. OALEVELNOTES.COM ORGANIC CHEMISTRY Organic chemistry is the study of the compounds of carbon excluding carbonates, carbides, carbon dioxide, carbon monoxide and carbon cisuiphe. The reason for the separate study is that there are far more compounds of carbon (about & milion) ‘than ofall the elements put together. (litle more than 100,000). Also their composition, structure and properties show a lot ‘of difference from the other compounds formed by the rest of the elements, ‘The ability of carbon to form numerous compounds is due to 1 ts abllty te catenate {ability of atoms to join to form along chain). The C-C bend is short and strong and as strong as C- (© bond. (350 and 360 ki mol * respectively). Hence conversion of C-C to C-O bond is not much energetically favoured. 2. High stability ofits covalent compounds. The octet obtalned is fully shared and cannot expand due to the lack of d orbitals of suitable energy. Hence carbon cannot act 2s donors or acceptors. The bonds are also not polarized. Thus bonds of carbon are not easily affected and are kinetically stable. 3. Ability of carbon to form four single bonds as well as double and triple bonds, Four different types of atoms or radicals ‘can oin and make the molecule really varied and complex. Formulae 1 Empirical formula of a compound is the simplest formula of the compound, which gives the rato of the ciferent «elements present in the compound 2. Molecular formula of a compound isa concise representation ofthe actual number of atoms of each element present in one molecule ofthe compound 3. Structural formula is a representation, which gves information about the way atoms are arranged within the molecule 25 wells the numbers of each atom present. Structural formula may be written in two ways. 3. Displayed (structural) formula / graphical formiuiais an explicit representation ofthe bonding arrangements of the various atoms present in a molecule ofthe compound. b. Condensed (structural) formula /tinear formula is a condensed structural formula depicting the various atoms or sroups in a molecule ofthe compound. The side chains are putin brockets Functional group. is the bond, atom or the group of atoms that confers the special properties to the classe. §.-OH in alcohols. -COOH in carboxylic acids, Organic compounds are cassie into a numberof classes depending on the type ot functional groups 1. alkanes: are hydrocarbons where the carbon atoms are joined to each other by single covalent bonds snd the rest of the valency of carbon satisfied by hydrogen. They may be represented by RH where R stands for CyHan 2. Alkones: are hydrocarbons codtaining atleast one C=C bond, the double bond being the functional group of the class 3. Halogenoalkanes: are compounds where one or more hydrogen atoms are replaced by halogen atoms. The simplest hhalogenoalkanes has the genéral formula RX; X being the functional group 4. Alcohols: Organic compounds containing one or more hydroxyl group, -OH; the functional group of the class is ‘OH 5: Carbonyl compounds: Compounds containing the functional group, carbonyl >C=0 There are two classes of compounds ‘that contain the carbonyl group namely aldehydes and ketones. (a) Aldehydes: carbonyl compounds containing the functional group “CHO? (b) Ketones: carbonyl compounds having the functional group °C= 0? attached to two alkyl groups 6. Carboxylic acids: compounds containing the functional group ‘COOH’ 7. Esters: compounds the functional group ‘COR’ 8. Amines: (primary) compounds containing the functional group "NH, 9. Nitriles: compounds containing the functional group °CN’ Homologous series: A series of compounds in which the consecutive members differ by a Ci, group. Members of a homologous series 1Late chemically simitar 2. differ in physical properties but show a gradation 3. can be prepared by similar chemical methods. 4, can be represented by a general formula “The only homologous series without a functional group is the alkaneOALEVELNOTES.COM) TUPAC SYSTEM OF NOMENCLATURE {international Union of Pure and Applied Chemistry Nomenclature) ALKANES: Hydrocarbons where the carbon atoms are joined to each other by single bonds General formula: GHonez 1. Thestraight chain alkanes are given their common names. methane, ethane———- decane ete. 2. Branched compounds are considered to be derivatives ofthe straight chaln compounds formed by the replacement of the H atoms by the alkyl groups, ‘3. The longest carbon chain possible is chosen and numbered from one end to the other in such a way as to give the least ‘number possible to the side chain, The positions of the side chains are indicated by numbers. 4. When there are many substituents the numbering is done from that end in which the first substituent has the least number 5. lf the numeral of the first substituent is the same from elther end then the other substituents are considered 6. When the numerals of the substituents are the same from either end, then the lowest is given to the substituent that ‘appears first in the alphabetical order 7. Names of the substituents should be arranged alphabetically regardless of their numbers ‘ALKENES: Hydrocarbons where at least one double bond exists between two carbon atoms General formula: CsHay 1. The suffix of the class is-ene 2 The longest chan containing the double bond is chosen and numbered in such a way so as to give the least number to the double bond, Ifthe number of the double bond is the same from either end then the side chains are considered ‘+13 funeonal group like OH oF COOH is present, preference i given first tothe funcional group, then to the multiple bond and finally to the atoms or groups designated by prefixes, HALOGENOALKANES: Derivatives of alkanes where one or more hydrogen atoms are replaced by halogen atoms General formula of monohalogen derivatives: CHa aX 1. These are named as the derivatives of the corresponding alkanes, 2 The longest carbon chains ist chosen and numbered so as to give the least numeral tothe carbon containing the halogen atom. ‘3. When there are more than one halogen atom, the least number Is given to the halogen appearing firstin the alphabetical order ALCOHOLS: Organic compounds containing one or more hydroxyl group -OH 4. The suffix ofthe class is ‘ol” which is added to the name of the parent hydrocarbon after dropping the lat letter‘e, 2 The longest carbon chain containing the OM group is chesen and numbered from one end to the ather so 2s to give the {east numeral to carbon atom containing the OH group. 3. Ifthe number isthe same from either end then the other atoms and radicals are considered. 4. While naming the polyhydric alcohols the last letter ‘eis not dropped, N fweconoante CHEMISTRY by N)RJAVANATHANOALEVELNOTES.COM ‘CARBONYL COMPOUNDS: compounds containing the carbonyl group > General formula: CoHanO There are two classes of compounds that contain, the carbonyl group namely aldehydes and ketones, ‘ALDEHYDES: carbonyl compounds containing the group “CHO 1. The suffi of the cassis ‘al and is added to the name of the parent hydrocarbon after dropping the last letter ‘e’ 2. The numberingis always done starting from the aldehydic carbon, 3+ When an ‘OH group is present along with the aldehydic group, the later takes the precedence and the OH group is considered as a substituent and the compound is named as hydroxy aldehyde 4. lf more than one aldehydic group is present the full name of the hydrocarbon is used KETONES: carbonyl compounds of the formula R,C=O 1. The suffix ofthe cassis ‘one’ ands added to the name of the parent hydrocarbon after dropping the last letter “e* 2. The numbering is done so as to give the ketonic carbon the least number 3. Ifthe number is the same from either end then the other atoms and radicals are considered ‘CARBOXYLIC ACIDS: Compounds containing the carboxyl group COOH The suffix of the classi ‘oi’ which is added to the name ofthe parent hydrocarbon after dropping the last letter “e The numbering is always done starting from the carboxylic carbon !¥ more than one carboxyl group is present the complete name of the alkane is used ‘when 2 carbonyl group and 2 carboxyic group are present the carboxylic group takes precedence and the compound is named as oxo- carboxylic acid ESTERS: +The sufix ofthe clas is ‘eat’, which is added to the name of the hydrocarbon after removing the lat letter ‘e’,The alcohol forming the ester is represented by the alky! group of the alcohol, which is written in front NITRILE: compounds containing the cyanide, ~CN group 41. The sux ofthe class is nitrile, which Is added to the complete name of the parent hydrocarbon * 3 Ranetional group like OH or COOH is present, preference i given first to the functional group, then to the multiple bond and finally to the atoms or groups designated by prefixes. * fan aldehyde and a keto groups are present the compound is named as oxo aldehyde * When a variety of functional groups are presentin a compound for numbering the carbon chain the order of preference would be as follows. Substituents _> multiple bonds > hydroxyl group -> carbonyl group > carboxyl groupOALEVELNOTES.COM|) HYBRIDIZATION The electronic configuration of the carbon atom is 1s, 2s, 2p¢, 2p Since there ae only two unpaired electrons avaltable carton should form two covalent bonds. However carbon forms four equivalent bonds and to explain ti its nen ane one ofthe 25 elacttons gets promoted to the 2p level thereby proving four unpaired electrons. Although the prenewing equires energy, ts mare than compensated by the release of energy, which accompanies the forotonetton pence ‘The orbitals are dumb-bell shaped and s orbitals spherical. Hence the four bonds formed by them would not be equal in suength, Further the bonds formed by the p orbitals would be at right angles to each other, while the one formed by the ¢ crbitl should be nor-irectional. But itis known that all the four bonds of carbon are identical in strength and face the four comers of a regular tetrahedron, In order to explain this, it is assumed that the s and p orbitals mix up and produce four new and equivalent orbitals. The rmising combining of atomic orbitals is known as hybridization and the resulting new orbitals are known as hybrid orbitals ‘Thes and p orbitals of carbon can form three different types of hybridization. Sp* hybridization ZThis involves the mixing up, of the 2s orbital and the three 2p orbitals giving four equivalent orbitals directed towards the four comers ofa regular tetrahedron and are referred to as sp° hybridized orbitals Its these four ap* hybridized orbital thea are involved inthe formation of single bonds. In methane each of the four sp° hybridized orbitals overlap with the 4s orbital of hydrogen to form four bones. Since the s orbital is non-directional there wil be a large amount of overlapping, The bord formed of linear overlap is referred to as the sigma bonds. Thus sigma bond isa strong covalent bond formed bythe end semana complete overlap of two orbitals with electron density concentrated between the nuclei ofthe two bonding atoms. Sp? hybridization Here the 2s orbital combines with only two of the 2p orbitals leaving one 2p orbital intact. The hybridization produees three auivalent orbitals lying in one plane and directed towards the apices ofan equilateral triangle. The unhybridzed orbital would ie at right angles tothe plane of the three hybrid orbitals. tis the sp” hybridized orbitals that are invohed in double bond formation, hus the double bond consists ofa strong sigma bond formed of linear and complete overlap and a weak pl bond formed of ‘ateral and partial overlap. The electrons forming the pl bond are referred to 2s pi electrons, Sp hybridization This involves the mixing up ofthe 2s orbital with one of the 2p orbital resulting inthe formation of two equivalent collinear Orbital referred to as the sp hybridized orbitals. The two remaining p orbitals would be perpendicular to each other and to the direction of the sp hybridized orbitals, Triple bonds between carbon atoms are formed by such sp hybridized carbon atoms. tere two sp hybridized carbon atoms bond with each ather by overlapping one of their sp hybrid orbitals. The other sp hybridized orbitals overlap with the 1s orbital of hydrogen atom. Thus all four atoms would be in a straight ine. Then each Carbon atom forms two further bonds with the other by the overlap of the unhybridised p orbitals, The former overlap I "near and complete while the latter i lateral and partial, Thus the triple bond consists of one sigma bond and two pl bones. *fomeroRcante CHEMISTRY by NJRJAYANATHANOALEVELNOTES.COM Shapes of some simple organic compounds Methane and ethane {mn the alkanes the carbon is sp* hybridised giving four identical sp* orbitals which avertap to form four sigma bonds cirected ‘towards the four apices of a regular tetrahedron, Thus in methane each of the four sp” hybridized orbitals overlap with the 1s ‘orbital of hydrogen to form four sigma bonds and thus the methane molecule is tetrahedral in shape. In ethene twa sp hybridized carbon atoms use one of their hybrid orbitals to form a sigma bond linking each other, The remaining three hybrid orbitals overlap with the 2s orbital of hydrogen to form three sigma bonds and thus the molecule would have two tetrahedrons linked, Ethene sp" hybridlsed carbon atoms are involved in double bond formation. The sp* orbitals are directed towards the opies of an ‘equilateral triangle and the unhybridized orbital would lie at right angles to the plane of the sp orbitals. In ethene each carbon atom forms one bond with the other carbon atom and two to hydrogen atoms by means ofits three sp* orbitals The {two unhyoridized p orbitals then overlap laterally, as they are at right angles to the plane of the sigma bonds to form a pi bond. Thus in ethene all the six atoms would lie in one plane Benzene Xray analysis and spectroscopic studies have shown that benzene isa flat hexagon with all the hydrogen atoms lying in the same plane and that all the angles are 120°, Hence each carbon atom is sp* hybrdised, These carbon atoms form six sigma C Conds and six C- H sigma bonds, Thus each carbon atom forms three localized bonds using the sp hybridised orbitels, The remaining unhybridised electrons in each carbon atom would bein ‘p’ orbital perpendicular to the plane of the ring. These electrons can be paired in two ways (a) and (b), both being equally good, Each orbital however overlaps its neighbours forming a delocalised molecular orbital embracing al sx carbon atoms. Since bond strength is determined by the extent of orbital overtap there is greater degree of overlapping and bonding and greater stability in benzene. {The bonds associated with p-orbital interaction in benzene are termed dolocalised pi bonds in contrast to the localised pl bond of an alkene, which is confined to oniy two atoms. The extra thermochemical stability between benzene and the alkene-tike structure is referred to as energy of delocalisation or energy of stabilisation Ethyne Triple bonds are formed by sp hybridized carbon atoms. sp hybridization involves the mixing up of the 2s orbital with one of ‘the 2p orbital resulting in the formation of two equivalent collinear orbitals referred to as the sp hybridized orbitals. The two remaining p orbitals would be perpendicular to each other and tothe direction ofthe sp hybridized orbitals In ethyne two sp hybridized carbon atoms bond with each other by overiapping one of ther sp hybrid orbitals. The other sp hybridized orbtale overlap with the 1s orbital of hydrogen atom. Thus al four atoms would be ina straight line. Then each carbon atom forms ‘wo further bonds with the other by the overlap of the unhybridised p orbitals. The former overlap Is linear and complete ‘while the latter is lateral and partial. Thus the triple bond consists of one sigma bond and two pi bonds ORGANIC CHEMISTRY by NJRJAYANATHANOALEVELNOTES.COM ISOMERISM 'somerism is the phenomenon where two er more compounds, which have the same molecular formula, exhibit diferent properties. There are two types of isomerism. 1. Structural isomerism 2, Sterecisomerism Structural isomerism When compounds have the same molecular formula but different structural formula they are said to exhibit structural 'somerism. Such isomerism is due to the difference in the arrangement of atoms within the molecule. Structural isomerism is {further subdivided into a number of categories. {) Chain isomerism / Nuclear isomerism ‘This arises from the difference in the structure of the carbon skeleton. 7) Positional isomerism This is exhibited by compounds in the same homologous series, which have the same carbon skeleton but differ in the position ofthe functional group. Ii) Functional isomerism ‘When two compounds have the same molecular formula but possess different functional groups they are said to exhibit functional tsomerism. These are compounds belonging to different homologous series, but having the same molecular formula. (a) thers and alcohols (6) ketones and aldehydes ( and enols) (¢)_ esters and carboxylic acids( hydroxyl carbonyl compounds) (@) alkenes and cycloalkanes Feercise Dravi the displayed formulae of all the structural isomers ofthe compound having the following molecular formula and give their IUPAC names (3) Cote (b) CsHio (6) Cute (4) GMO ——(e) CHO STEREOISOMERISM ‘When compounds having the same molecular and structural formula have different spatial arrangements they are said to exhibit stereoisomerism. Stereolsomers have similar structures but differ in configuration. There are two types of stereoisomerism. 1. Geometrical isomerism . Optical isomerism, Geometrical isomerism, This is also referred to as cs - trans isomerism. This is exhibited by compounds where there is lack of rotation eround at least ‘one bond of the molecule. Alkenes satisfy the condition as the pi bond restric freedom of movement, Cis - trans isomerism arises when the double bonded carbon atoms have different groups joined to them.**[The four groups could be diferent] \Wwhen simitar groups le on one side, the isomer i referred to as cis isomer but when they are on the oppasite side, 3s trans isomer. The cls and trans isomer dtfers in all physical properties and some chemical properties particularly Involving ring formation. ‘The trans. isomer is more stable than the cis isomer as similar groups lie further apart and experience least repulsion. The {rans isomer has a high melting point than the cis as in the latter, similar groups lying on one side prevent compact arrangement. The values for the dipole moment, enthalpy of combustion, solubllty in water, the dissociation constant if an ‘acid are high for the cis than for the trans isomer. ‘When the number of sites that can exhibit cis-trans isomerism isn the number of stereoisomers would be 2" purer oRGantc CHEMISTRY by NJ RJAYANATHANOALEVELNOTES.COM OPTICAL ISOMERISM cons tty i the name given to the phenomenon shown by compounds which when placed in the path of beam of pobrit light are capable of rotating the plane of polarization to the left orto the right. Such compourde wre eee to be Sotial active. If the plane of the plane polarised light is rotated to the right the compound is deseined ne dextro-rotatory and if to the left. as laevo-rotatory. us oatical somersm isthe phenomenon where two compounds which have the same molecular and structural formula rotate the plane of the plane-polarised light in opposite directions. corte 2ctity aries due to the chirality ofthe molecule, When a carbon atom i joined to four ciferent atoms or groups It peter to 3s an asymmetric carbon atom and the described as chiral. The molecule containing a chra carbon would not ‘ave centre or plane of symmetry. Molecules that are asymmetii are said to possess chirality. when an asymmetric carbon atom is present the atoms could be arranged in space in such a way that one arrangement Sbpears Xo be an object and the other its mirror image.. These two structures, called the enestomare cannot be crmoctn) Seed as one isa mirror Image ofthe other. Due tothe difference in the spatial arangement of the errs they have ‘opposing effects on the plane of polarized light. fone were dextro-rotatory, the other would be levo-rotatory. The former is ‘referred to as the de-isomer and the latter as i of the other, and the mixture is sald to be optically inactive due to external compensation, The shone referred to as the dl Frese Of racemic mixture. The two enantiomers have identical physical and chemieal properties They differ only in the Thine cecombound containing an asymmetric arbon atom is synthesized always the optically active dl mixture is obtained, Tas because the probability ofthe formation of d and lis 3:1 since the number of molecules Involved a really enormous. Naturally occurring chiral compounds occur as one isomer only. This is because the ensynes thee produce them are 50 stereospecific that only one isomer forms When one chiral centee is present in a molecule two isomers are formed, For a molecule Containing n different chiral centres the number of isomers would be 2” * Write down the structure of each of the following. (2) The simplest alkane that exhibits optical isomerism, (b) The simplest hydrocarbon that exhibits cis-trans isomerism, {c)_ The simplest alcohol that shows optical isomerism (d) ‘The aldehyde with the formula CsH1.0, than can exhibit optical isomerism * Draw the displayed formulae of all the stereoisomers ofthe following compounds. (a) CHsCH=CH-CH=CHCsHs (b) CHyCH(OH)CHCH=CHCH, pee ORGANIC CHEMISTRY by NJRJAYANATHANOALEVELNOTES.COM|) Introduction to organic reaction mechanisms {n organic reactions covalent bonds are broken and new ones are formed. There are two different ways by which covalent bonds can be broken. 1. Homolytic fission 2. Heterolytic fission homolysis is breaking ofa covalent bond in such a way that each atom retains an electron The products formed in homolysis are referred to as free radicals, Free radicals have odd number of electrons and are extremely reactive. Presence of sunlight and peroxides favour homolysis and it usuelly occurs In che gaseous phase or in non-polar solvents Heterolytic fission or Heterolysis: is the unsymmetrical rupturing of a covalent bond where one atom takes complete control ofthe shared pair so tht it acquires a negative charge while the other acquires aposkve charge, The postive fon formed is referred to asthe electrophileo electrophilic reagent anit attacks a melecule atthe port of high ity. The negative ion formed i referred to as the nucleophile or nucleophille reagent and itattocks the molecule at the point of low electron density. ‘When 2 carbon atom has positive has a postive charge itis called a carbocation or carbonium ion andi it has a negative Nearer terred to 2s carbanion. Heterolyticfision occurs in polar solvents since the resultantions canbe temporarily stabilized by solvation The organic reactions are often classified based on the outcome ofthe reactions. They are namely substitution, addition nd elimination, Substitution: when one atom or a molecular fragment is replaced by another Addition: when a double bond opens and new molecular fragments are added at both ends ofthe broken bond, with ‘nothing being removed Elimination: when atoms or molecular fragments are removed from adjacent atoms on a molecule leaving double bond, with nothing being added These three reactions may be also classified mechanistieally depending on whether the reaction is initiated by an clectrophile, nucleophile ora free radical. Inductive effect ‘When two unlike atoms are Involved ina covalent bond the electron cloud forming the bond Is not shared equally due tothe Litfering electronegativitis. Asa result polarisation occurs imparting the more elecro-negative atom a sight negative charge and a corresponding positive charge on the other. The positive charge then wil influence the electron distribution on the neighbouring atoms causing a further but smaller polarisation on the neighbouring atom. This type of electron displacement along a chain of atoms i referred to as the inductive effect, Itis a permanent effect and decreases rapidly as the distance from the source increases. Inductive effect may be represented as C-~Cl or C—-Cl. For measurement of relative inductive effect hydrogen is chosen as the reference Any 3tom or group which attracts electron more strongly than hydrogen i sid to have a negative inductive effect (effect). Any atom or @ group, which attracts electron less strongly than hydrogen is sald to have a positive inductive effect (electron releasing effect) -leffect: NO, > Cl> Br > 1 +leffect —(CHs)yC > (CHy).CH > CHACH, > CyOALEVELNOTES.COM ALKANES Alkanes are the saturated hydrocarbons. Most of them exist as branched or unbranched chains but some of them are cyclic. The former has @ general formula C,Hon. awhile the latter has the general formula C,Hiy Alkenes are not prepared as thay are readily obtained from crude oil. Physical properties: Alkanes are non-polar compounds, the dipole moment being zero. The intermolecular forces are the ‘weak van der Waals forces. Because of the weak intermolecular forces they are highly volatile. At r.tp. the first four Compounds are gases, from the Sth to the 17th or so are liquids and the higher ones are solids. Liquid hydrocarbons are the: components of petrol, kerosene, diesel and lubricating ols. Paraffin wax is made of the solid hydrocarbons ‘As the series is ascended due to the increase in the number of electrons and the surface area exposed, the strength of the van der Waals foreas Ineeases. Consequently the melting and boiling point, density and viscosity increases, while volatility ®nd vapour pressure decreases. For any one sat of isomers the boiling polnt decreases as branching increases, ‘This is because as branching increases the molecules become more nearly spherical and expose less surface area. Hence loss intermolecular forces are exerted, The melting point depends besides the above factors also on the packing of the molecules, Closer packing leads to higher melting point. 2,2-dimethylpropane being more compact and symmetrical has an unusually hhigh melting point (benzene has a higher melting point than methylbenzene) Chemical properties Being saturated and non-polar the alkanes are generally unreactive. Thus oxidizing agents, reducing agents, acids, alkalis, sodium and phosphorus pentachloride have no action on alkanes. Polar reagents have no action, as the compounds are non Polar. Due to their comparative inertness they are used as solvents. However alkanes burn readily and undergo substitution reactions Combustion Ail allanes burn exothermically forming carbon dioxide and water.* Incomplete combustion produces soot (carbon black) and /or carbon monoxide. Complete combustion produces nor-luminous flame while Incomplete combustion produces Yellow luminous flame or even a sooty flame. Methane burns with a non-luminous flame but ethane with a slighty luminous {Tame due to Its higher carbon content. Combustion reaction is the basis for the use of alkanes as fuels in home, industry and transport. Nota: A given volume of gaseous hydrocarbon produces as many volumes of carbon dioxide as the number of carbon atoms Present in @ molecule ofthe compound, Ths fact was used in the past to determine the molecular formulae of hydrocarbons (Eudiometry) Example. 41, 10 cm’ ofa gaseous hydrocarbon were exploded with 100cm* of oxygen. The gaseous product was treated with aqueous potassium hydroxide when the volume diminishes by 40 cm*. if the oxygen left over was 35 cm? calculate the molecular formula of the hydrocarbon, 2, Caleulate the volume of air required for the complete combustion of 100 cm? of propane, assuming air to contain 20 % by volume of oxygen. 2 Bicatofatyrocaton exe were but noes of nn ttm enpeiureand pressure When he teenie and pressure returned to the original value there was a decrease of 15 em? in volume. When treated with aqueous potassium hydroxide solution there wes a further decrease of 20 cm* Calculate the molecular formula of the hydrocarbon 4. Draw displayed, structural and skeletal formula of the isomers of the compound of molecular formula Cs Hsz and give their IUPAC names Substitution Alkanes undergo substitution reactions with chlorine and bromine in the presence of diffused sunlight to form mono and oly: substituted products. in the presence of u.v light chlorine undergoes homolysis to give CI’ free radicals.* ‘The free radicals then attack the methane molecules abstracting @ hydrogen atom to form hydrogen chloride and a methyl Cis" free radical which in turn attack the chlorine molecule to form chloromethane regenerating the C free radical to attack ‘more of the methane molecules. When the concentration of chloromethane increases, the CI’ free radicals attack them Instead of the methane molecules ‘thus continuing the process until all the hydrogen atoms are replaced, 3 i z B = > z & 5 a = é S 2g S 3° 2 i 4OALEVELNOTES.COM|) Wowever there are other reactions which can intervene to stop the continuation of the substitution reaction. These are reactions in which the free radicals combine with each other to form molecules ‘These reactions are negligible since the concentration of the free radicals at any instant is very small compared with the ‘molecules and hence the chances of collision between the free radicals are rather remote, ut at the end of the substitution of all the hydrogen atoms the Cl’ free radicals combine to terminate the process ‘The chlorination of methane is a typical example of free radical chain reaction. In chain reactions there is an initiating step followed by propagating steps and finally the terminating step Initiating step : the formation of free radicals. Propagating steps :free radical reacting with a molecule to give another free radical and @ molecule Terminating step : Combination of free radicals to form molecules. ‘+ When ci" reaets with methane, HCI and CHa’ form in preference to H’ and CHCl as the products HCI and CHy" are energetically stable than H” and CHCl. The former reaction is exothermic (+413 - 436) while the latter is endothermic (+413 -327) * The wv rays that reach the earth are not energetic enough to rupture the C - H bond but is sufficient to rupture the ‘weaker Cl-Cl bond, ‘* The above reaction can take place in the absence of sunlight at high temperatures When ethane is substituted with bromine/ chlorine nine compounds form some of which are isomers. ‘When a liquid alkane and liquid bromine are mixed and exposed to sunlight the red brown colour of bromine gets discharged and gaseous fumes can be seen escaping NOTE: Free radical chain reactions involving initiation, propagation and termination are thought to occur during thermal cracking. In thermal cracking also described as steam cracking) the heavy fractions are treated with superheated steam at 800°C. Under the high temperature homolysis of carbon ~ carbon bond occurs giving alkyl free radicals. While some free radicals take part in propagation producing other free radicals and smaller alkanes others expel hydrogen free radical to form alkenes Write equations to show how methane, ethane, pent-t-ene, but-1-ene may form from hexane chain reactions also occur during the polymerization of alkenes PETROLEUM Petroleum refers to the complex mixture of naturally occurring liquid hydrocarbons including the dissolved gases ‘and solids as well as to the gases above the liquid. Its believed to have been formed from small marine animals and plants that were buried in the beds of the sea millions of years ago. Under the influence of heat and the pressure of the overlying strata and also due to bacterial activity the remains of these animals were thought to have decayed to give petroleum. Petroleum is 2 non - renewable resource and should be used more prudently. If not we have to find alternate sources of tenergy sooner than later ‘The composition of petroleum varies with the source of the oil. Hydrocarbons are the main and the most important component of petroleum. Alkanes and cycioalkanes constitute 90% of the hydrocarbons, Aromatic hydrocarbons also comprise an appreciable amount, thus crude oil is a source of both aliphatic and aromatic hydrocarbons. in addition to the hydrocarbons there are also present compounds containing nitrogen, sulphur, oxygen and metal Cracking The lower hydrocarbons e.g, naphtha and gasoline are in great demand as they find wider applications and also serve as starting materials for most petro-industry but their supply Is limited, The long chain hydrocarbons, the heavier fractions, are not in much demand but are found in larger proportions. Hence long chain hydrocarbons are broken down to smaller hydrocarbons industrially. The thermal decomposition of long chain hydracarbons into smaller hydrocarbons in the absence of oxygen is referred to as cracking. Cracking is usually carried out in the presence of catalysts. Cracking produces smaller alkanes along with alkenes and sometimes hydrogen. The nature of the products depend on the (a) nature ofthe starting material (b) nature of the catalyst (c) temperature ALKENE Z Z 2 zB > = a 3 a z é g g % © @ SOALEVELNOTES.COM Sant 2t@ the unsaturated hydrocarbons, which contsin atleast one double bond. The simplest homologous series of alkenes with single double bond have the general formula CH, Methods of preparing alkenes 1. Dehydration of aleohol (2) Passing the alcohol vapour over alumina at 350°C (6) By heating the alcohol with excess concentrated sulphuric acid at 170 180°C 2. Dehydrohalogenation wean halogencalkanes are heated with ethanolic solution of potassium hydroxide hhydrogen halide is eliminated to give alkene. The yild is poor with haloethane but quite high for higher halides "Note: in industry alkenes are obtained by cracking both thermal and catalytic Properties Prt petezmolecular forces in the alkenes being the van der Waals forces the alkenes resemble alkanes in their Eiysca properties. However they are slighty lower than alanes a6 the dousle bates being rgd prevent them coming Closer. They also show the usual gradation as the series ls asconced, Reactivity of alkenes onal ect teplaced by two stable sigma bonds. Thus alkenes undergo addition reaction. Due to the presence of the double Lond thare isa layer of negative charge above and below the carbon ators and hence alkenes are susceptible to lectrophilic attack, Thus the majority ofthe reactions of alkenes, are electrophilic addition reactions. 1. Hydrogenation, Amisture of alkene:and hydrogen when passed over Ni catalyst at 200 -200°C reset to, give alkanes ‘ikenes adc onto liquid or gaseous bromine at room temperature to give vie - dibromoatkanes Mechanism: When a bromine molecule approaches the double bond the electron coud of the pi bond repels the outer lection ofthe nearest bromine atom and the molecule becomes polarised, The rechiny slightly positively charged bromine iton then attracted to the pi bond, As the postive Br atom joins the one ofthe eereay ‘atoms the Br - Br bond and the pi bond rupture resulting inthe formation of BF and a carbocation, The intermedine carbocation then joins with the Br. The reaction Is cs aeat® ionic reaction. The carbonium fon is free to add to any negative lon In the system, This is seen if the reaeon scarred out in the presence of CI when ethene gives I-bromo-d-chiorecthone ‘along with 3,2- dibromoethane confirming that the carbonium ion is free to add to the fi an electrophile the reaction is electrophilic addition reaction, Note: Chiorine reacts in the same way as bromine. 5. Alkenes react with bromine water to form mainly bromoalechols with a negligible amount of cibromoalkanes. The ceneeot i Similar to that of quid bromine but the carbocation attacks the water molecule hevtod as itis found in large concentration. Very small amount of dibromoalkane Is formed. ‘4 Alkenes when mixed with gaseous hydrogen bromide or hydrogen lodide add on to form haloalkanes. HCl reacts in the presence of anhydrous aluminium chloride ‘spies ORGANIC CHEMISTRY by NJRJAYANATHAN ‘groups. Since the charge is spreac formation of 2- bromopropane. Premise ete Steet 4OALEVELNOTES.COM 5. When an alkene is passed through cold dilute alkaline manganate (Vil) diol is formed. During the reaction the purple colour of manganate (VIl)is removed. Brown specks of WInO. may be seen setting down ‘Note : Green colour of manganate (VI) may be seen ifthe solution is not dilute enough. 6. When an alkene is passed through hot concentrated aqueous manganate (Vl) the double bonds rupture giving two carbonyl compounds. if the carbonyl compound Is an aldehyde it s further oxidised to the corresponding acd, By identifying the products the structure of the alkene ie the position ofthe of the double bond can be ascertained 7. When a mixture of alkene and steam is passed over phosphoric catalyst spread on an inert solid e.g, silica at 200° C and 70 atmosphere pressure alcohol Is formed. 8. Alkenes undergo polymerisation to give polymers. (Refer polymerisation ) Exercises 1. Draw displayed formulae ofall the products that could form when propene is passed through bromine water containing sodium chloride 2. Draw displayed formulae of all the structural isomers of pentene, Give their IUPAC names. Give the names of the products that would form if the alkenes were treated with hot concentrated aqueous potessium manganate (Vl) 3. Draw the displayed formulae of the hexene that would give the following compounds when treated with hot concentrated aqueous potassium manganate (Vil) 2) CHsCOCH, and C,HscOOH ) C.HsCOOH only ©) CH:CH:CH,CH,COOH ) CH,COCH, only ) CH.CH,CH,COCH, f) CH,CH(CH,)COOH and cH,cOOH 8) CH,CH(CH,) CHCOOH hh) CH.CH,CO CH.CHs fisveroRcante CHBMISTRY by NJRJAYANATHANOALEVELNOTES.COM HALOGENOALKANES ea robe derivatives of alkanes are referred to as allyl halides. They have the general formula Caan nX and are written Fee ne” are classified as primary, secondary and tertiary depending on the number of ally! Groups attached to the halogen - containing carbon. General methods of preparation + Photohalogenation: applicable to ony chloro and bromoalkanes; nota good method as polysubsttution takes place, 2. Addition of HX to alkenes 3. Action of FXs on aleohols: Por. and Pl are prepared in situ. The ally! bromide and lodide are repated by treating the ‘leohol with a mixture of red phosphorus and the halogen at room temperature 4 Aation of 4X on alcohols: The chloroalkanes are obtained by bubbling cry HCl gas into the cleohol in the presence of 2grvarous zinc chloride, The bromo and the fodoalkanes are prepared by heating the alcohol undecratie: with constant bolling hydrobromic or hydroiodic acid. 5 few of Phosphorus pentachloride/Sulphur dichloride oxide on aleohol: The chloralkanes may be obtained by treating alcohol with SOG, /PCI, at room temperature Physical properties Trooe atte, chloroethane and bromomethane ae gases at room temperature. The others are mosty liquids. However agen wt high My are solids The gases and the quis have a pleasant odour. The nar molecunn ts prevailing in Ualenoalanes are the van der Wat's forces, the ciple ~ dipole atractons being not ven cece monchalogen cenuatves Thus al the heloatkanes are insoluble in water (as they cannot form hydrogen ordhn are woter). They are 00d solvents for organic compounds, *__ Fora given alky! group the volatility decreases as we move from F to 1 CoHsCl(-12.5°C) CoHsBr (38.4°C) C,Hs!(72.8°C) © he straight chain isomers have a higher boiling point than their branched isomers (CHsCHgCHaCl (47°C) CHyCHCICH (36°C) “oy h0r halogenoatkanes ofa given molar mass the volatility increases as we move from Fto | Calta (183°C ) CeHssBr (130°C) Chil (62°C) i z 2 z Reaction mechanisms of halogenoalkanes _ ‘The C - X bond is polarised because of the higher | electronegativity of the halogen, giving the C atom a slight positive charge, > a aes nal toradeophicatack Nasgeronines encoun mcspcusveaonrecoe en these radios the C- bond undergoes heterosis and the aloe som gts elacains seca ne 5 sere zeroes team om of he CX bond am thee oppose ble ate itacls steenspecte. A dest ens to forma bond with te erton atom siulancousy weateong de Gentes ‘At one stage the C—-OH bond would be half formed and the C—- X bond would be half broken. The intermediate will havea trigonal bipyramidal structure. Later the C—- OH bond becomes stronger and the C —- X bond ‘Tuptures forming the X’ion and O the moles gets inverted Tiss a onestep proces, two species simultaneously undergoing ence oe ee 2 determining step. E a 3 2 6 Reactions of RX ++ When 3 halogenoalkane i heated under reflux with an equeous alal itundergoes hydrolysis to give alcohol 2. When warmed / heated under reflux with ethanolic solution of potassium cyanide nitrile Is formed.OALEVELNOTES.COM| 3. When a halogenoalkane is heated with ethanolic solution of potassium hydroxide the higher members mainly undergo RBr > RC >> RF [Ts is Because the rate of hydrolysis depends on the ease with which heterolsis of the CX bond occurs. As the atom becomes smiler bond length decreases, bond strength increases and hetealyis becomes more dificult Hence the rate of reaction decreases, bond C1 CBr ced or bond energies / I mot 200 28040 485 Uses of Halogenoalkanes seeratanes have anaesthetic properties. The introduction of increasing number of chlorine atoms into a molecule of thane reduces flammabilty and increases anaesthetic properties as walla toil. Also chlorinated alkenes avo seein Heasttuction of fluorine atoms brings about inertness (CF bond is very strong) The fluroalkanes commonly referred to as fiorpearbons are thus very stable, non-toxic and norifammable. The polymer PTEE i highly resistant fo a cheeiaks aoa also has very low coefficient of friction, Hence used as covering in non-stick pans and moules, [The fluorochloroderivatives (CFC) of methane and ethane referred to 2s Freons are Used 22 refrigerants and in aerosols, air- Conditioning systems and in packaging as these compounds are volatile, adouress, colourless, stale, onfizmmable, chemically Inert and have low toxicity. CFCs are also not affected by ultraviolet radiation inthe troposphere. solvent for degreasing Effect of CFCs on the ozone layer The reactions involved inthe formation and breakdown of ozone inthe stratosphere helps to absorb the harmful ultraviolet ‘adiation ofthe sun and prevent it reaching the surface ofthe earth.* The ozone is broken down to onygen by rctng ait other molecules ike NO and the level of ozone remains constant under normal conditions, The molecules of CFCs diffuse in the atmosphere and ultimately rach the stratosphere where they encounter the high- enerey uv ratlation. The C ~ Cl bond undergoes homalyss to give CI free radicals. The Cl free rats reat with onre {Paring molecule oxygen and ClO fre racials which in turn react with Ore rales to give further enygenregeneratng the Cl’ free radicals which continue the attack on ozone thus bringing about a chain reseron, The CI’ free radicals act as, Catalysts n the conversion of ozone and O” to exygen gos, thus destroying the ozone layer, Cal 2 few compounds can substitute the CFCs as the combination of all the desired properties like inertness, Tonflammabilty and nontexicity and required volatility in a compound is hard to come by. Some hydrofluoroalkenes are found to meet the requirements e.g 3,,1,2-etraflucroethane, CFSCH4F. The advantoge ofthe HFCs/pas is that hte there iso chlorine to damage the ozone layer, C- H bond is fatly reactive. The hydrogen atoms ean be replaced by reactive Giemicals ike the OH radical In the troposphere and hence these compounds breakdown more quickly thon CFCs, Nntorunately the HFAs are able to absorb the infra-red emissions from the earth's surface and may contloute to glebsl warming, [Chapters ORGANIC CHEMISTRY by NJRJAYANATHANOALEVELNOTES.COM ALCOHOLS ‘The general formula ofthe menchydric alcohols is C,HanyOH. These form a homologous series and are classified as primary ‘Secondary and tertiary alcohols depending onthe number of aly groups present on the carbon having the OM group.” Reactions where alcohol is formed 4. alkaline hydrolysis of halogenoalkanes. 2. Hycrolysts of esters ‘hen an esters bolled with aqueous alkalis it undergoes hydrolysis to gve alcohol and the salt ofthe acid, Hydrolysis can be done also by heating with dilute acids but the reaction attains equilibrium, 3. Reduction of carbonyl compounds When a carbonyi compound is treated with s followed by the decomposition by the a while ketones give secondary alcohols. Properties of alcohols Fiero eutral compounds, The lower members ae Iqulds and have characteristic odours and burning taste, The higher members are solids. The lower aleohols dissolve in water freely and the solubility decreases with Increasing My, rr anol would dissolve in water ony if the energy liberated during the formation ofthe hydrogen bond bythe aloholc [Ox with water i sufficient to overcome the intermolecular forces existing between the aly grours, Ac the cox of the alkyl £roup increases the intermolecular forces would increase thereby reducing solublity. £0" 2 Sroup of isomeric aleohols straight chain isomers dissolve less than the branched isomers due to the comparatively larger intermolecular forces existing in straight chain compounds, ire alcohols have higher bolting points than alkanes of comparable molar mass due to the association through hydrogen bonding existing over a chain of molecules, For @ troup of isomeric alechols the belling points of branched isomers are lower than those of the straight chain compounds ighels are weaker acids than water. The aly group being an electron selessing group decreases the polarisation ofthe 0 H bond hindering the release of proton Reactions of alcohols 1. Combustion: All alcohols burn exothermically in air or oxygen giving carbon dioxide and water 2+ Strongly electropostive metals like sodium and potassium liberate hydrogen from aleohols forming the alkoxide 3. With PX; they react to give halogenoalkanes (refer RX) 4. With HX acid they react to RX (refer RX) 5. With PCI, and SOC, alcohols give RX (refer RX) fs ec ORGANIC CHEMISTRY by NJRJAVANATHANOALEVELNOTES.COM| Note: All hydroxy compounds liberate white fumes of HCI when treated with PCl. Hence used asa test for the presence of ‘OF group. Since as many moles of hydrogen are liberated as the number of OH groups in a molecule, the reaction is made use to determine the number of OH groups present in a molecule of the compound. 6. Ester Formation ‘Alcohols react with alkancic acids to form esters. The reaction of alcohol with alkanoic acids is referred to as esterification. ‘The reaction is reversible attaining equilibrium. The backward reaction is hydrolysis. Acids catalyse the reaction. Normally esterification Is carried out by heating a mixture of carboxylic acid and alcohol in the presence ofa litle concentrated sulphuric acid, The sulphuric acid acts as both a catalyst and a dehydrating agent, thus increasing the rate and the yield. Esterification done using alcohol with labelled 0 produces water whose M, is 18. This Indicates that OH from the acid has combined with the H ofthe alcohol to glve water unlike neutralization 7. Oxidation Primary and secondary alcohols are readily oxidised to aldehydes and ketones respectively. Tertiary alcohols resist oxidation, ‘Oxidation is normally carried out by warming the alcohol with acidified sodium dichromate solution, The aldehydes may be obtained by distilling off the products. i refluxed aldehydes undergo further oxidation to give the corresponding acids.. the group >CH-COH< are dehydrated to give alkenes. . The reaction may be carried out either by passing the alcohol vapour over Al,03 at 350°C or by heating the alcohol with excess concentrated sulphurie acid to 170 to 180°C ‘Test for the presence for the presence of ‘OW’ group. +1 Phosphorus pentachloride give white fumes of HCI 2. Sodium liberates hydrogen (sodium sinks and gives out bubbles) ‘Test for alcohol Esterification: When an alcohol is heated with a carboxylic acid in the presence of a few drops of concentrated sulphuric acid ‘and poured into water or aq, NaHCOs solution a fruity odour can be detected. Tests to differentiate primary, secondary and tertiary alcohols ‘1. Warm the aleohol with acidified sodium dichromate. If the orange colour of dichromate turns green, distill and warm the product obtained with Fehling’s solution a) Tertiary alcohol: The orange colour remains unaffected b) Secondary alcohol: The orange colour turns green but Fehling’s solution is unaffected ¢} Primary alcohol: The orange colour turns green and with Fehling’s give a brick-red precipitate, ‘Manufacture of ethanol: Hydration of ethene (Refer alkene) and by fermentation Uses of ethanol: as a solvent, for alcoholic beverages, blending into motor fuel, for the manufacture of ethanal and ethanoic acid, Uses of methanol: to obtain methanal for the production of plastics; used as solvent for varnishes, paints and polishes. Uses of ethane-1,2-dlol: for the manufacture of Terylene, as antifreeze and de-icer i 2 2 Z = » Z 2 3 a = & ° z zg & 2% $ BOALEVELNOTES.COM Carbonyl compounds General methods of preparation 41. Oxidstion of aleohols Aldehydes are prepared by the controlled oxidation of primary alcohols while ketones are prepared by the mild oxidation of secondary alechols. The oxidation is carried out by warming the alcohol with acidified solution of sodium dichromate and distilling off the products formed. 7 General properties of carbonyl compounds, Both aldehydes and ketones have the >C=O group in common and hence in all reactions involving >C=0 group they show similarities, Aldehydes have an easily oxidisable C - H bond attached to the carbony! group. Hence aldehydes differ from. ketones in that they are good reducing agents. ‘The C=O double bond like the double bond of alkenes is formed of one sigma bond and one pi bond but the electrons are not equally shared due to thee high electronegativty of oxygen giving the carbon atom a slight positive charge, This makes the carbonyl carbon susceptible to nucleophilic attack. (Electrophlic attack on oxygen isnot favoured as the carbonium ion is less stable than the ion having a negative charge on oxygen) ‘The reactivity ofthe carbonyl compounds decreases with increasing size of the alkyl group. This i attributed to the decrease of the positive character of the carbonyl carbon due to the inductive effect of the alkyl group. Also the stereic hindrance of ‘the lage alkyl group does not allow the reagents meeting the carbonyl group. Physical properties of carbonyl compounds ‘Methanal fs 2 gas. Other short chain carbonyl compounds are liquids. Bling points of carbonyl compounds are higher than Of the alkanes of comparable molar mass due to the appreciable dipole-dipole attraction prevaliing but much les than thoes of alcohols where there exists hydrogen bonding. Reactions of carbonyl compounds 1. Addition reaction Cerbony| compounds add on to hydrogen cyanide to give nitriles. The reaction is carsied out by treating the carbonyl ‘compound with excess of aqueous sodium cyanide and dilute sulphuric acid, Mechanism: The reaction is a nucleophilic addition reaction initiated by the attack of CNwhich acts as a catalyst. The CN ion adds on the carbonyl compound forming an intermediate which then abstracts @ proton from the HCN molocule +o regenerate the CN ‘The reaction rate is proportional to the concentration of CN’ and is also dependent on the pit of the solution as a high concentration of the H” lowers the concentration of CN’. Note: The reaction may be carried out with aqueous sodium cyanide containing litle of alkali. The intermediate formed abstracts proton from water. The aikall maintains @ high concentration of the CN by suppressing the hydrolysis of CN. Note; The hydrony-nitriles are easily hydrolyzed to hydroxy-acids by heating under refiux with concentrated (dilute hhydrochloric acid.(or 70% sulphuric acid) This reaction provides a convenient method to prepare 2-hydroxyaclds, 2. Condensation reaction Carbonyl compounds undergo condensation reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH) to give a yellow or ‘range precipitate of the corresponding hydrazone. The reaction is used as atest for the presence of carbonyl group. ‘The reagent 2.4-dinitrophenylhydrazine is used either dissolved in methanol or concentrated sulphuric acid. The former is referred to as Brady's reagent. pte ORGANIC CHEMISTRY by NJRJAYANATHAN %OALEVELNOTES.COM__ 3. Reduction ‘The carbonyl compounds are reduced to the corresponding alcohols by treating the compound with lithium aluminium hydride dissolved in dry ether and then adding water or dilute acid to it. Reduction may be carried out with sodium end ethanol or with hydrogen in the presence of nickel or platinum catalyst or with sodium borohydride in aqueous solution Aldehydes give primary alcohols while ketones give secondary alcohols. 4. Oxidation Aldehydes are oxidized readily to their corresponding acids by ac donot undergo oxidation ed sodium dichromate or manganate (Vl). Ketones Reactions given by aldehydes only. Since ketones are not easily oxidized, mild oxidizing agents have no effect on them unlike aldehydes, which are easly ‘oxidized. This difference is made use to differentiate aldehydes from ketones. 1. Aldehydes answer the silver mirror test. Aldehydes when heated with Tolten’s reagent preferably in a water bath reduce it to metalic silver The sliver deposits as 2 mirror on the wall of the test tube ifthe tube is spotlessly clean. it may come down as a black powder if the tube is not Clean, Tollen’s reagent or (Ammoniacal silver nitrate) is diammine silver(I) hydroxide. it is prepared by adding a few ‘drops of aqueous sodium hydroxide to aqueous silver nitrate and then dissolving the silver(I) oxide formed in minimum quantity of aqueous ammonia, 2. Aldehydes reduce Fehling’s solution Fehling's solution contains copper (I!) hydroxide inthe form of a deep blue complex. Aldehydes reduce it to red copper (0) oxde when heated with i. The colour changes from deep blue to green, to yellow to orange and finaly to a brick red Precipitate. Note: Fehling's solution and Tollen’s reagent are mild oxidizing agents and they do not affect the double bonds. Hence ‘unsaturated aldehydes can be oxidized to thelr corresponding acids without rupturing the double bond, Uses of carbonyl compounds ‘Methanal: Manufacture of thermosetting polymers, phenol-methanal plastic and urea-methanal plastic eg, Formica Bakelite Melamine and as formalin - 40% aqueous solution of methanal Ethanal: Manufacture of paraldehyde (sleeping drug), metaldehyde (slug killer) DDT. Propanone: As solvent, to make plastics e.g. Perspex Exercises 4. Three compounds E,F and 6 allhave the molecular formula CsH,0. Eis an alcohol, Fis a ketone, and G isan aldehyde, (a) Draw possible structural formulae for E, Fand G. (©) Describe tests (reagents ,congitions and observations with each compound) that would allow youtoshow that 1, Elsanalcohol whereas Fand G are not, + Fand G are carbonyl compounds, whereas Eis not. Gisanaldehyde, whereas € and Farenot. 2D, molecular formula C,H40, gives an orange precipitate with 2,4-dinitrophenylhydrazine Teagent but does not give 2 precipitate on boiling with Febling’s solution. D undergoes catalytic reduction with hydrogen ‘give liquid E, which on dehydration give a colourless gas F. On passing F through hot concentrated aqueous manganate (Wi)a single product 6, with molecular formula C4402 s formed. Identify E, F and G and write equations for the reactions. fseroncanic CHEMISTRY by NJRJAVANATHANCarboxylic Acids General methods of preparation \ 2. Carboxylic acs may be prepared by the oxidation of primary alcohols or aldehydes using aisha Schoen 2+ Acids canbe also prepared by hydrolsing the nitriles. Tis is caried out by heating the miss wndes some with Toe Sulphuric ator with ut /concentrated HCL Heating under efx, wth aqueous solution cf st ane ee sag the produets ean aso carry out. Physical properties of carboxylic acids ‘The lower members are colourless liquids with pungent odour and dissolve in water readily, The solubility decreases with Increasing molar mas. Solubility ofan acid is greater than thet of the corresponcing alcohol due tothe greater polareavon of the 0-H bond, together with some ionization Boiling points of the acids are much higher than that of the ‘corresponding alcohol because of the stronger hydrogen bonding, prevailing due to the greater polarity of the O—H bond. Reactions 1, Being acids they dissolve in alkalis forming salt and water. 2. Carboxylic acids are weak acid (ionise about 1-2%) but they are stronger than carbonic acid. They liberate carbon dioxide from carbonates. 3. With alcohols they form esters. Refer alcohols 4. With strongly electropositive metals they react giving hydrogen. 5. None of the acids excepting methancie acid undergo oxidation Note: Methanoie acd has a unique structure in that besides the carboxy group effectively contains an aldehyde group, Hence It gives the reducing reactions of the aldehydes. Thus itcan be oxidised by acidified manganatetVil) and acidified ichromate to carbon dioxide and water. Further it reduces Tollen’s reagent and Febiing’s solution when heated. Tests for carboxylic acids L.Liberetes carbon dioxide from carbonates. 2. Esterification ~Refer test for alcohol Uses, methanoie acid: Dyeing, electroplating, tanning and coagulating rubber. «thanoic acid: polyvinyl ethanoate, (pva) cellulose ethanoate (acetate rayon) and metallic ethanoate benzoie acid: food preservative Esters Lower esters are liquids with pleasant fruity odour. The higher ones are solids. The melting and bolling points are below ‘hose of the comespending acids 2s they cannot associate by hydrogen bonding. For the same reason esters are insoluble in water. Esters are hycrciyue to alestial Sy water slowly. The reaction attains equilbrium. The reaction is catalysed by acids and clkals. Acid catalyses Ingciaiisis Goes mot eo compiition. Alialine iiroiysis is faster and goes to completion, The alkaline hydrolysis of estes i sseses So as ssponifcstion (soap making) since soaps are made by such reactions from naturally Ccouring esters, Ss ana ai Seine iS comin’ out by esting the ester mith dilute mineral acid or aqueous alkalis. Hydrolysis of estes siti Ei S seeaie iat the CO Sond formed between the carbonyi carbon and oxygen only ruptures Uses of esters: ArSficcl aman as peiumes, aescthent: for Gruss Manufacture of soaps. OALEVELNOTES.COM | J (FSS ond ols ae eames af tage coctmepic Sc ant proper 1 Serci Wane: 32 ees ater cetenpic acs ant higher aichck eg beeswae 7 EMISTRY by NJRJAYANATHANa Pr ee POLYMERISATION Ty Polymentsation is the process of forming giant molecules by the repeated combination of small molecules. The small molecules are known as monomers and the giant molecules are referred to as polymers. There are two types of 22 properties ofthe polymer Ike tense strength, flexbilty, hardness and softening temperature depends on a number of $2i2g Is Polmeric chain length, branching, the type of intermolecular forces and cross linking. suenath and softening | Soybeetne mainly depends on the average length of the polymeric chain. Unlike stright chain palymere traces | EexEes do not pack closely. Hence branched polymers have low density and low softening tempersture wile eke | BeGached polvmers have high density and high softening temperature. Strong intermolecular forces ace ge fasta high ‘Softening tempereture and hardness. Extensive crosslinking makes the molecule hard and brittle Addition polymerisation. ‘These are made.from alkenes and substituted alkenes. Double bonds open up linking the molecules to each other. The eave taited out ip the presence of catalysts, The catalysts discovered by Zlelor and Netia ep Te, ord Sebitlumintum (Cat) sAl have the advantage thatthe polymers formed are unbranched and canbe tallotes to setae Sitiene: Polythene is obtained by heating ethene under high pressure (1500-2000atm) to 200°C in the. presence of traces S225, The polymers obtained thus are branched and hence af low-density polythene, Low density polymers are used for ‘does not have a sharp meting point. It softens ‘Over @ range of temperature. This is because the polymeric chains S Srssial lengths. The softening temperature is low as the linear polymer is held only by von dr Wiese eae ne) oF polyvnyichlorde (pve): The polar C~ Cl provides stronger inter-molecular attraction between the ins. Hence pvc is much stronger polymer than polythene Sestroyed by bacterial action. Thus these polymers are nor-biodegradable. Further they cannot be ‘economically, Sais of the dificult in separating the sifferent types of polymers inthe plastic. Some ofthe polymers da aoc Desies, some of the combustion products are also polsonous, for example HCL from PVC. Hence synthetic disposal problem. GHEMISTRY by NJRIAYANATHAN