GOVERNMENT ARTS AND SCIENCE COLLEGE NAGERCOIL — 629 004 [ Affiliated to Manonmaniam Sundaranar University, Tirunelveli ~ 12 ] DEPARTMENT OF PHYSICS NAME OF THE SUBJECT: ALLIED CHEMISTRY SUBJECT CODE SACHIL YEAR IB.Sc. PHYSICS SEMESTER 1 STAFFIN-CHARGE _ : Ms. R.S PRIYA DHARSHINI, Dr. G.M. CARMEL VIGILA BAL DEPARTMENT OF PHYSICS Government Arts and Science College Nagercoil Email: [email protected] Mobile No: 7871759528 PAPERS HANDLED BY: Dr. G.M. CARMEL VIGILA BAI Ms. R.S PRIYA DHARSHINIMSU / 2017-18 / UG-Colleges / Part-II (B.Sc. Chemistry) /Semester ~ Il / Allied ~ ALLIED CHEMISTRY - I Objective To learn about atomic structure and bonding. To learn the principles of reactions of organic compounds. To study about photochemical reactions. To learn about the importance of polymers and polymer science. To study about lubricants and some cosmetics in the modern world, Unit I- Inorganic chemistry Atomic structure : electronic configuration - Aufbau principle - Pauli's exclusion principle- Hund's rule. Bonding :electrovalent, covalent, hydrogen bonds-orbital overlap - 5-5, sp. Hybridization and VESPR theory - CH4, C2H4, C2H2- BeCl2, BF3, NH3, H20, PCIS, IFS, IF7 Unit II Organic chemistry — Principles of reactions Heterolytic and homolytic cleavage - nucleophiles and electrophiles-reaction intermediates - preparation and properties of carbonium ions, carbanions and free radicals - type of reactions - substitution, addition, elimination and polymerisation reactions. Unit I Physical chemistry - Photochemistry Definition-comparision between thermal and photochemical reactions-Laws of photochemistry-Beer Lambert's law-Grothus Draper law-Einstein’s law-Quantum yield-low and high quantum yield-determination of quantum yield-fluorescence, phosphorescence, thermoluminescence, chemiluminescence and bioluminescence-definition with examplesphotosensitisation. Unit Iv- Polymer Chemistry Definition- Monomers, Oligomers and Polymers - Classification of polymers- natural, synthetic: linear, cross linked and network- plastics, elastomers, fibres- homopolymers and co-polymers Thermoplastics: polyethylene, polypropylene, polystyrene, polyacrylonitrile, poly vinyl chloride, nylon and polyester - Thermosetting Plastics : phenol formaldehyde and epoxide resin- Elastomers: natural rubber and synthetic rubber - Buna - N, Buna-S and neoprene. Unit v- Applied Chemistry Lubricants-classification-criteria of good lubricating oils-synthetic lubricating. oilspoly glycols and poly alkene oxides-greases or semi solid lubricants-examples-solid lubricants- graphite Prepration and uses of shampoo, nail polish, sun screens, tooth powder, tooth paste, boot polish, moth ball and chalk piece. Reference Books 1.B.R. Puri, L.R. Sharma and K. C. Kalia, Principles of Inorganic Chemistry2. P. L. Soni, Text Book of Inorganic Chemistry 3. K.S. Tewari and N. K. Vishnoi, A Text Book of Organic Chemistry. 4, Arun Bahl and B.S. Bahl, Advanced Organic Chemistry, S. Chand and Sons. 5. M.K. Jain and S, C. Sharma, Modern Organic Chemistry 6. K.K.Rohatgi Mukherjee, Fundamentals of photochemistry , Wiley Eastern Ltd. 7.B.R. Puri and LR, Sharma, Principles of Physical Chemistry, Chand & Co. 8, Malcom P. Stevens, Polymer Chemistry ~An Introduction 9. V.R. Gowariker, Polymer Science, Wiley Eastern, 1995, 110. Sawyer.W, Experimental cosmetics, Dover publishers, New york, 2000MSU / 2017-18 / UG-Colleges / Part-Ill (B.Sc. Chemistry) /Semester Ill / Allied Practical -I Inorganic Quantitative Analysis Objective: To enable the students to acquire the quantitative skills in volumetric analysis. Acidimetry and alkalimetry 1 Estimation of oxalic acid ~ Std. oxalic acid 2. Estimation of Na2CO3 ~ Std. Na2CO3 3. Estimation of hydrochloric acid ~ Std. oxalic acid Permanganometry 4. Estimation of ferrous ammonium sulphate - Std. ferrous ammonium sulphate 5. Estimation of oxalic acid ~ Std. oxalic acid 6. Estimation of ferrous sulphate — Std. oxalic acid Internal -50 marks 25 marks - Regularity 25 marks — Average of best four estimations in regular class work External -50 marks 10 marks — Record (atleast 4 volumetric estimations)* 10 marks — Procedure 30 marks — Result “Experiments done in the class alone should be recorded (Students having a bonafide record only should be permitted to appear for the practical examination)UNIT-1 INORGANIC CHEMISTRY ATOMIC STRUCTURE ELECTRONIC CONFIGURATION An atom consists of a charged body at its centre. It is called the “nucleus”. It is surrounded by electrons in various orbitals. The distribution of electrons in various orbitals is known as “electronic configuration”. The order of filling of orbitals with electrons is governed by the following rules: 1. Pauli’s exclusion principle According to this principle, no two electrons in an atom cari have all the four quantum numbers identical. If two electrons have the same value for n, /and m, they must have different values of s. n=1 1=0 m=0 s=+1/2 (for one electron) n=1 1=0 m=0 = -1/2 (for second electron) “ Significance of the principle It predicts that i) A sub-orbital can accommodate a maximum of two electrons with opposite spin x Pde ee J Since it excludes the probability of accomodating more than 2 electroiis in a sub-orbital, the principle is called roa Principle.“)( The maximum number of electrons. that can be accomodated in an orbital = 4/+ 2. Value of / Obital No. of electrons 0 s 2 q p 6 zg d 10 3 f 14) 2. Aufbau principle (German : Aufbau = building up) (According to this principle, the electrons are filled in various orbitals in the order of their increasing energies) This means that ar orbital with lowest energy will be filled first)T e (energy of an orbital depends upon its n + | value) The orbital: with the lowest n + | value is filled first))hen two orbitals have the same n + | value, the one with the lower n value will be fille first. This is known as (n + /) rule. di Orbital n I n+l 1s1.Uo Itis evident from the above table that order of increasing energies and hence the order of filling up of orbitals is 1s <2s < 2p <3s < 3p < 4s < 3d < 4p <5s<4d The order is diagramatically illustrated below: 3. Hund’s rule of maximum multiplicity According to this rule, electrons never pair in a p, dorf orbital until all the available sub-orbitals have one electron each.) 2P—6 elechony 38 ~ Seleckvon etc . Explanation of Hund’s rule: The repulsive force between electrons will be minimum when they have parallel spins and occupy different sub-orbitals. Consider the three p sub-orbitals (P,, Py and p,) of equal energy. If three electrons are to be accommodated they prefer to enter different p sub-orbitals singly rather pair up in the same sub-orbital.1.04. | Example Pee Ps (x-7 =o Bee Py oe ~@ The correct configuration is (2). It may be written as N =7 = 1s? 2s? 2p,1 2py' 2p)! ) Significance of the rule: Hund’s rule explains the stability of half-filled orbitals. For example, np3, nd° and nf’ configurations are the most stable. The cause of stability is the minimum repulsive force between the electrons which are singly filled in p, d or f sub-orbitals. For this reason, the following elements tend to have electronic configuration with half filled orbitals. Cr = 24 = [Ar]'® 3d5 4s! Mo = 42 = [Kr]°° 4d° 5s! Gd = 64 = [Xe]®4 4f7 5d! 6s? Element Electronic configuratio3 Hydrogen Is! Helium 1s? _ Lithium 7 1s? 2s! Beryllium 1s? 2s? Boron 1s? 2s? 2p! Carbon j © 1s?2s? 2p? Nitrogen ‘ ee ie 2p?1.05 8 Oxygen oO 1s? 2s? 2p* 9 Fluorine F 1s? 2s? 2p* 10 Neon Ne <\} et2s? 2p? ll Sodium Na-. 4194125? 2573s! 12 Magnesium Mg_| 1s? 2s? 2p’ 3s? 13 Aluminium Al | 1s? 2s? 2p°3s? 3p! 14 Silicon Si 1s? 2s? 2p°3s? 3p? 15 Phosphorus P 1s? 2s? 2p®3s? 3p? 16 Sulphur Ss 1s? 2s? 2p°3s? 3p* 17 Chlorine ca 1s? 2s? 2p®3s? 3p* 18 Argon Ar | 1s? 2s? 2p$3s? 3p® pe Potassium K 1s? 2s? 2p® 3s? 3p%4s! 20 Calcium | Ca U/LISIBS 2p°3s' Sp ee CHEMICAL BONDING LJONICBOND = (“TRanshe) Tonic bond is formed by the transfer of electrons from e atom to th her, The atom which loses the electron produces cation while the atom which gains the electron forms anion, The electrostatic force of attraction between the ions is called ionic or electrovalent bond. Na Bu ant ie Cokionsy + Change Cl+e eee Cl ANION = = Charo Na‘+Ct > Na’Ch 4 Favourable conditions for the formation of anionic compound M*X- 1. The ionisation energy of atom M should be low. ja! c\ 2. The electron @iffinity of atom X should be high. opfinty -ge 1.U0 3. The atoms M and X snouia have high electronegativity difference) am 2 2. COVALENT BOND (Sto)siry) Acovalent bond is formed between two atoms when they equally share one, two or three pairs of es other. aR - QD > WEF: @ F -F a G26: ory! 50 RGN) mes NEN (or) NEN Favourable conditions for the formation of covalent compound 1. Thetwo atoms A and B should higher val: ues fi ionisation potential. 2. Electomegativity of A and B should be equal or almost equal Overlapping of Atomic orbitals According to valence Bond theory (VBT) i) A covalent bond is formed by the pveeeree of two atomic orbitals with unpaired electrons, ii) The strength of the covalent bond is Proportional to the oe overlapping of orbitals. Types of f overlapping dD) s-s Overlapping :-e. g. Hydrogen The Is orbitals of two hydrogen atoms overlap to f = S: (orm an s-SSS overlapping 0.0 3agen H H ii) s-p Overlapping: e.g. HCl The 1s orbital of hydrogen and the half filled 3p, orbtial of chlorine overlap and form a S-p covalent bond. OOO? OD 5-p overlapping OCO- CO + #0 H cl iii) p-p Overlapping: e.g. Chlorine. The 3p, orbitals of two chlorine atoms with one electron each overlap to forma P-P covalent bond, CO-CO-CxDOs a6bere 1.08 “The strengths of the covalent bonds are in the order s-s bond _ pres14 5p IN) ATA) CT I (ground sate) , [4] [AT 4T 4] | (excited astate) Sp? hybridisation VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY Postulates of VSEPR theory 1. The shape or geometry of a molecule depends upon the number and nature of the electron pairs. present in the valence shell around the central atom. 2 When the valence shell 9-bonding electron pairs (o- a regular geomerty. The number of o-bps which tend to keep away from one! another to have minimum | > electrostatic repulsion. Thus, the geometry with large bond angle is more stable1.15 No of «-bps Geomeiry Bond angle Example 2 Linear 180° BeCl, 3 Trigonal planar 120° BF, 4 Tetrahedral 10928" ~~ CH, 5 Trigonal bipyramid 120° PCI, 6 Octahedral 90° SF, 7 Pentagonal 72°and 90° —sIF, 3. Whe the valence shell of the central atom has bonded (o-bps) as well as non-bonded or lone pairs (Ips) of electrons, the molecule will have distrorted or irregular geometry. Consequently, the bond angle decreases from the regular value. The magnitude of distortion and the decrease in bond angle depends upon the number of lone pairs of electrons. This is due to greater repulsive force of the Ips. The repulsion is in the order Ips - Ips > Ips - bps > bps - bps 4, The presence of x-bps does not influence the spatial ar- rangement of o -bps and hence the geometry of the molecule.| | Applications of VSEPR theory 1. Molecules with regular geometry i) BeCl, molecule: The central Be atom in BeCl, molecule in the vapour phase has two o -bps in its valence shell. They ar- range themselves at an angle of 180° to have minimum repul- sion. Thus, the molecule assumes a linear shape. 180° Cl - Be - Cl.| 1.16 ii) BF, molecule: The B - atom in BF, is surrounded by o-bps. There will be minimum repulsion when they ate ar- ranged at an angle of 120°. Thus, the molecule has trigonal planar geometry. iii) IF, molecule: The centrai I - atom in IF,n molecule . tains five bond pairs and one lone pair of electrons. They are directed towards the six corners of an octahedron. Due to greater lone pair - bond pair repulsion, the geometry is dis torted and IF, molecule assums square pymidal geomeiry. 2. Molecules with Irregular 9) NH, molecule The valence shell of the geometry central N-atom : if ; Pair of electrons, NH, cont g117 In order to have minimum re- pulsion, the electron pairs are directed towards the four corners of a tetrahedron. The repulsion among the electron pairs is not equal. The lone pair_ - bond pair repulsion is greater than the bond pair - bond pair repulsion. As a result, the bond pairs move away from the lone pair and come closer to each other. Thus, NH, molecule has an irregular or distorte i tetrahedral geom- etry and the bond angle is decreased forn 2 109928’ to 107°. This distorted tetrahedral geometry is also known as pyrami- dal geometry. ii) H,O molecule The central O - atom in water has four electron paris viz two bond pairs and two lone paris in its valence shell. Haid Has They are directed towards the four comers of a tetrahedron so that there will be minimum repulsion between them. Since the lone pair electrons exert more repulsion on the adjacent lone pair and bond pair electrons, HO molecule has an irregular ar tetrahedral | geometry. It is also known as bent c t or angular or V- Shaped ! geo. Presence of: two lone pairs of electrons the omeiry. Due to the “Steased from 19°28’ to 104°27' rips saaiat-3. HYDROGEN BOND Definition } The weak electrostatic force which binds the H- ai ofone molecule with a small but highly electronegative atom like F, O or N - atom of another molecule is called hydrogen pond H-F—-H-F-—-H-F t H-bond Thus, the electronegative atoms of two neighbouring molecules are bridged through a H - atom. For this reason, H - bonding is also called H- bridging, _ . ‘Types of H-bonding — i) Inter molecular H - bonding : This type of H bond is for between H atom of one molecule and F, O or N atom of another: ecule. c Examples ; i)Hodrogenflourde H-F--H-F--H-F . ii) Water H-0--H-0--H-0 | Linear [ink ‘ H H H- 2. Intramolecular H - bonding: This type of H bond is formed tween H - atom and O - or N - atom of the same molecule, Examples i) O-Nitrophenol a ii) Salicylaldchyde aT ONG 0. a “oo?1.19 Effects of H - bonding 1. Abnormal boiling points: Molecules get associated by H-bonding. Alarge amount of energy is needed to separate such molecules. Therefore, the boiling points of hydogen bonded compounds are: much more than similar compounds without hydrogen bond. For example, HF, H,O and NH, have higher boiling points than the hydrides of other elements of the same group. 2. H,0 is a liquid while H_S is a gas: Boiling point usually varies with the molecular weight. However, H,O (mol.wt= 18) isa liquid (b.pt = 100°C) while H,S (mol.wt = 34) is a gas (b.pt = -59.6°C) at ordinary temperature. The abnormally high boiling point of water is due to molecular association through H- bonding. 3. Difference in melting points of nitrophenols: The m - and p-nitrophenols have higher melting points than o - nitrophenol. This is because of molecular association by H - bonding. ' - Nitrophenol forms intramolecular H - bond. But m - and P-nitrophenols form intermolecular H - bond and the molecules get associated. t 4. Solubility of alcohol in water : Covalent compounds whieh can show the property of H - bonding are highly soluble in water. For example, ammonia, alcohol and sugar are readily soluble in water due to intermclecular H - bonding with water. St Renan gH R aevi a principle d) None of these 5. Density of ice is lower than that of water: In ti crystal structure of ice, each O-atom is surrounded by for H-atoms, two of them are covalently bonded and the of two by H-bonds. H-bonds are weaker and hence longer thai covalent bonds. Due to this arrangment, ice attains a like structure with large empty space. Consequently, volume of ice is increased. We know that, Density = Mass/Volume Thus, density of ice is less than that of water. That is why ice floats in water. QUESTIONS PART-A 4. The shape of NH, is a) Pyramidal b) Tetrahedral c) Bent shaped d) V-shaped 2. Maximum electrons present in “s” orbital is a)4 b) 2 c) 6s d) 1 3. Which orbital is having the lowest energy? aa b) 2p c) 4s d) 3d 4. Electrons never pair up i / available htnorta Fave et {Orbital until al itals have one elect called Ton each: a) Pauls exclusion Principle b) Hund’s ruleal 5. Two atoms with almost equal electronegativities form a) Electrovalent bond b) Covalent bond c) Hydrogen bond d) None 6. IF, molecule is formed by a) sp*d hybridisation b) Sp3d? hybridisation c) sp°d° hybridisation d) None of these PART-B 7. Explain sp*d hybridisation with an example. 8. Write notes on hydrogen bonding. 9. State and explain Hund’s rule. ' 10.Explain s-s and s-p overlap of orbitals. PART-C 11. Explain VSEPR theory. 12. Explain sp*d and sp*d? hybridisation with an example. 13. Explain the geometry of C,H, by hybridisation principle. 14. Explain the geometry of BF, molecule by VSEPR theory. ) 15. Explain the consequences of hydrogen bonding.4 ws ORGANIC CHEMISTRY Pee PRINCIPLES OF REACTIONS CLEAVAGE OF BONDS A covalent bond is nothing but a pair of electrons shi by two atoms. There are two modes of cleavage of a coy ra bond. 1. Homolytic bond fission In homolytic fission, the covalent bond breaks i way that each fragment retains a single unpaired elec Such fragments having one unpaired electron are called, radicals or simply radicals. molecules where the covalent bond links two atoms o1 or of equal electronegativity, CH,+-CH, / Ethane2.02 2. Heterolytic bond fission This type of cleavage usuallyl occurs at a covalent bond between two atoms of different electronegativities. The bond breaks up in such a manner that the pair of electrons remains with one of the fragments producing charged species called ions. nN A-B — (At Bg CN A-B — :A+ Bt The more electronegative atom or group acquires the electron pair and becomes negatively charged ion (anion). The other atom or group forms the positively charged ion (cation) due to the loss of electrons. A cationic species carrying a positive charge on carbon is called a carbonium ion (or carbo cation) while the anion carrying a negatively charged carbon centre is termed carbanion ( or carbo anion) N ean CE ae Carbonium ion \ CH, SH CH. + He Carbanion ATTACKING REAGENTS An organic reaction proceeds by the attack ofa reagent a substrate molelcule. Depending on the nature of the ee ane gs2.03 ‘ ws a definite mechanism reagent, the reaction follo =r a 4 reagents may be broadly divided into tw? sai i) Nucleophiles ii) Electrophiles 1. Nucleophiles Nucleophiles are electron rich species which affinity for electron deficient substrates. They havea H* which is the smallest nucleus and hence named nucleoph (nucleo = nucleus ; philic = loving). They possess an unsh pair of electrons and have the tendency to supply them substrate. Nucleophiles can be classified as 1 i) Negative nucleophiles ii) Neutral nucleophiles Negative nucleophiles : are those which carry a charge owing to the possession of an electron pair. Examples Bi: Halideion = y- 2 Hydroxyl ion -_ _* GiHo- Amino ion s2.04 - Neutral nucleophiles : possess unshared electron pair (s) but are electrically neutral. < Examples Ammonia :NH, Water H- 0 -H Alcohol R-0-H 2. Electrophiles Electrophiles are electron deficient species which have strong affinity for electron rich substrates (electro = electron; Philic = loving). Electrophiles usually have six electrons in the outermost orbit and are thus short of'a pair of electrons to attain stable electronic configuration. Therefore, they have a tendency to take a pair of electrons from electron rich substrates. Electrophiles are of two types $ i) Positive electrophiles ii) Neutral electrophiles Positive electrophiles are those which carry a positive charge. They are short of a pair of electrons from an octet and hence behave as electron seeking reagents. Examples Proton Hta 2.05 " Hydroniumion HO" NUY, Ammonium ion Carbonium ion REE CH; Chloronium ion cr Bromonium ion Br* Nitronium ion NO,” se which have six electrons i Neutral electrophiles : are tho: the outer most orbit but are electrically neutral. ‘Examples i cl ' t 1° Ba. Al-Cl Oo ' Cl REACTION INTERMED) i 1. Carbonium ions ne Definiti a2.06 CH, t ty ' CH,-C- Cl —+ CH,-Ct + Cr 1 ' CH, CH; Methods of formation 1. Directionisation : Many organic halides undergo ionisation ina highly polar medium such as SO, to form stable carbonium (CH),C-Cl —» (CH), C+ t. Butyl chloride : (CH),C-ch +. (CH) Coe Tripheny! chloride CH, = CH - CH, Cl — CH, = CH - CH,* + Cr Allyl chloride f 2. Protonation of unsaturated compounds : Carbonium ions may be produced by dissolving olefins, carbonyl compounds and nitriles in proton donating solvents or treating them with Lewis acids. n + -CH=CH- + Ht —+ -CH-CH, eee £20. +... — BF -6h' <— 2.07 += Ne , -coN ard a oe Properties 1. Elimination of p proton to form an olefin roton : Acarbonium ion may eli H 1 CH,-CH-CH, 7° CH,-CH Propyl carbonium ion Propylene | 2. Rearrangement to form a more stable carbonium io + + CH, - CH, - CH,-CH, —+ CH, - CH, - CH- (1°, less stable) (2°, more stable) 3. Combination with nucleophile beste | CH,CH + Br __, CH, CH,Br Ethyl carbonium i C ium ion Ethyl bromide| 2.08 a R-Caere oe > R- Che CH, | R R Tertiary Secondary Primary . Carbanions efinition These are organic ions possessing a negative charge and a air of electrons on the central carbon atom (carbo anion). They we three bonds and an unshared pair of electrons. The presence f an unshared pair of electrons makes them very reactive. arbanions are formed by the heterolytic fission of a covalent nd. H i CH,-C-H — > CH,CH, +H* | ss H lethods of formation - Byremoval of proton from an aromatic hydrocarbon in the Presence of a base (CH),CH + OH =, (C,H),C° + H,0 Tripheny| methane Triphenyl methyl 3 carbanion2.09 F nds . By breaking of carbon-metal bo compounds of organometa R-MeX —»+ R +MgX jon 3. By decarboxylation of: carboxylate an! RCcoo — R+CO, Properties ‘ a} a 1. Addition reactions : Carbanions add ©: ‘4 i reactio group of aldehydes and ketones in condensation c I Ns teas Rit. 60 Let Cbg. | : 2. Substitution reactions : Carbanions take p nucleophilic substitution reactions at saturated carbon BOHN eS lea CH, + x Structure The carbon centre of a Carbanion is in sp* hybridized State and the unshared electron pair occupies one of the corners of a regular tetrahedron, ’This Rives rj, © the carbanion wi than 109%2g> Se toa ith bond angle Jess a2.10 Stability The order of stability of carbanions is e Loa R-C < AE = R-CH,; < GH | R R Tertiary Secondary Primary 3. Free radicals Definition Free radicals or radicals are electrically neutral species carrying an unpaired electron. These are formed by the homolytic fission of a covalent bond by heat or light. 3 CH,+ CH. —~ | 2a (Methyl radicals) Types of Free radicals Free radicals have been divided into two classes on the basis of their stabilities: 1. Short-lived (or transient) free radicals C1" (Chlorine radical) OH* (Hydroxyl radical) CH, (Methyl radical) CH, (Phenyl radical)eal * (Trimethyln y C,H.CH, (Benzyl radical) (CH,),C Cine 2. Long-lived (or stable) free radicals wes (CH);C (Triphenylmethyl radical) Methods of formation 1. Pyrolysis (CH,,Pb 4, 4CH, + Pb TML Methyl radical C.H,CO-0-0-COC,H, 4, 2C,H,COO: =2602 Benzoyl peroxide Phenyl ' CH,-N=N-CH, _4, 2CH, +N, : Azomethane + Methyl radical 2. Photolysis CHCHO *Y, cH: 4 CHO: Acetald : i j cetaldehyde Methyl radical Formyl radical eater, ta CH,CO” A cetone Methyl radical Acetyl radical Cl, hy, 2¢¢ . Chlorine Chlorine Tadical | CH,-N=N-¢ Meo dbve 2 CHS +N, iA... aa2,12 Properties of Free radicals 1. Dimerisation : Free radicals readily undergo dimerisation to form stable molecules. CH; + CH, —? CH,-CH, CH,+CH,.— CH, Cah 2. Disproportionation : At higher temperature, ethyl radical undergoes disproportionation to form ethylene and ethane CH, CH, + CH,CH, —4 CH, =CH, +CH,-CH, 3. Addition reactions : Free radicals react readily with iodine, zine etc to form addition compounds 2CH,+1, —+ 2CH,I 2CH,+Zn —+ (CH,),Zn 4. Rearrangement : Free radicals undergo rearrangement to form more stable free radical. CH CH, eae -h CH, - Cc ~ CH, - CH, CH, (1°, less stable) (2°, more stable) : t S. Reaction with olefins : Free radicals add on the double bond of olefins during polymerization reaction,__. R-CH,- CH "ar {CH,-CH,#R R+CH,=CH, TYPES OF REACTIONS Organic anil such as substitution, addition, elimination, po! 1. Substitution reactions ; : Reactions in which an atom or group linked to carb reactions. There are three types of substitution reactio n i) Free radical substitution ii) Electrophilic substitution iii) Nucleophilic substitution f 1. Free radical substitution reactions e These are substitution reactions initiated radicals Example : Chlorination of methane Rasch CH,Cl+Hcl Mechanism2.14 CH,+Cr —+ CH, +HCl CH; +Cl, —+ CH,CI+CTr i Cl +GCh — + Cl, (Termination) . Electrophilic substitution These are substitution reactions initiated by Jectrophiles. In the case of aromatic compounds, the H - atom f the benzene ring is displaced. mples i) Nitration of benzene HNO, +H,SO, — NO,* +HSO,; +1,0 ©) 0: — Ope. on (Benzene) (Electrophile) (Nitrobenzene) ii) Chlorination of benzene cl, 4, cr +cr ®o— Oa (Benzene) (Electrophile) (Chlorobenzene)“lee Ae ‘Aii) Alkylation of benzene © £1} eee AICI, RCI+AICI, On ©)» — C7 (lectrophile) (Alkylbenzene) | (Benzene) iv) Acylation of benzene RCOCI +AICL, —+ RCO". +AlCl, (o) + ROOM sags (O)- cor +H +H* (Benzene) (Electrophile) (Acylbenzene) 3. Nucleophilic substitution These are substitution reactions initi: icleophiles. RX+ OH __, ROH + x (Nucleophile) ,2.16 (oer OH ay (O)-on+er ~ presst're Chlorobenzene "Phenol } 2. Additoin reactions Compounds containing a double bond (C=C) ora triple bond (C =C) have a tendency to adda molecule of the attacking reagent (addendum) without eliminating any atom or group. Such reactions are called addition reactions. There are three types of addition reactions. i) Freeradical addition ii) Electrophilic addition iii) Nucleophilic addition 1, Free radical addition Addition of halogens to alkenes in the presence of light takes place by a free radical mechanism _ Cl, —» Cli+ GE (initiation) eH = CH Chey CH,Cl- CH, (Propagation) CH,Cl- CH,+CP-— CH,Cl - CH,Cl+ Cr, at Clt as Cl, (Termination) 2. Electrophilic addition Addition of halogens to alkene in the absence of sunlight is initiated by electrophiles.woe cc — cr+cr CL, CH,CI-CH,C] Ethylene dichlo; di : ‘ a cH,=cH, ©", cH,C!- CH, Ethylene. 3. Nucleophilic addition ie Addition of HCN to carbonyl ¢! the nucleophile, CN" HCN —+ Ht + CN CN CN 1 .c=0 wy 5C-O =f =C - OH compounds is initia 3. Elimination reactions Elimination reactions are those groups are lost from the adj acent carbon atoms to product C=C double bond. This is called /,2.0r B - elimination. ‘3 in which two aton E ale. = os ca KOH CH, =CH, + HBr Ethylene Ethy! bromide 2 H,S0, & ; cu,-cH, 8%, CH=CH, +H,0 Ethylene / thylalcohol ~ ‘ ‘Sn 4. Polymerisation reactions The combination of several simple molecules to form a long-chain high molecular weight compound is known asa polymerisation reaction. The high molecular weight compound thus formed is called a polymer (GK : poly = many: meros = parts). The simple molecules from whicha polymer is formed is called monomers. Polymerisation is of two types : 1. Addition polymerization 2. Condensation polymerization Addition polymerization These are reactions in which a polymer is formed by the addition of the monomer molecules without el simple molecule. ineples i) nCH,=CH, —_, €CH,cH, >, Ethylene Polyethylene vithout eliminating any ii) nCH, = CHC! __, €CH,-CHCI >, Vinyl chloride Polyvinylchloride Mechaaism i) Initiation Re+ CH, = CH 2 —+ R-CH,-CH, Initiator Manomer li) Propagation : R-CH,- CH, +nCH,=CH, —_, R €CH; - CH, 3,219 iii) Termination ~ : R: ++4CH, 5 CH} R-€CH,- CH, — Polymer 4 2. Condensation polymerization [These are reactions in which a polymer is for the addition of the monomer molecules followe elimination of simple molecules like water, t Addition followed by elimination of simple molecule referred to as condensation. Example 1 : The condensation of adipic acid hexamethylenediamine yields nylon 6,6 3 HOOC (CH,),CO HN(Cti,). NH, Adipic acid Hexamethylenediamine -H,O HOOC(CH,), ,CONH(CH,).NH, | at OC(CH,)CONH(CH,) NH ; a Nylon 6, 6 2 Example 2 : The condensati 5 is tion of ethyl terephthalate yields polyester, oe __- nHJOCH,CH,o EF] oc-c,x,cof0 CH,. Ethylene glycol2.20 | -nCH,OH £0-CH,CH,OOC-C,H,CO +, Polyester (Dacron) QUESTIONS "ART -A / . Homolytic bond fission leads to the formation of a) Carbonium ion b) Carbanion . ¢) Free radical d) None of these . CH,CH, isa a) carbonium ion b) carbanion c) catalyst ’ d) catalytic poison . NH, isa a) electrophile b) free radical c) nucleophile d) carbonium ion ” Which is a nucleophile ? ‘ a)H* b) OH ©) BF, d)SO, - BClisa a) nucleophile b) electrophile ¢) carbonium ion d) carbanion . Which one of the following pairs represents a set of electrophiles ?‘ CN and a)AlCland cr ») c) BR* and CCl, © d) H* and H, o 7. Which alkyl radical is the most stable be 1 a) methyl b) primary c) secondary d) tertiary Pensions is anucleophile Ee b)AICl, c) BF, d)NH, ‘a PART-B 4 9. Explain the electrophilic substitution reaction in 10. How are carbonium ions formed ? Mention any properties. 11. Describe the classification of organic reactions examples. ~ 12.Give any two methods of preparation of carbo Write its structure, .UNIT - III PHYSICAL CHEMISTRY PHOTO CHEMISTRY Introduction . Ithas been found that some substances are sensitive to light. They undergo chemical reaction when exposed to light. Such reactions are called photochemical reactions or photolysis. Photochemistry mainly concerns with the physical changes and chemical reactions brought about by the low frequency electromagnetic radiations such as visible and UV rays. The chemical reactions brought about by the high frequency fadiations like X-rays are studied under Radiation chemistry such reactions are called radiolysis. Distinction between Thermal and Photochemical reactions | Thermal or dark reaction Photochemical reaction i) are initiated by activation are initiated by activation due to molecular collisions s ii) are temperature dependent iii) can occur in darkness due to absorption of light. « are temperature independent, proceed only in light. iv) reaction rate changes with Teaction rate changes with temperature light intensity3.02 us vy). have high temperature have negligible tem- * coefficient perature coefficient, vi) are always accompanied by some of them involve decrease of free energy increase of free energy vii) some of them cannot take occur invarialy at place at oridinary ordinary temperature temperature LAWS OF PHOTOCHEMISTRY 1. Grothus-Draper law “When light falls ona substance, a fraction of light is absorbed and the remaining transmitted. It is only the absorbed light that can bring about a chemical change. This is known as Grothus-Draper law. The law is purely qualitative and gives no quantitative relationship between the amount of light absorbed and the number of molecules reacted. 2. Beer-Lambert’s law ~ Beer-Lambert’s law States that when a beam of monochromatic light is Passed through a solution containing a light sensitive substance, the intensity of radiation decreases exponentially with increase in the thickness and concentratien of the solution.Mathematically, T= 1% I (or) In ieee (or) 2.303 log ip kex I kex (or) 109 > = ~ 355 = -e8Cx where, in intensity of the incident light I = Intensity of the transmitted light x = Thickness of the medium ¢ = Concentration of the solution k = Proportionality constant =k. inctic ie © = F309 |S called extinction coefficient Significance of the law - Beer-Lambert’s law is the basis of colourimetric analysis. 3. Stark-Einstein’s law of photochemical equivalence The law states that each molecule taking part in a Photochemical reaction absorbs only one quantum of light3.04 quantitative relationship betwee, The law implies a he number of quanta the number of reacting molecules and tl of light absorbed. i) Energy of one quantum of lighis « se =hv=he/, where, h = Planck’s constant (6.626 x 10°4J sec) v=Frequency of light ii) Energy of one Einstein of light is E E = Né =Nhv=Nhc/, where, N = Avogardo number (6.023 x 1073) Imonl _ Solved Problems 1. Calculate the energy in calories associated with one Einstein of light with wavelength i) 800nm ii) 2000A° i) E=Nhv= “2 (., y=e/,) — 8.023 x 10?3-x-6.626 x 10-4 x 3 x 108 800 x 10-9 (1 nm = 10° m) =~ 1.4958 x 105 J mol = 1.4958 x105 4.184 = 3.575 x 104 cal molt6.023 x 1075 x 6.626 x 10-4 x 3 x 108 2000 x 10-7 (1A°= 10m) = 5.983 x 105 J mol" 5.983 x 10° 4.184 = 1.43 x 108 cal mol! 2. Calculate the energy in joules a) per quantum b) per Einstein for radiation of wavelength 1000 A® . he i ea 6.626 x 10-4 x3 x 108 = F000 «107 ——« (A= 10m) = 1.988 x 10° J molecule ii) E=Ne = 6.023 x 10? x 1.988 x 10°18 = 1.196 x 10° J mol") _ expressed i . be unity (@ = 1). But in most cases, ¢ is greater or less that 3.06 Quantum yield The efficiency of a photoche! in terms of quantum yield mical reaction is often which is defined as the numbér of molecules reacting per quantum of light absorbed. inagiven time Number of molecules reacting L din the same time | Number of quanta of light absorbet $s Number of moles reacting ina given time = Number of Einsteins of light absorbed in the same time Deviations in Quantum yield : ‘ The Einstein’s law of photochemical equivalence implies that the quantum yield of photochemical reactions shouli E r . P According to Bodenstein, molecules are activated, eact u unity. This is due to secondary thermal reactions. molecule absorbing one quantum of light. This is called E primary process. The molecules thus activated undergo! series of thermal reactions without further absorption 0! light. These are called secondary processes. The quantut * yield of a reaction is determined by the nature of tht ‘secondary process. I) Reactions with 6 =1 Ase the activated molecules instantaneous!)- 3.87 decompose into the product without entering into secondary processes. the quantum yield becomes unity. : Examples i) CL+O, — CLO, ii) H,+0, —. HO, ii) HS —. HS iv) CH,,+Br, — CH,Br+H 2, Reactions with 6 <1 6=1 o=1 ¢=1 6=1 In this type of reactions, the activated molecules get deactivated to certain extent by collision in the secondary process. That is, the active species of the primary process reunite to give back the reactant molecules in the secondary process. Thus, the quantum yield of the reaction is less that unity. Examples {) 24. 1“ *h+3n, ii) H,+Br, —+» 2HBr iii) CH,COOH —-+ CH,+CO, ~ iv) CH,COCH, —- C,H,+CO 4 =0.2 $6 =0.01 6 =0.5 6 =0.33.08 3. Reactions with § >J1 There are phtochemical reactions in which the activated molecules produce free radicals in the Primary process. The free radicals may then start subsequent secondary reactions with other molecules without the Use oflight. As a result, for every quantum of radiation absorbed more than one molecules can enter into reaction. Thus, the quantum yield of such reactions is greater than unity. Examples UC ii) 2HI — iii) 2NO, —> iv) 2HCIO —. In some cases, involving sev Examples i) CO+ cl, — coc ii) H, + Cl, 20, e=2 H,+1, 6=2 2NO+0, o=2 2HCI+0, o=4 — ?HCI @ = 10!- 106 a series of secondary processe! eral thousands of molecules may This leads to a chain reaction with very high quantum yield 2 = 108 al ti de Cr Tea the giv Teahe nt ise ved the ssseS lace. field. 3.09 Determination of Quantum yield The experimental arrangement for the measurement of quantum yield is schematically given below: Quartz cet (X) “Thermostat (D) i) The reaction mixture is taken in a glass or quartz cell X with optical plane windows W, and W,. The cell is kept in athermostat, D. A narrow beam of monochromatic light is allowed to pass through the reaction mixture for a known time. The reaction mixture absorbs a portion of light. The residual portion of light is then allowed to enter a detector which measures the light intensity. Thermopiles or Chemical actinometers are generally used as detectors. Then, the intensity of light is determined keeping the reaction vessel empty. In case of solutions, it is filled with the solvent. The difference between the two readings will give the amount of light energy (Einstein) absorbed by the reaction mixture.3.10 > ii) The rate of reaction of the mixture under investigation is determined by the usual methods used in chemical kinetics. This gives the number of moles reactitig in a given time. _ __ No.of moies reactingin a given time ~ No.of Einsteins absorbed in the same time a Rate of the reaction ~ ‘Amount of energy absorbed Significance of Quantum yield 1. The rate of a photochemical reaction may be studied by the measurement of quantum yield. 2. The nature of a reaction can be determined from its _ quantum yield. A chain reaction has very high quantum yield whereas a thermal reaction will have zero quantum yield. Photophysical processes © . tc Absorption of light Tifts the atoms or molecules of ap, material to an excited state. Since the excited state is ct unstable, the atoms or molecules return to the ground state with emission of light. This is a photophysical process and the light thus emitted has the same or higher wavelength tha) E: that of the incident light._ 3.11 ; pes of Photophysical process Fluorescence , _ Definition When a beam of light (visible or UV) is allowed’ ‘o fall on Certain substances, they emit visible light which stops as soon as the incident light is cut off. This ‘phenomenon of instantancous emission of light is called fluorescence. The light thus emitted has the same wavelength as that of the incident light. Examples i) Minerals - Fluorite (natural CaF,), . Petroleum, uranyl! sulphate ii) Dyes - F Juorescein, cosin iii) Metals . Vapours of mercury and sodium. 2. Phosophorescerice Definition : What a beam of light (visible or UV) is allowed _to-fall on certain substances, they emit visible light which persists for-some more time even after the incident light is cut off. This phenomenon of delayed emission of light is called phosphorescence. The light thus ‘emitted will have wavelength greater than that of the incident light. Examples i) Phosphors (CaS, SrS, BaS) ii) Zinc sulphide: a 3.12 ifi)Dyes in fused boric acid iv) Aspirin, cocaine, procain, nicotine escence and Phosphorescence Phosphorescence delayed process Distinction between Fluor i) instantancous process i) life-time is short life-time is long persists for some time even after the incident light is cut off. iii) stops as soon as the incident Jight is cut off. given mostly by solids. - iv) given by gases, liquids and solids, carried out mostly with UV ‘light at low temperature ¥) less selective and sensitive vi) carried out with visible or UV light at room temperature 3. Chemiluminescence Definition The phenomenon of emission of visible light as a result of chemical reaction at a temperature at which a black body normally does not emit visible light is known as chemiluminescence. It is ‘the reverse of photochemical reaction which occurs by absorption of light. ee» 3.13 Examples . : i) Yellow phosphorus glows with a greenish yellow light, It is due to the oxidation of phosphorus vapour by atmospheric oxygen. 4P +50, —+ 2P,.0,+hv ii) When a solution of strontium chloride is added to dil.H,SO, inthe dark, a feeble glow is observed.. _ SrCl, +H,S0, + SrSO,+2HCI+hv iii) A red light is emitted when Cl, or hypochlorite ion is oxidised by alkaline H,0, solution. iv) A solution. of p - bromopheny! magnesium bromide in ether undergoes oxidation by air emitting a brilliant green light even in day time. : .) Ared light is emitted when a mixture of pyrogallol and formaldehyde is oxidised by hydrogen peroxide. vi) When a stream of atomic hydrogen is allowed to fall on the surface of mercury, a blue light appears. vii) When a mixture of siloxene and rhodamine - B (dye) is oxidised by acidified KMnO, solution, a red light _ Characteristic of the dye is observed. This is an example . of sensitised chemiluminscene. re3.14 4. Bioluminescence | ' Definition Certain living organisms emit visible light as a result of chemical reaction. This phenomenon of chemiluminescence in living organisms is called bioluminiscence. Examples i) _Fire-flies produce an yellowish green li ight. It is believed to be due to the oxidation of luciferin, a proteinby - - atmospheric oxygen in the presence of an enzyme luciferase. The intensity of light thus emitted is very.low and hence-observed only in the dark. ii) Certain marine animals like jelly-fish emit visible light. iii) Fox-fire which occurs in marshy places is probably due to some luminous bacteria present in the decaying wood. 5. Thermoluminescence ; : Definiton 7 Certain substances can absorb light at room temperature and emit itas visible lightat higher temperatures. This phenomenon i is known as. thermoluminescence. ° Example Phosphor (SrS) is illuminated -with light at: room temperature. Then, the light i is turned off and the phosphor is3S heated steadily at the rate of 2.5° per second. Visible light is emitted and its intensity increases upto a certain temperature and then decreases. Photochemical processes 1. Photosensitisation Definition : There are some photochemical reactions in which the reacting substances are not light sensitive. They are unable to absorb light directly. However, when a light sensitive material is added, it absorbs light and passes on the absorbed light to the reactants without itself taking part in the reaction. Such an added material is known as a Photosensitiser and the phenomenon is called Photosensitisation. _ . Examples : i) Plants synthesise carbohydrate by reaction between atmospheric co, and H,O. Being colourless, co, and H,O can not absorb light but chlorophyll which is a green ’ pigment can do so. Thus, chlorophyll present in plant leaves absorbs light and passes on the absorhed light to CO, and H,O molecules. Thus, the reaction starts in the process of photosynthesis (photo = ligh; synthesis =to build up) Chlorophyll + hv ——, [Chiorophyli]*: CO, +H,0+[Chlorophyll]*. ~ 5 / 1/6 (C,H,,0,) + O, + Chlorophyll ——YO rrr——“—SOSsSs—s—srss—s—s—s—s—sesSCSseSPsS, | - 3.16 a ie, . ii) The dissociation of molecular hydrogen into atomic hydrogen is photosensitised by mercury vapour. Hg +hy —+ Hg* : | Hgt +H, Hg +241 eae iii) Chlorine acts as a photosensitiser in the decomposition of ozone by UV light. : “\ 7 \ Cl+hv — 2Cl ‘ Cl+0, — clo, 2Cl0, -—+ Cl+30, iv) The decomposition of oxalic acid is Photosensitized by uranyl sulphate. U0,so, —+ U0*+s07 UO;*+hy —+ [O27 nee 5 : Oey +1 | = —+ U07*+C0,+CO+H,0 mo, fT COOH : 2 y é QUESTIONS PART=A 7 “ \. The quantum yield of N, and EH, photochemical reaction is3.17 a) 1 b)<1 c)>1 d) None ofthese . Plants synthesise their food by the process a) Photosynthesis b) Fluorescence c) Phosphorescence d) Luminescence . Absorption of light by chlorophyll of plant leaves is an example of a) fluorescence - _b) phosphorescence c) photosensitization d) chemiluminscence . The quantum yield of H, - Br photochemical reaction is a)<1 b)1 e)>1 . d) None of these . 2HI _t_, H, +1, . The quantum yield of this photochemical reaction is a) 107 b).10° c) 2.0 d) 0.01 . The element which exhibits photosensitization is a) cadmium b) calcium c) chlorine © d) sodium . Fire-flies emit light in the night due to .a) Chemiluminescence b) Thermoluminescence c) Bioluminescene d) Fluorescence ,318 PART -B 18.i) Explain 8. Explain the laws of photochemistry. ps “9, What do you understand by photochemical reaction ? ii) Write sh How can the rate of such a reaction studied ? 19. Distinguish 10.Define and explain the quantum yield of photochemicaj i) Thermal z reaction. 11.E ii) Phosphor 2 20. ti xplain Stark-Einstein’s law and quantum yield. What is mea : . Stand by pho: 12. What is meant by quantum yield ? How can we determine 21. What is f the nature of a photochemical reaction with quantum oan of certain “yield ? - 13. What is quantum yield ? How is it measured ? 14. Bring outthe differences between thermal and photochemical reactions, “ s PART-C 15. Write a note on Photosensitizatio; ; . 16. State and explain the various laws of, Photochemisery. 17. Write notes on : 4 i) Fluorescence ii) Phosphorescence iii) Chemiluminescence3.19 18.i) Explain the Grothus - Draper law and Beer - Lambert’s law. ii) Write short notes on photosynthesis. 19. Distinguish the following: i) Thermal and photochemical reactions. ii) Phosphorescence and fluorescence 20. What is meant by photochemistry ? What do you under- stand by photosynthesis ? : 21. What is quantum yield ? Explain why the quantum yield of certain reactions very high.UNIT-IV POLYMER CHEMISTRY Oe Monomers A polymer is made up of many small molecules. 7, individual small molecules from which the polymer is mai. « are calledgnonomers (meaning, single part). The monomer, 7 are usually tle repeating chemical units which are held togethe, by covalent bonds in a polymer. For example, ethylene is the monomer or repeating unit of polythylene (polymer). Polymers A polymer (GK : poly = many ; meros = parts or units) is2 macromolecule of very high molecular weight. The molec: weight of a polymer is in the range of 10,000 to several millions For example, polybutadiene (synthetic rubber) has a moleculz weight of about 2,00,000. Apolymer may be defined as a macromolecule containing @ number of repeating chemical units held together covalent bonds. Oligomers A low molecular weight macromolecule composed of a fe* repeating units is termed a oligomer Oligomers are usually liquid Polym the order of 2,000 or so, (oligo meaning a few)- ers of molecular weight of— 4.02 CLASSIFICATION OF POLYMERS polymers may be classified in different ways : fT. Natural and Synthetic polymers i)* Natural polymers : These are the polymers which are jsolated from natural materials. Typical examples are : Cellulose, starch, silk, wool, shellac and rubber. ii) Synthetic polymers : These are the polymers which are synthesised from low molecular weight compounds. Typical examples are : Polyethylene, PVC, nylon and terylene. 2. Linear, Branched and Net work polymers i) Linear polymers : These are polymers in which the monomeric units are linked in a linear fashion to form a straight chain —CH, - CH,— -A-A-A-A-A-A- ii) Branched polymers : These are polymers in which some ofthe monomeric units are attached as side chains to the main linear chain. é ~CH, - CH, - CH-CH, - | CH, A-A-A-A-A-A A im i A (LDPE)4.03 iii) Net work polymers : These are polymers in en many chains are cross-linked through side chains at random positions. These are having a network of chain segments in all the three dimensions. Thus, cross-linked polymers are also k1own as network polymers. “OW OH 107 oH (Bakelite) (Crosslinked) 3. Homopolymers and Copolymers i) Homopolymers : Polymers containing identical monomeric units are called homopolymers, ~A-A-A-A-A-A-A- Examples: {CH, - CH, - CH, - CH, }, (Polyethylene) ii) Copolymers : Polymers having diferent types of momeric ; units are called copolymers. Copolymers are further divided into four types : 4) Alternating copolymers : If two monomer units are arranged alternatively, the polymer is called alternating copolymer. Example : copolymer b) Random monomer un Example: S ©) Block ce monomers ar Example : 81 d) Graft cop made of one r of another mo Example : Sty4.04 -A-B-A-B-A-B- ple: jymer Random copolymer : Arandom copolymer has the different Vinyl chloride (A) - Vinylidene chloride (B) nomer units arranged in a chain at random. -A-B-A-A-B-B-B- ple : Sty rene (A) - Butadiene (B) copolymer ¢) Block copolymer : In block copolymer, the different “monomers are arranged in blocks. graft copolymer, the main chain is ) Graft copolymer : \n h chains are made de of one monomer unit while the branc! - ofanother monomer unit. + Styrene (A) = Acrylonitrile (B) copolymeroy 4. Plastics, Fibres and Elastomers i) Plastics ‘ * Plastics are materials which can be moulded into any desired shape by the application of heat and pressure. * Examples : Polyethylene (PE), polypropylene (PP), polystyrene (PS), PVC. ii) Fibres * Fibres are polymeric materials which can be drawn into long filaments or threads. * A fibre is atleast 100 times its diameter. * Examples : Nylon, terylene, orlon iii) Elastomers * Elastomers are rubber like materials that can be stretched to atleast twice its original length by applying force. * They come back to their original length when the force is relgased. * Examples : Natural rubber, silicone rubber, neoprene (synthetic rubber) 5. Thermoplastics and Thermosetting plastics i) Thermoplastics : These are the polymers which soften on heating and harden on cool ing. Hence, they can be remoulded into articles of desired shape.: ‘a Jes : Polyethylene, polypropylene, polystyrene. polyvinyl chloride (PVC), nylon ii) qThermosetting plastics : There are rigid polymers which soften on heating and set to a hard infusible mass on cooling. Once set, they can not be remoulded. THERMOPLASTICS 1 Polyethylene (or polythene) There are two varieties of polyethylene. a) High density polyethylene (HDPE) b)Low density polyethylene (LDPE) a) High density polyethylene Preparation High density polyethylene (H DPE) is prepared under low pressure (2 - 4 atm) and at temperature in the range of 50- 75°C using triethyl aluminium - titanium tetrachloride catalyst (Ziegler - Nutta catalyst) nCH,=CH, pu yanet-€ CH= OH, i Ethylene HDPE + Uges : HDPE is used for making toys, detergent bottles anc household articles like buckets, dust bins etc.4.07 E 6) Low density polyethylene (LDPE) Preparation Low density polyethylene is prepared under high pressure and at temperature in the range of 180 2S using oxygenas the initiator. ~ n CH,=CH, Neeser ess -Ethylene CH, I CH, | LDPE Uses i) LDPE films are used for packing frozen foods, bakery items and textile products. ii) LDPE sheets are used as table cloths. iii) LDPE pipes are used for irrigation purposes. iv) LDPEis used in cable insulation in rador, TV and telephone. 2. Polypropylene (PP) Preparation Polypropylene is produced by the polymerisation of propylene using Ziegler - Natta catalyst (e.g. Et, Al- TiCl,) n CH, me ea CH,- CH CH, bu, Propylene PP |Peat: 4.08 Uses j) PP is used for making components of refrigerator, radio, T.V and washing machine. ii) It is also used for making automobile seat covers, carpets, ropes, pipes, package films and storage tanks. 3. Polystyrene (PS) Preparation Polystyrene is prepared by the polymerisation of styrene at 90°C using benzoyl peroxide initiator. nCH,=CH — 4CH,-CH} \ | CA, CHE Styrene PS Uses Polystyrene is widely used for making TV cabinets, toys, jars, bottles, combs, buttons, buckles and refrigerator parts. 4. Polyacrylonitrile (PAN) Preparation PAN is prepared by the be senesiasas of acrylonitrile using Peroxide i initiators. +e cH aa cH, cH, ae ow es yAcrylonitrile PANUses f i) PAN is used to produce synthetic fibres such as acrylon. orlon ete. li) Itis copolymerised with butadiene to produce nitrile rubber, 5. Polyvinyl chloride (PVC) Preparation PVC is prepared by the emulsion polymerisation of vinyl chloride at 20°C under pressure in the presence of benzoyl chloride in an outoclave. cmc — +CH,- CH}, | cl cl Vinyl chloride Pvc There are three varieties of PVC i) RigidPvc ii) Plasticized PVC iii) Chlorinated PVC Uses i) Rigid PVC is used for making irrigation and drainage pipes, ii) Rigid PVC sheets are employed for m: aking trays, helmets and mud guards.iy) Chlorinated PVC is produced by dissolving rigid PVC in chlorobenzene. The main use of chlorinated PVC is to » produce adhesives, coatings and fibres (e.g. Saran and Vinyon) # 6, Nylon . Aliphatic polyamides are generally called nylons. There - gre anumber of varieties of nylons : i) Nylon - 6,6 ii) Nylon - 6 iti) Nylon - 10, 6 iy) Nylon - 11 The number indicates the number of carbon atoms present in the monomer molecules from which the polymer is made. a) Nylon 6,6 Preparation ~~ Nylon 6, 6 is produced by the polycondensation between adipic acid and hexamethylene diamine. ‘nHOOC (CH,), COOH + nH,N(CH,),NH, (Adipic acid) | (Hexamethylene diamine) ~ £0C(CH,),CONH (CH,), NH}, + 1 H,0 +. Nylon 6, 6Al eat 1) About 60% of nylon 6, 6 production goes to make carpets, Uses parachute cloth, glider rope, conveyor belt, fishing net, socks and under garments, i) About 10% of nylon 6, 6 is used to produce tyre cords iii) Itis also used as a substitute for metals in gears and bearings, Nylon moving parts do not require lubrication, ‘b) Nylon 6 Preparation Nylon is prepared by the ofa polyamide e.g, caprolactam, HN(CH, ring opening polymerisation O — HN (CH,), CO my Caprolactam Nylon 6 A mixture of caprolactam, Water and acetic acid is introduced into a reactor in the Presence of nitrogen. The mixture is heated Date to 25°C for 12 hours at 15 atm Pressure, After polymerisation, the unreacted monomer and the low : ture Of tyre cord and non-woven fabrics,4.12 ; polyester (Terylene) ~ preparation a polyethyleneterephthalate (PET) is a polyester which is ld in the market under the name terylene (in England) and “qocron (in USA), It is prepared by the condensation of dimethyl "jeephthalate (DMT) with ethylene glycol. e “gHC-0-0C-{Q)-CO- 0 -CH, +n HO-CH,- CH, - OH (DMT) | (Ethylene glycol) £0c{Q)CO-0-CH,- CH, -O% + nH,0. 4 (Terylene) Uses ) Polyester is extensively used to make textile fibres. _ Garments made from polyester fibres resist the formation ofwrinkles. They retain crease and can be washed repeatedly _ Without subsequent ironing (wash and wear cloths) ) PET is made unto film called mylor which is used for making _ £assette tapes and photographic films. Polyester fibres are used in the manufacture of conveyor _ elts, fishing nets, parachute cloth, glider ropes and felts (thermal insulator in refrigerators).4.13 1. THERMOSETTING PLASTICS 1. Phenol-formaldehyde resins Preparation Phenol fromaldehyde (PF) resins are obtained by the polycondensation reaction between Phenol and formaidefiys The reaction is catalysed either by acids or bases. The Catalysed reaction proceeds as follows: 1. Phenol combines with formaldehyde to form addition compounds called methylol phenols. OH OH On H,OH } +HCHO ——>» Or CHOH 2. Further condensation between the methylol phenols phendls occurs to form compounds with methylene bridges. OH OH OH OH On 8 Sag 3. The reaction continues and a linear formed. Polymer cailed reso/S & andy ag ad4.14 4. eso on heating gets converted into a cross-linked three- dimensional polymer called bakelite. 1 AA, OH oH CH; CH; cH, CH- OH CH, CH, OH -CH; CH; cH; cH- OH OH CH. | 2 Uses i) Phenolic resins are widely used as adhesives for plywood, in cementing electric bulbs, for making adhesive wheels, sand Paper and brake linings. ii) Phenolic resins compounded with wood, paper or convas cloth are used in making decorative laminates. (eg. sun mica Sheets). Laminates are used for counter tops, wall coverings, wall clock cases and TV cabinets. iii) Phenolic resin compounded with absestos powder or _ Sawdust is called bakelite. It is used for making electric Switches and plugs, telephone parts etc. 'V) The resol type resin is used for making plastic articles. Y) The alkaline solution of PF resin is used as protective Coatings (paints, varnishes and lacquers)."| 4.15 vi) PF resin is used as cation exchange resin in water softening vil) Resols mixed with sand find use as binders in foundariss. 2. Epoxy resins Preparation Epoxy resins are polyethers prepared by the condensation’ of epichlorohydrin and bisphenol in presence of a base (catalyst) cH, Pe ope) c8 + Ro FH—cH, cl _ Biopenal [= St, 0 OOo inca Ch, OH ew) Epoxy resin Epichlorohydrin Uses i) The liquid epoxy resins (e.g. Araldite, M-seal) are used - as adhesives for glass, metals, etc, ii) Expoxy resins compounded with Polysulphides or polyamides give very tough materials. These are used as surface coatings for skid resistant roads in highways and in industrial flooring.Yr ji) They are applied on cotton, rayon and bleached fibres to jmpart crease resistance and shrinkage control. jy) They are used as dental cement. y) The cured epoxy resins are used to mould aircraft and automobile parts. ELASTOMERS 1, Natural rubber Natural rubber is a high molecular weight polymer of isoprene, in which the isoprene units have the cis - 1,4 configuration. + H,C CH, & a 7 H,C H (Cis 1, 4 - Polyisoprene) Natural rubber Preparation Natural rubber is obtained from the saps (latex) of rubber s especially Hevea brasiliensis. The latex is dilute 1 and ited with 1% acetic acid (coagulant). The coagulated mass lid rubber is washed and sent through rollers when rubber - ts are obtained. es atural rubber is used for making automobile tyres and tubes.oo 4.17 Drawbacks of Natural rubber 4 i) It becomes soft and sticky at high temperature and is too brittle at low temperature. ii) It perishes due to oxidation in air iii) It swells in organic solvents and gradually disintegrates. iv) It has low tensile strength. The above properties of natural rubber make it unsuitable for use as automobile tyres and tubes. To improve the Properties, tubber is cured by what is known as vulcanization. It is carried out by heating rubber with sulphur or S,Cl,. Vulcanination improves the tenside strength by way of cross linking. | 1 I oe CH CH Ss mead ple i : me a CH CH —- §~ cy | I I a mR oy,4.18 peral oil Was used as the initiator and hence the butadiene pers were named Buna rubbers. It is a copolymer of styrene with butadiene (SBR). It is by emulsion polymerisation of styrene and butadiene in g cumene hydroperoxide as initiator. _m CH,=CH-CH=CH, + nCH,= cH (Butadiene) CH, (Styrene) Regs CH CH, CH, CU ars CH (Buna - S) ic ) SBR is a good substitute for natural rubber in making _ automobile tyres. {tis superior to natural rubber for the manufacture of : conveyor belts, shoe soles, gloves, tank lining, floor tiles, kets and electrical insulation. litrile rubber (Buna - N) It is a copolymer of acrylonitriie with butadiene ‘NBR). It is prepared by emulsion polymerisation of tylonitrile and butadiene using azo initiators.} 4.19 | m CH, =CH-CH-CH, +n Saas (Butadiene) | CN | Acrylonitrile + CH, - CH= CH - CH, - CH, - CH Yen CN (Buna - N) Uses i) Nitrile rubber has better oil resistance than natural rubber and hence used for making hoses for oil transport. ii) It is also used as oil seals (oil resistant cable insulation) c) Neoprene rubber Preparation , Polychloroprene is called neoprene. It is made by the emulsion polymerisation of chloroprene. nCH, = CCH CH, —_— iG Gan Cll; GH. 5, cl cl (Chloroprene) _ Polychloroprene (Neoprene) Uses Neoprene rubber has better oil resistance than natural rubber and hence used for making industrial hoses to chy oil | and for oil resistant cable insulation. | |Fae 4.20 QUESTIONS pART-A 1. The polymer formed between styrene and isoprene is classified under a) Random copolymer b) Alternating copolymer c) Block copolymer d) Graft copolymer | 2. The monomer of neoprene rubber is a) acrylic acid b) methyl acrylate c) chloroprene d) acrylonitrile 3. Phenol - formaldehyde resin is called a) PVC b) Nylon c) Bakelite d) Shellac 4. Buna - S rubber is prepared from a) Vinyl chloride + Vinyl acetate b) Butadiene + Acrylonitrile c) Butadiene + Styrene d) Styrene + Divinyl benzene 5. The monomer required to synthesise nylon 6 is a) Adipic acid b) Caprolactam c)Hexamethylene diamine _d) None of these 6. Which among the following is a natural polymer ? a) Cellulose b) Nylon ©) Terrylene d) None of these421 7. Which is acrylonitrile ? a) CH,CN b) CH, =CH-CN c) C,H,CN d)CH,CONH, 8. Trade name of polyester is a) Dacron b)Terylene * c) Orlen d) Both (a) and (b) 9. The polymer used in the manufacture of toys is a) HDPE b) LDPE c)PVC d) None of these 10. The compound used in vulcanisation is a)S,Cl, b) TiCl, c) MnCl, d)CCl, 11. Which of the following is a thermosetting plastic ? a) Bakelite b) PVC c) Nylon d) Terylene 12. Block copolymer type is a)m,m,m,m,m, m,m, b)m, m, m, m,m,m, c)m, m,m,m,m,m, 4) m, m, m, m,m, PART-B 13. Discuss the preparation and uses of PVC. 14. Write the applications of LDPE and HDPE.a ee : "422 f Explain homopolymer: and copolymer with suitable examples. Explain the term HDPE. How is it prepared ? Hos is polypropylene prepared ? Write its uses. 8. What are nylons ? Discuss the preparation of various types | __ ofnylons and their applications. '21.How is PVC prepared ? Wirte the applications of rigid, _ plasticised and chlorinated PVC. : .List out the uses of phenol formaldehyde resin and buna - S | rubber. | 23. What are epoxy resins ? How are they prepared ? Write | __ their applications. |UNIT-V APPLIED CHEMISTRY LUBRICANTS Definition Any substance fnrederet between two moving or sliding surfaces with respect to one another, with a view to reduce the frictional resistance between them is called a /ubricant. Classification Lubricants are classified into three groups : i) Liquid lubricants or Lubricating oils ii) Semi-slid lubricants or ee iii) Solid lubricants 1. Lubricating oils Lubrication in watches, clocks, guns, sewing machines, cycles, scientific instruments etc are done with lubricating oils. Properties of Lubricating oils 1. Viscosity index The rate of change of viscosity of an oil with temperature is measured in terms of viscosity index. It is defined as the average decrease in viscosity per degree rise of temperature. i