellow In alkali solution) (Pink I ink In acid solution)pyes a 327 o mer eet Its prepared by coupling tetrazotised benzidine with 2 molecules of mil pty Mechanism NH2 OO + me( VL ree Tetrazotised benzidine aphhylamine —-ulphoni ald NHp og 00 OO ae (i) It isa dark red dye. (ji) Itis red in alkaline solution and blue in acidic solution, (iii) Itis a direct dye employed for dyeing cotton. (iv) The “en in colour from red to blue in acid solution is due to the following structural change. [it medium) SO3 Onn SIOO+ METS (Blue Colour). 803 4. Triphenyl methane dyes. These dyes are obtained by introducing - NH, ~ NRp or - OH groups into the rings of triphenylmethane. The compounds so obtained are colourless (the leuco Compounds) and these on oxidation get converted into tertiary alcohols (the colour bases). They readily change from the colourless benzenoid forms to the quinonoid dyes in the presence of acid, the to salt formation. These changes are reversible. oxidation id Leuco-base <== colourbase === dye (coloured) (colourless) seduction _-*Colourless)— alkali Some important dyes of this class are : | \CHg 1 OnHeci Yohei N(CHs)a at : yl cup Melachite green cH NC nrotin LEUCO BASE pboztHci]() N(CH3)2 <> (cHapJor Ho ¢ hn N(CHske COLOUR BASE Ni(CHg)e MELACHITE GREEN Application. With this dye, cotton is fist reacted with tannin (mordant) while wool and silk can be dyed directly. (6) Para-rosaniline. It is prepared by the oxidation of mixture of aniline (2 molecules) and ptoluidine (1 molecule) with nitrobenzene. ; : 1 42(0) + oO alicead tS \ ’ . nC? wn _Y%euco ase p-TOLUIDINE (1mole) Jo c ist Ha << PARA-ROSANILINE (Dyes) Application, Wool and silk can be dyed directly with it producing a violet-red ccolour while cotton is first put to mordanting. 4H; a Qe Magenta or Fuchsine. It is o-methy! derivative of para-rosaniline. It is prepared b ion of an equimolar mixtut ‘line, o- toluidi oe : ionfilings. intare of ailing, o- and p- toluidines with nitrobenzene in presence of The ‘ crystals of this dye show a green metallic lustre, It gives deep red colour in water solution. ‘The solution is decolourised wit Fi The som ae with $0, to give Schiff's reagent, ‘The pink cotour of this reagent can beoe and silk dir 329 Ircan dye wool and silk directly and imparts a violet red colour Oreo) Saito, > ene ANTHRAQUINONE (Alizarine) ° (ANTHREQUINONE) Clearly, alizarine is a dihydroxy derivative of anthraquinone, To support the presence of two hydroxyl groups, it is found that () Alizarine on acetylation with acetic anhydride yields a diacetyl derivative, (ii) Alizarine is soluble in water while anthraquinone is notae MODERN COLLEGE CHEMISTRY (SEMESTER VI PAPER XII ‘AND XIV) 4. Position of hydroxyl groups. (a) When alizarin is subjected to vigorous oxidation, it yields phthalic anhydride. Vigorous, . “oxidation” Or 20H —aranne PATHALIC. ee "Ths feaetion prowes thet both the ~ OH srouge art om, the exme fing. IPE were hot eo thea hydroxyphthalic acid would have been obtained. (@) As alizarine can be synthesised by the condensation of phthalic anhydride and catechol, we say that the two hydroxyl groups must be in the ortho positions with respect to each other, Thus, the structure of alizarine is either I or IL fe} OH Oo i or OH = OC CO OR Cy “are” CO ‘OH CATECHOL § Q PATHALIC ANHYDRIDE 5, Exact positions of OH groups. When alizarine is oxidised with MnO; and HySOz, we get purpurin. Clearly, alizarin is 1, 2-dihydroxy anthraquinone as this compound on oxidation can yield purpurin odie OE" (Alizarin) (Purpurin) Purpurin was found to be 1, 2, 4-trihydroxy anthraquinone by its synthesis 1 OH Oo OH oO (OH {OH \y — 2, 7 of a 5 on 7: os PATHALIC ANHYDRIDE — QUINOL, QUINIZARIN PURPURIN Structure If cannot explain the formation of purpurin on oxidation. Hence, structure Il for alizarin is ruled out. 6. Further support to structure I. Alizarin on nitration or on acetylation produces two isomeric mononitro or monoacetyl derivatives. This is only possible from structure I. Structure II yields only one isomer.pves x 333 0 OH : on 9 OH mea OH CO =o - fo} A if : TWO ISOMERS ° NO OR COCH3 oR o oH ‘Nitraton “Sraseylaton” I ‘OH ‘OH 0 1 ° Synthesis of Alizarin. The structure of alizarn is further confirmed by synthesis. 9 ° ° rane i so9h sOsNa EXCESS 1804 Nao (7 OF NaOH Taree = KOs i ° ° |ANTHRAQUINONE: ANTHRAQUNONE. 2SULPHONICACID Preparation of alizain, 1. From madder rools. On hydrolysis, the glucosides present in it break to yield glucose and alizarin, = 2, Synthesis. It is synthesised by starting from anthraquinone. Anthraquinone is treated with coleum at 160°C. The sodium salt of the product formed is fused with sodium hydroxide containing a calculated quantity of potassium chlorate at 90-100°C under pressure. OsNa O° Oo ONa 9 OH ONa oH COC "C0 = (From KGI09) Oo fe) °O ALIZARIN Properties, (a) Physical. The uby red crystals of alizarin mel at 190°C. It is insoluble in crater a ahay dasolves in alcohol. 1 soles on heating. (Purified by sublimation). Its soluble in alkalies. (b) Chemical. 1. Oxidation When heated with Map and sulphuric acd, it gives purpurin ie, 1, 2, 4-tihydroxy anthraquinone. _ Q OH 9 OH pu OH COW i COO WeSOWA 1 1 ° OOH ALIZARIN PURPURIN Note’| Vigorous oxidation gives phthalic acl334 MODERN COLLEGE CHEMISTRY (SEMESTER VI PAPER Xill AND xiv) 2. Reduction, On reduction with zinc dust and ammonia, it forms anthrarobin (dihydroxy anthranol).. ‘ Oo OH OH OH oH oH OU = COCO nts & ANTHRAROBIN, ALIZARIN 3. Mordant dye. It is a mordant dye. With aluminium, it forms red lake. Chromium gives eo brown violet while ferric salts form violet-black lake. These are employed for dyeing wool —~ [are + Uses. 1. It is an important mordant dye, The colour varies with metal used for mordanting i.e, Red colour with Aluminium, Violet black with ferric and brown violet with Chromium. 2. It is also used as a purgative, (®) Indigo (From Natural sourees). The plant containing indigo is cut just before flowering and treated with water at room temperature in a wooden tank. The enzymes present in the leaves of the plant hydrolyse the glucoside indican into indoxyl and glucose. The liquid extract is agitated in the presence of lime in open vats when indoxyl is oxidised to indigotin which consists of insoluble blue flakes. The crude indigotin so obtained is boiled with water. - Itis then filtered and dried to get indigo (dye) OcsH1105 on ' Crt te, + CoHts20s N’ ‘Glucose NW : ' v H Indican Indoxyt { ‘4 H N © 0 H LO Gut Indigo 4 Heumann’s Commercial Synthesis of Indigo. Starting from Anthranilic acid, the synthesis of indigo is described below : co ‘COOH cicHycooH FA 00H poo KOH on ——~ I ae | SA Nant NHg fH ce N-COOH ‘ ; H Anthiranilic acid Phenylglycine-o-carboxylic acid 5 Heat | ~Coe H N © OH i : Indigo at Compared to natural indigo, the synthetic one is much cheaper.ones ies. I 335 properties. It a dark blue ; * ents. With sodium ienbuciaeie ells at 390°C. It is insoluble is water and many organic Sol ndgofin whit. Its be ecou i eee aes mol towatersoble leo compound, exposed to air. Reduction “Oxidation — Indigotin blue ofa Indigotin white (Leuoo-soluble in water) Application. It is used in dyeing cotton. Its colour is stable to light, washing etc. EDIBLE DYES Food colouring of colour additive, is any dye pigmst or substance that imparts colour when it is added to food or drink. They come in fae forms consisting of liquids, powder, gels and pastes. It is important to note that all foods have colour. Thus, colours are automatically introduced ivhen we eat different foods. It is said that rainbow eating can be beneficial. Thus, we should include foods in our diet that correspond to different colour of the rainbow. At present colour additives may te harmless or not. It depends upon the quantity of colour used. It is recommended that not only the use of synthetic colours but the use of natural pigments as food additives may be restricted. Different food colours in the diet and their source are described below : . (i) Red - Tomatoes, beet roots, Red peppers , (ii) Blue — Blue berries, blue sage, blue fish (iii) Pink ~ Raddish, Pink grape fruits. (iv) Yellow - Bananas, Lemons (v) Green — Pear, Spinach, Green peppers, leafy greens.” (vi) Purple ~ Purple leaf lettuce, black grapes —— SHORT. QUESTIONS WITH ANSWERS 4. Give the classification of dyes on the basis of their chemical constitution. ‘ns. () Azo dyes : THY contain (- N= N ~) 220 g16uP @g. Congo red, Orange |. (i) Phthalein dyes = They contain phihalein group : 94 phenolphthalein. (ii) Tripheny! methane dyes ¢ Which contain tipheny| methyl group e.g. Melachite green. (iv) Indigoid dyes + Which contain indigoid group 2.9. |ndigo. , (v) Anthraquinone dyes * Which contain anthraquinone group €.9. Alizarin. 2, What are disperse ayes ? ; Ans. These aie dyes in which the minute particles of the dye are dispersed or spread from a suspension into the fibre when they diffuse, These are used for Nylon, polyesters: and polyacrylonitrile. 3. Write what you know about mordant dyes. - ; ‘Ans. These dyes require an ‘additional substance for fixing, generally, a metal ion. The metal eee ayes abric and the dyes Forms the link with the metal ion, Depending upon the