Chapter - 7 Spectroscopy‘CHEM ACADEMY INTRODUCTION The molecular spectroscopy is the study ofthe interaction of electromagnetic waves and matter, All different forms of electromagnetic radiations travel at the same velocity but characteristically differ each other in terms of frequencies and wave length. (Table 1) Table 1: The Electromagnetic Spectrum Radiation type Wavelength Frequency ‘Application 2, (A) v=clh (Hz) Radio| 10" 3x10" ‘Nuclear magnetic Resonance 10" 3x10" Spin orientation 4 Television | 10" 310 Radar 10 3x10” i 10 3x10 Rotational 3x10 Vibrational 3* 10) 37x 107-75 * 10 Be1O— 4x10" ‘Ultraviolet 3x10, 1x10" Electronic X-rays 1 310" Gamma rays 107 3x10 ‘Nuclear transition ‘Cosmic rays 107 3% 10" The propogation of these radiations involves both electric and magnetic forces which give rise to their common classname electromagnetic radiation. In spectroscopy, only the effects associated with electric component of electromagnetic wave are important. Absorption of Different Electromagnetic Radiations by Organic Molecules In absorption, through the mechanism ofenergy is different in the ultraviolet, infrared and nuclearmagnetic resonance regions, the fundamental process is the absorption of a discrete amount of energy. The energy required for the transition froma state of lower energy (E,) to state of higher energy (E,) is exactly equivalent to the energy of electromagnetic radiation that causes transition, E, Energy transition for any electromagnetic radiation Since E = hv =he/A, higher would be the energy and longer is the wavelength, lower would be the ‘energy. As we move from cosmic radiation to ultraviolet regions to infrared region and then radio frequencies, as we move gradually to the lower frequency region. Ultraviolet-Visible Spectroscopy: (2.200 - 800 nm) studies the changes in electronic energy levels within the molecule arising due to transfer ofelectrons from or non-bonding orbitals. It commonly provides the knowledge about x-clectron systems, conjugated unsaturations, aromatic compounds & conjugated non-bonding electron systemetc, Infrared Spectroscopy: (7 400 - 4000 cm-) studies the changes in the vibrational and rotational movements ofthe molecule, It is commonly used to show the presence or absence of functional group which have the specific vibration frequencies viz C=O, NH, OH, CH, C—O ete. Spectroscopy | 917 1e information ab, a rovides the i abou MT-JAM/M.Sc. Entrar 600 MHz) pr io frequency v 60- Nuclear Magnetic Resonance = (radio freq > ele "Hand changes in magnetic properties of certain atom ment signal nuclei for their different environments and provi inthe le. nuclei of the same atom present in the same molecu! 13¢ are the most commonly studieg 1 magnetically non-equivaley ULTRAVIOLET-VISIBLE SPECTROSCOPY 1 2 Introduction va Ultraviolet-visible spectroscopy (electronic spectroscopy, Se (spectrophotometry) which uses light in the visible, and mare tionbya molecule leads to the transitions (NIR) ranges. The absorption of radiation in the UV- Visible ra at - radiation in the UV-Visible rein amongst different electronic levels of the molecule. The absorption of eee RSE of the spectrum is dependent on the electronic structure ofthe absorbing, eee ions on complexes. t forms the basis of analysis of different substances st Sere ‘hemical. UV-Visible spectroscopy is of most use for identifying conjugated sys have strong absorptions. Ives the spectroscopy of photons Itraviolet (UV) and near infareq Electronic spectra arise fiom transitions between electronic energy levels accompanied by changes in both vibrational and rotational states. At room temperature, the majority of the molecules are inthe lowest vibrational state of the lowest electronic energy level, (the ground state). When continuous radiation is passed through a transparent material, a portion ofthe radiation may be absorbed. As a result ofabsorption molecules or atoms pass from a state of low energy (ground state) to high energy (excited state). The electromagnetic radiation that is Vv, — —— Electronic energy levels Ser, a } Rotational energy levels Ey absorbed this energy exactly equal to the energy difference between the excited and ground state. Due ‘o the absorption of electromagnetic radiation in ultraviolet-visible region, the transitions take place between different electronic energy levels As arole energetically fvoured electron promotion willbe from the highest occupied molecular orbital (HOMO) to th lowest unoceupie, ital (LUMO), and the resulting species is called an excited state, Pied molecular orbit Different regions of Ultraviolet-Visible Spectroscopy The UV-Visible portion is divided into three regions; the vacuum or Fare % sear. (200-380 nm) and Visible (380-780 nm). ‘UV (10-200 nm), Near-UV Vacuum or Far-UV region Visible-region 10m 200 nm 380 nm The different regions of UV-Visib le spectrum faa SpectroscopyCHEM ACADEMY ‘The near ultraviolet region (200-400 nm) out to 200 nm extends this energy range to 143 kcal/mole and the visible region (400-800 nm) ofthe spectrum comprises photons of energies 36 to 72 keal/ mole. The above energies are sufficient to promote or excite a molecular electron to a higher energy orbital, Different electronic transitions in Ultraviolet-Visible spectroscopy The electrons ofall the compounds other than alkanes, may undergo several possible transitions of different energies. When sample mokecules are exposed to light having an energy that matches. possible electronic transition within the molecule some of the light energy will be absorbed as the electronis promoted to a higher energy orbital. For most ofthe molecules the lowest lying molecular orbitals are the o bonds. The n-orbitals lie at somewhat higher energy levels, and the nonbonding orbitals, that holds the unshared pair of electrons lie even at high energies. The unoccupied, or antibonding orbitals (o*, n*), are of highest energy. The most possible electronic transitions of 0, x and n electrons are given in Figure, Antibonding -——— Antibonding xt 2 n-o* a Nonbonding aa a -o* Inalkane compounds (strong) coe o-n* In carbonyl compounds mat ‘n-n* In unsaturated compounds (strong) Bonding ” n-o* In O,N, S, halogen compounds ont n-a* In carbonyls compounds (weak) Bonding o Different electronic transition in UV-Visible spectroscopy. o-o*transitions ‘Anelectron in a bonding orbital (o) is excited to the corresponding antibonding. orbital (o*). The energy required is large, as the bonds are very strong, For example, methane (which has only C- H bonds, and can only undergo 6-c* transitions) shows an absorbance maximum at 125 nm. ‘Absorption maxima due to s-s* transitions are not seen in typical UV-visible spectra (200-700 rim), but occurs below 200 nm. The study of such transitions is done in vacuum ultraviolet region since below 200 nm the oxygen present in air begins to absorb. n-o* transitions Saturated compounds containing one hetero atom with unshared pairs (i.e., non-bonding electrons) are capable of n-c* transitions, such as alcohols, ethers, amines and sulfur compounds. These transitions usually need less energy than o-o* transitions, They can be initiated by light whose wavelength isin the range 150-250.nm. For example, in saturated alky| halides, the energy required for this transition decreases with an increase in the size of the halogen atom (or a decrease in the electro negativity ofthe atom). Due to the greater electronegativity ofthe chlorine atom (than. Spectroscopy | 93NTJAM/M.Sc. Entrance . iodine) the non bonding (n) electrons on chlorine are electrons are tightly bounded to the nucleus. Since this He 50 its molar excitation coefficient isalso higher than methyl! chloride. Ie, alcohols from hydro Also, these transitions are sensitive to hydrogen bonding. For example, eee gen bonds with the solvent molecules which occurs due to the presence ofnion bonding} n the hetero atoms and thus v-s* transitions requires greater energy. comparatively difficult to excite, a these transition is more probable in methyl iodigy a-n* transitions , f ‘These transitions require an unsaturated group in the molecule to provide the nail examples alkenes, alkynes, aromatics, carbonyl compounds etc. These transitions usually need less energy than n-o* transitions. In the case of alkenes, there are several transitions possible, but then" are of lowest energy and are observed nearly 175-190 nm. The saturated carbonyl compounds shows the n-x* transitions (~150 nm) in addition to n-n*. n-n* transitions Compounds containing one hetero atom with non-bonding electrons (n) are capable of n-n* transitions. These transitions require the least amount of energy than all other transitions and therefore absorption bands are generally observed at longer wavelengths. Carbonyls-unsaturated systems incorporating nitrogen or oxygen atoms can undergo n-r* transitions (~285 nm). Despite of the fact this transition is forbidden by the selection rules (¢ = 15), it is the most often observed and studied transition for carbonyls. This transition is also sensitive to constituents on the carbonyl. 4. Selection ruleand Beer-Lambert law: The following selection rules are: 1. Electronic transitions are allowed ifthe orientation of the electron spin does not change during the transition. Ifthe symmetry of the final and initial functions are different; these are called the spin and symmetry selection rules, respectively. However the forbidden transition can still occur, but will give rise to weak absorptions. According to the Beer-Lambert law, the absorbance A, ofthe solution is directly proportional to the path length (I= the length of the cell containing the solution, in cm) and the concentration: ofthe absorbing. species (c, in moles per litre), according to equation: A=log (Iy/l)=e.c Where, A isthe measured absorbance, I is the intensity of the incident li the transmitted intensity, ¢ isa constant known as the molar absorptivity or molar extinction eoefcrent, and isa characteristic ofthe molecule. The molar absorptivity is expressed in 100 cm? mol! Iting measure ofthe tensity ofthe absorption and usualy ranges fiom 0-105 (unit o 100 em? mot). The sreater the probability ofthe absorption and its associated electronic transitions, the greater thes vale for that transition. 7 ight ata given wavelength, lis 5. Solvents used in the UV-Visible: ‘spectrophotometry A good solent should not absorb ultraviolet radiation inthe same region a the substance whost spectrum istobe determined. Also, solvent has lage effect ofon the fine stctnne veo nen on band. For example, the non polar solvent does not H-bond with solute eer ; » and the spectra solute closely approximates the spectrum that Would be produced inthe gaseous state vere fin tres 94 | SpectroscopyTable: CHEM ACADEMY can often be observed. In polar solvents, the hydrogen bonding forms a solute-solvent complex, and the fine structure may disappear. The solvents also have the ability to influence the wavelength of ultraviolet light that will be observed. For example polar solvents shifs transitions of the n-x* type to shorter wavelength. A list of common solvents is given in Table, Amongst the solvent given in table, water, ethanol and hexane are commonly ‘used because they remain transparent in the ultraviolet region of the spectrum where interesting absorption peaks from the sample molecules are likely to occur. Wavelength (2,,4,) values of some common solvents used in UV-Visible spectrophotometry S.No. Solvents Aimar Values 1 Acetonitrile 190 2. Chloroform 240 3. Cyclohexane 195 4. 1,4-Dioxane 215 5. 95% Ethanol 205 6. n-hexane 201 7. Methanol 205 8. Tsooctane 195, 9. Water 190 Some useful terms in Ultraviolet-Visible spectroscopy Chromophores “The coloured substances owe their colour due to the presence of one or more unsaturated groups responsible for electronic absorption. These groupsare called chromophore (color loving), €.g.: C=C, C=C,CEN, C=C, C=0,N=N, NO, ete are the common examples ofthe compounds containing chromophorie groups. ‘Table: Absorptions of simple chromophores in the UV-Visible spectrophotometry. Chromophoric Examples Transitions Aya(MM) Emax Group ROH Methylaleohol not 180 200 ROR Di-ethylether no* 188 1995 R,C=CR, Ethylene nent 71 15,000 RCsCR Acetylene mnt 170 10,000 R-X, X=Cl Methyl chloride n-o* 1B 200 X=Br nPropylbromide — n-o* 208 300 X=1, Methyliodide not 259 400 RCHO ‘Acetaldehyde nent 290 15 a-n* 180 10,000 R,cO Acetone nent 280 15 mnt 180 900 Spectroscopy | 954l NT-JAM/M.Sc, Entrance . a RCOOH Acetic acid net a 5 RCOOR Ethylacetate na* ae ° RCONH, Acetamide aa a" 7 RNO, Nitrobenzene zy * 00 an * RNH, Trimethylamine n-o* ' ” a R-CaN Acetonitrile nen is R-N=N-R Azomethane nen* 340 96 Jat having an energy that matchesa possible electronic Veli « When sample molecules are exposed to UV-lig! lectron is promoted to transition within the molecule, some ofthe light energy will be absorbed as the electro t a higher energy orbital. The nuclei that the electrons hold together in bonds play an ee E role in determining which wavelengths of radiation are absorbed. The nuclei determine the strengil wit which the electrons are bound and thus influence the energy spacing between ground and excited states, Hence the characteristics energy of a transition and the wavelength of the radiations are absorbed are proerties ofa group of atoms rather than of electrons themselves. Since similar functional groups will have electrons capable of discrete classes of transitions, the characteristic energy of these energies is more representative ofthe fimnctional group than the electrons themselves. Structural or electronicchanges in the chromophore can be quantified and used to predict shifts in the observed electronic transitions. Effect of Substitution on the chromophore Substituents may have the following effects on a chromophore: Bathochromic shift (red shift) The shift ofan absorption maximum towards longer wavelength (lower energy) is commonly known as bathochromic shift or red shift. It may be produced by a change of medium (solvent) or by the presence ofan auxochrome. Hypsochromic shift (blue shift): The shift towards shorter wavelength (higher energy) is known as hypsochromic shift or blue shift. This may be caused by the change of medium (solvent) and also by the removal of conjugation, ¢ 2 £ a 2 Hyposochromic —_Bathochromic eS testin gern z 4 200mm Wavelength (nm) —* 700 am Effect ofsubstituents on the position and intensity ofan absorption ba a nd, Spectroscopy \8. CHEM ACADEMY: Hypochromic shift: ‘An increase in intensity leads to the hyperchromic shift. For example, the intensities of primary and secondary bands of phenol are increased in phenolate. Hypochromic shift: A decrease in intensity leads to the hypochromic shift. For example, the intensities of primary and secondary bands of benzoic acids are decreased in benzoate. Effect of conjugation on the chromophore Increasing conjugation 2,4, increases because the energy gap in between HOMO and LUMO decrease | , , LUMo--~< 7 LUMO - wr Yue = 20TH 7 HOMO , HOMO: -~< CH=CH, i 7 According to quantum mechanies, conjugated olifines assumed asa 1-D box AE = Exysto — Enomo . 2 a= s[rtawe Miao] AE & us Lv Conjugation causes bathochromie shifts in the absorption maxima of chromophores, this can be explained ‘on the basis of the relative energy levels ofthe z-orbitals. When two double bonds are conjugated, the four p-atomic orbital combine to generate four n-molecular orbitals (two are bonding and two are antibonding). The energetically most favourable n-n* excitation occurs from the highest energy bonding p-orbital (HOMO) to the lowest energy antibonding p-orbital (LUMO). Increased conjugation brings the HOMO and LUMO orbitals closer together. The energy (AE) required to effect the electron promotion is therefore essand the wavelength that provides this energy is increased correspondingly (remember 2.=he/AE). Thus, the more highly conjugated the system, the smaller the HOMO-LUMO gap, E, and therefore the lower the frequency and longer the wavelength. The colours we see in inks. dyes, lowers etc. are typically due to highly conjugated organic molecules. Effect of solvent on the chromophore ‘The solvent in which the absorbing species is dissolved also has an effect on the spectrum of the species. The Frand Condon principle states that electronic transitions involve the movement of electrons, including those of the solvents, but not the movement of atoms. Increasing polarity of solvent Ange increased for n-r* transiation (allowed transiation) and 2.,,,, decreased for n-m* transiation. Order of interaction of orbital with polarity of solvent = nonbonding > Antibonding > Bonding Increasing in polaity i. increased because due to polarity m*-antibonding orbital are more stabalized than m-bonding molecular orbital, due to this the energy gap between HOMO and LUMO decrease Spectroscopy | 97IT-JAM/M.Sc. Entrance hens Ayugx increase z hon polar HOMO solvent Polar solvent a bonding orbital are Increasing the polarity 2, ,. decrease in n—>7* transiation because of non! iB More ; F 0 and LUMO in stabalized than the x*-orbital and due to this the energy gap in between HOM ease a*___ LuMo poe HOMO “non polar yn solvent Polar solvent 9. Effect of pH on the chromophore ‘The UV-Visible spectra of some ofthe compounds, especially certain substituted aromatic compounds, show the dramatic changes with a change in the pH ofthe solvent. Phenols and substituted phenols are acidic and display striking changes to their. absorptions upon the addition to base. The removal of the acidic proton increases the conjugation of the lone pairs on the ‘oxygen with the p-system of the aromatic ting, leading to a decrease in the energy difference between the HOMO and LUMO orbitals, resulting in red shift along with an increased intensity of the absorption. 6d §-8 1) ) (2a) 2b) Perl Phenoxide anion yy 2c) When aromatic amine is treated with acid, a blue shif is observed with a due to the loss of the overlap between the amine lone pair and the conjugation ofthe lone pair of electrons onthe ritrogen atom of anilinem (3) with the-borel systemof the benzene is removed on protonation (4). Aniline absorbs at 230 nm, but in acidic condition the main peak is almost identical with that of benzene which absorbs at 203 nm, decrease in intensity whichis ‘aromatic t-system. For example, the ae ‘NH, "NH, somance_. fF tei. a) @ Go) Bf Aniline inc Protonated Neutral or basic condition Acidic eonivion Many pH indicators owe theiutlityto their absorption inthe visible region ofthe UV-Visible spectrum. Changes to the pH lead to changes in the indicator chromophore, and result in reliable colons chant at predictable pH values, One such examples that ofthe phenolphthalein (3), which phenol and can be deprotonated at elevated pH to give the anions (6), extend ing the chromophore and leading t0 98 | Spectroscopy10. ul. CHEM ACADEMY a substantial bathochromie shift. Thus the anion of phenolphthalein is deep magneta in colour, whileun- ionised form phenolphthalein is colourless. OH eo o (6) 6) Magenta Colourless The pKa of the acid-base equilibrium is 9.4, at acidic and neutral pH there is insufficient anion todetect the colour by eye, and it appears colourless. As the pH approaches the pKa, the concentration of anion increases and at pH 8.2, the colour becomes visible to the eye. As the pH 8.2 is close to neutrality, phenolphthalein is widely used to show the end point in weak acid-strong base titrations. Isosbestic point: Ifthe two substances, each of which obeys Beers law, are in equilibrium, the spectra ofall the equilibrium mixtures at a total concentration intersect at a fixed wavelength. This point, is termedas isoesbestic point, is the wavelength at which absorbance’s of the two species are equal. The presence of the two species in equilibrium can be identified by the appearance of an isoesbestic point in the UV spectrum. Woodward-Fieser rules Woodward-Fieser Rules for calculating the 2,,,, values in dienes The conjugated diene exhibits an intense band in the region from 217 to 245 nm, owing to the n-r* transition. The position of this band appears to be quite insensitive to the nature ofthe solvent. Many simple conjugated dienes exists in a planar conformation. Generally, allkyl substituents produce bathochromic shifis and hyperchromic effects. However, with certain patterns of alkyl substitution, the wavelength increases but the intensity decreases. The 1, 3-dialkylbutadienes possess too much crowding between alkyl groups to permit them to exist in the s-trans conformation. They convert, by rotation around the single bond, s-cis conformation which absorbs at longer wavelengths but lower intensity than the corresponding trans conformation. But in cyclic dienes, where the central bond is apart ofthe ring system, the diene chromophore is held rigidly in either the s-trans (transoid) or the s-cis (ciboid) orientation. The incremental contribution of substituents is added to this base value from the Table. ‘Table: Empirical rules for calculating X,,., Values in case of different dienes. Diene with appropriate | Add anincrement forany | Add increments to any parent value extra conjugated x-bonds in | substituents in specific specific dienes dienes @ Acycheandheteroannular_| C=C +30 RICH) + (double bond in two adjacent | C=C-C=C +40 ell +5 ring) diene = 217 nm Exocyelic +5 OH, OR +5 cc ocor 0 (6) Homoannular o - (double bonds within one ring) SR +30 = 253 nm NRo +0 Spectroscopy | 99AT-JAM/M.Sc. Entrance Ayclic Dienes The base value for the acyclic dienes is 2 17nm. Mlustration: Calculate the 4,,,, of different acyclic dienes: Acyclic butadiene One alkyl substituent Calculated value Experimental value Acyclic butadiene 2alkyl substituent (2 * 5) 1-Exocyclic C=C Caleulated value Experimental value Cyclic Dienes: =217nm =+5nm = 222 nm =220nm =217nm +5nm =+10nm 232 nm =237nm There are two types of cyclic dienes, with two different base values. These are heteroannular diene and homoannular diene. The base value for the heteroannular diene (12) is 217 nm whereas for homoannular diene (13) is253 nm. CO Of (12) (13) Illustration: Calculate the A,,,, of different cyclic dienes: is v 100 Heteroannular diene 3-alkyl substituents (3 x 5) 1-Exo C=C Calculated value Exocyclic C=C Experimental value Heteroannular diene 4-alky| substituents (4 » 5) I-Exo C=C Exocyelic C#C Calculated value Experimental value Spectroscopy =214 nm =+15nm =+5nm =234 nm =235 nm 214nm =+20nm =+5nm =239 nm =240 nmdo Homoannular diene 4-alkkyl subs (4 5) Fxocyclic C= -Exo C=C Calculated value Experimental value CHEMACADEMY — =253 nm =+20nm =+5nm =27eam =275 nm Woodward-Fieser Rules for caleulating the ,,,, Values in unsaturated carbonyl compounds (Enones) ‘The carbonyl compounds have two main UV-transitions (i) n-r* (ii) n-*. The conjugation of the double bond witha carbonyl group leads to intense absorption corresponding to x-n* transition of the carbonyl group. The absorption in simple enones normally occurs in the region between 220 and 250 nm. The n-m* transition in less intense and occurs in between 310-330 nm. ‘Table: Empirical rules for calculating A max Values in case of different enones. Enones Enones with | Addan increment for | Add increments to any Bow g appropriate | any extra conjugated | substituents in specific Enones 4 =¢-dy | parentyaiue |” -bonds in specific Enones Ja [6 Ty Ts 1, XH 207m 30 ([R X=C(part of | 202 nm C=C-C=C +40 | (CHy) 10 | 12 }18 | 1s ci Exocyelic {cl 1s | 12 |- membered c=c OH 35 |30 |- ring) OR 6 jo |- SEC (Agyelic [25am ocor |- a5 |- Or part of six- - Membered — 78 I~ ring) SR - Jos |- NRy ‘The structural modifications of the chromophore have pronounced effects on the n-1* transitions, but no efféct on the n-n* transitions. The incremental contribution of substituents is added to thig base value from the Table. Milustration: Calculate the d,,,, of different enones: : AK ‘Acyclic enone c-alkyl subs bealkyl subs. Calculated value Experimental value =215 nm =+10nm +12nm 237 nm =240 nm Spectroscopy | 101UT-JAM/M.Sc. Entrance Cyclic six memberd enone Extending conjugation Homoannular diene Bering residue Calculated value Experimental value Cyclic five memberd enone OH o-substituent =215nm =+30nm =4+39nm =+18 nm = 302 nm =300 nm 202 nm +35nm Brring residue +18 nm Calculated value 249 nm - Experimental value =249 nm 4. Cyclic six memberd enone =215 nm Extending conjugation =+430 nm Os ‘ring residue =+18nm A dering residue =+18nm wry Exo-eyclic double bond =+5nm Calculated value = 286 nm Experimental value = 288 nm 5. Cyclic six membered enone =215nm Extending conjugation =+30nm ‘pring residue +18nm 2-B-ring residue =436 am ‘Woodward-Fieser Rules for aleulating the2,,,, values in aromatic ea Woodward and Fieser rules can be used to calculated the ae Depending on the nature of the aromatic carbonyl compounde ti following different base values are taken for aromtic carbonyl com, Exo-cyclic double bond Calculated value Experimental value (For aromatic aldehydes base value is 250 nm, Gi) For aromatic ketones base value is 246 nm. =+5 nm =338nm_ =339 nm -arbonyl compounds wax Value for the n-n* transition. ifferent base values exists. The pounds. (id) For aromatic carboxylic acid or esters base values are 230 nm, ‘The incremental contribution of substituents is added to this base Value from the Table, 102 | SpectroscopyCHEM ACADEMY ‘Table: Empirical rules for calculating 2.,,,, values in case of different aromatic carbonyls. ‘Aromatic ‘Aromatic carbonyk with ] Add increments to any substituents in carbonyls appropriate parent value specific Enones ot ° m P TX B0nm Cis 3 3 7 246mm a 0 0 10 Bom OH, OR 7 7 25 OcoR - - : o 15 15 80 SR - : a = NR: 2» 20 85 Mlustration: Calculate the 2.,,,, 0f different aromatic carbonyl 1. Ox-CH; Aromatic carbonyl compound =246 nm -Cl subtitution at para position =+10nm Calculated value 256 nm a Experimental value = 254 nm Ox CH ‘Aromatic carbonyl compound = 246 nm OH subtitutionat meta position =47 nm OH subtitution at para position =25nm oo Calculated value =278 nm Experimental value =281 nm 3. Ox 0H ‘Aromatic carbonyl compound =230.nm -Br subtitution at para position =+15nm Calculated value 245 nm be Experimental value =245 nm 12, Application of Ultraviolet Spectroscopy Detection of functional grou This technique can be used to identify the presence ofa chromophore. The absence ofa band at a particular wavelength may be regarded as an evidence for the absence of a particular group in the compound. Ifthe spectrum of the compound is transparent above 200 nm, it shows the absence of: (Conjugation (i) A carbonyl group (ii) Benzene or aromatic compounds (iv) Bromo or iodo atoms Spectroscopy | 103NT-JAM/M.Sc. Entrance As isolated double bond or some other atoms or groups may be present ae that no definite conclusion can be drawn if the molecule absorbs at a wavelength lower th 5 Extent of conjugation aa . The extent of conjugation can be estimated by using ultraviolet spectroscopy. Aadition in nsatraton With the inerease in the number of double bond shifts the absorption to longer wavelength, Distinction between conjugated and non-conjugated compounds: a Italso distinguishes between conjugated and non-conjugated compounds. The delaying isomers can be readily distinguished since one is conjugated and the other is not. The forbidden band for the carbony| group in the compound (14) will appear at longer wavelength than that of the compound (15). oO CH; O Wey \ ‘CH; x nyc7 Nc cHy (14) (13) Identification ofan unknown compounds: An unknown compounds can be identified by comparing its spectrum with the known spectra. Ifthe two spectra coincide, the two compounds must be identical. Ifthe two spectra do not coincide, then the expected structure is different from the known compound. Quantitative analysis: UV-Visible spectrocopy can be used to determine the concentration of.a particular compounds ina solution. Since itis based on the Beer-Lambert law states that the absorbance of. solution is directly Proportional to the concentration of the absorbing species in the solution and the path length. Thus, for a fixed path length itis necessary to known how quickly the absorbance changes with concentration, A=log (Iy/l)=e.0.1 For example estimation ofanthracene and naphthalene can be carried In ethanol anthracene absorbs at 375 nm (loge = 3.87), naphthalene absorption does not interfere in this region. A standard solution of anthracene-napthalene mixture can be prepared and the measurement ofanthracene can be done at 375 nm, From Beer Lambert law the concentration of pure anthracene can be calculated and hence, the proportion ofanthracene in the mixture, Examination of polynuclear hydrocarbons: out using UV-Visible spectroscopy. Benzene and polymuclear hydrocarbons have characteristic s Thus the identification of the polynuclear hydrocarbons can known polynuclear compounds. The presence of substituent maximum to longer wavelength. For example, the napthaler added conjugation in anthracene and tetracene causes bath pectra in the ultra violet and visible region. be made by comparison with the spectra of ts on the ring generally shifts the absorption ne shows absorption at 210 and 272nm, the hochromic shifts of these absorption bands. IRSPECTROSCOPY Important Points 50em*__ 667em" 400m" 12500enr 667-1500enr —1500%. 4000 em 4 4 Finger Print region Functional group region 104 | SpectroscopyCHEM ACADEMY Condition For IR Active: Molecule which changes there dipole moment during vibration can gives TR Ou tra 20 spectra > Note: Except HOMO diatomic molecule all molecule can give IR spectra. Molecule which contain permanent dipole moment there all fundamental vib modesare IR active. Molecule which have parmanent dipole moment is zero except HOMO diatomic some mode’s are IR active and some modes are inactive. al and rotational energy levels of the molecule or LR. spectrumarises due to excitation of vibration: region of the individual functional groups. It is also called Vibrational spectroscopy. The 1 electromagnetic spectrum may be divided into three main sections : (a) Near infiared (overtone-region) 0,8 -2.5 pm (12500-4000 em!) (b) Midale infrared (vibration-rotation region) 2.5 ~50 jum (4000-200 em!) (6) Far infrared (rotation region) 50-1000 um (200-10 cnr) The LR. spectrum in the frequency range 4000 ent! to 666 ent is important for organic chemistry. In the LR. spectroscopy the absorbed energy brings about predominant changes in the vibrational energy which depends upon: (a) Masses of the atoms present ina molecule. (b) Strength ofthe bonds and (c) The arrangement of atoms within the molecule. Tthas been found that no two compounds except the enantiomers can have similar infrared spectra. The value ofthe stretching vibrational frequency ofa bond can be calculated by the application of Hooks law which may be represented as: ‘THE MODES OF STRETCHING AND BENDING ‘The simplest types, or modes, of vibrational motion in a molecule that are infrared active—that is, which give rise to absorptions—are the stretching and bending modes. Ga A —— CoH wY Stretching Bending However, other, more complex types ofstretching and bending are also active. The following illustrations ofthe normal modes of vibration for a methylene group introduce several terms. In general, asymmetric stretching vibrations occur at higher frequencies than symmetric stretching vibrations; also, stretching Vibrations occur at higher frequencies than bending vibrations. The terms scissoring, rocking, wagging, and twisting are commonly used in the literature to describe the origins of infrared bands. In any group of three or more atoms, at least two of which areidentical, there are two modes of stretching: symmetric and asymmetric, Examples of such groupings are~CH,,~CH}~ (see page 17), — NO,,-NH,, and anhydrides. The methyl group gives rise to asymmetric stretching vibration at about 2872 cm”! and an asymmetric stretch at about 2962 cn“. Theanhydride functional group gives two Spectroscopy | 105UTJAM/M,Sc. Entrance absorptions in the C=O region because of the asymmel phenomenon occurs in the amino group, the N-H stretch region while a secondary amine ( similar bands. There are two strong N=O stretch peaks fora appearing at about 1350 cm! and the asymmetric stretch ap] aa N Syma th (2889 em) ‘Asmmmetic seth (2826 em} STRETCHING VIBRATIONS Methyl Anhydride Amino Nitto The vibrations we have been discussing are called fundamental abson from the ground state to the lowest-energy excited state, ofthe presence of weak overtone, combination, and differ from the ground state to higher energy states, which corre: 106 | Spectroscopy where a primary ay Nw Selssorng (1480 on) eal al Focking (720 on) ric R,NH) has only one al and symmetric modes of stretch. 4 Simi amine (NH,) usually has two absorptions : sorption peak. Amides exh, nitro group, with the symmetric stretch, pearing at about 1550 cnr, woasing (125069 4 / Ne LX wsting (1280 en) fu ‘BENDING VIBRATIONS ‘Symmetric Stretch ~1350 en! also set up at several overtone fi Asymmetric Stretch 1 Si a 2962 emt 1550 em Ptions, They arise from excitation Usually the spectrum is complicated becaus? rence bands. Overtones result from excitation Spond to integral multiples ofthe frequency of the fundamental). For example, you might observe weak overtone bands at >¢, 5 ny physical vibration generates overtones. Ifyou pluck astring on cello thes frequency. However, less intense vibrations are at 2¥, 3¥,.... Anykind of tring vibrates with afundamental requencies. An absorption‘CHEM ACADEMY in the infrared at 500 cm! may well have an accompanying peak of lower intensity at 1000 cnr! and overtone. When two vibrational fiequencies (¥, and ¥,) ina molecule couple to give rise to a vibration of anew frequency within the molecule, and when such a vibration is inftared active, itis called a combination band. This band isthe sum of the two interacting bands (V4, = V; + V2) - Not all possible combinations occur. The nules that govern which combinations are allowed are beyond the scope of our discussion here. Difference bands are similar to combination bands. The observed frequency in this case results fromthe ¥,) One can calculate overtone, combination, and difference bands by directly manipulating frequencies in wavenumbers via multiplication, addition, and subtraction, respectively. When a fundamental vibration couples with an overtone or combination band, the coupled vibration is called Fermiresonance. Again, only certain combinations are allowed. Fermi resonance is often observed in carbonyl compounds. difference between the two interacting bands (Vyie =¥, Although rotational frequencies of the whole molecule are not inffared active, they often couple with the stretching and bending vibrations in the molecule to give additional fine structure to these absorptions, thus further complicating the spectrum. One of the reasons a band is broad rather than sharp in the infrared spectrum is rotational coupling, which may lead to a considerable amount ofunresolved fine structure, Fundamental Vib, Mode Stretching Mode Bending Mode + + During Vibration not During vibration not change in bond angle change in bond length bout bond length must, but bond angle may be change change Symmetric Asymmetric ‘On the plane Out ofthe plane Stretching stretching a“ Rocking Seissoring __ Wagging ‘Twisting Number of Fundamental Vibration Mode’s ‘Number of vibration modes = 3N— (Rotation Mode + Translation Mode) N=Number ofatom in the molecule For linear molecule rotational mode= 2 For nonlinear molecule rotastional mod Translation mode for atom, molecule (linear or non linear) =3 allways Vibration Mode For Linear Molecule ForNon Linear Molecule For atom For Activated Complex 1 + ‘ 4 3N-5 3N-6 3N-3=0 3N-7 Seching Bending Stetshing Bending ‘ wW-1) QN-5) (W=1) @N-4) y (allways) Spectroscopy | 107NT-JAM/M.Sc. Entrance de for the following nal mode stretching or bending mot Q. Calculate the number of fundamental vibration molecule ; Molecule Shape Vibrational Mode Stretching (N~!) Bending H,O Nonlinear = 3x3-6=3 2 d NH, Nonlinear 3x4-6=6 3 a SO, Nonlinear 3x4-6=6 3 a C,H, Linear 3x4-5=7 3 2 C,H, Nonlinear 3x6-6=12 5 ¢ SF, Nonlinear 3x7-6=15 6 9 XeF, Nonlinear 3x5-6=9 4 5 Benzene Nonlinear 3x12-6=30 Wl 19 In cyclic compound like benzene, cyclohexane have a specific vibrational mode known as breatching vibrational mode. Important Group Frequencies Fundamental Peak Dueto 3300-3650 em- due to O-H stretching frequency 3200 ~ 3400 cm N-H frequency in 1°—amine—> two peak 2°— amine —> one peak 3°—amine -> no peak = 3300cm™ due to =C—Hyeaing (I-Alkyyne) 2900-3050 cm~ C= C—Hewceing (Inalkene, cyclo alkene aromatic compound) sy 2800 —2950 cm- CH (InAlkane, cyclo alkane 4p \ CCHS, -CHy, cH) 2720 em-—2820 m= Character stic peak of aldehyde C_H fh retchi (due to fermiresonance) a 2500-3000 cm- Broad peak Character stic of-COOH group due to OHgretching 2200 -2400 cm- C= Coreeings C= Necching 2050-2200 em- C=C=0,,,C=C=C,, O0=C=0,C= i NH,, 108 | Spectroscopy1750 ~ 1980 cm~ 1790-1800 1810-1870 1750 — 1780 em, 1800 ~ 1830 em~ 1740-1760 cm- 1730-1750 em~ 1720-1740 cm™ 1700 - 1720 cm= 1690 = 1700 cm~ 1650 cm~ 1490, 1555, 1605, 1655 emo 1530, 1360 cm~ 1450-1485 cm 1450 1050-1300 900-960 690-730 800-850. cm~ 750 — 800 cm-, 680-715 em- 690-750 cm~ 300 — 480 cm~ ‘CHEM ACADEMY M>CO,, Il ‘Acid Halide —C-Cl 9 i —C-F 9 °9 AK Anhydride 9 tl —C-oR — Ester {| —C-H Aldehyde i GOH Carboxalie acid tl R-C-R Ketone an (Amide) C=Cyyetcning (Alkene) Aromatic C=Cytetching 2 Character stic of — group Nao \ HE Moenaing Clyrctching C-X (X=0,N,F) CH, bending in trans Alkene CApending in cis Alkene Pera substituted Meta-substituted Ortho substituted M-Ligand,.iching Spectroscopy | 109UT-JAM/M.Sc. Entrance Hydrogen Bonding Stronger the hydrogen bonding, greater is - the normal value. Generally, bands due to intramolecular hydro} are ere intermolecular hydrogen bonds give rise to broad bands and these dep . inal O-H bond is lengthened (weakend) due to electrostatic en atoms of the other, and thus the absorption shift towards lower wavenumber thay gen bonds are sharp wheregg Due to hydrogen bonding the or n attraction between the hydrogen atoms of the molecule and oxygen atom 0 the force constant of the O-H bond is reduced resulting ina decrease in its stretching frequency, R \ 4 a Hydiogen 2R-O- a? (OH 0 Free-on | OnE tT SR (i) increase in bond length (ii) decrease in force (iii) decrease in ¥ . . Further, the hydrogen bond can be regard as a resonance hybrid ofthe following resonating strucures so that hydrogen bonding involves a kengthening of the original O-H bond. This bond is consequently weakend, So the stretching frequency is lowered. H H I 8 | R-O-H O-R <> RO H-O-R Tl H O—R 4 increase in O-H bond length Hy, Oo 0 oO AL AA HC ‘CH3 HC c ‘CH; Keto Enol Vac 1650 em= ¥ =o 1720 1645 Vou = 3350 em- Distinction between Inter-and Intramolecualr Hydrogen Bondings ‘A compound with intramolecular hydrogen bonding shows almost the same O-H stretching in the Concentrated solution asin the very dilute solution, this means O-H stretching value does not change with dilution in the cases of intrmolecular hydrogen bonding while the same changes with dilution inthe case of intramolecular hydrogen bonding. Thus dilution ean be used to diet inguish between inter and intramolecular hydrogen bonds, Electronegativity As the clectronegativity ofa bonded atom increases, the shortening of bond length occurs and the large force constant leads to increased vibrational frequency. For example, the decreasing order of 110 | Spectroscopy‘CHEM ACADEMY electronegatvity of carbon in alkane, alkene and alkyne is: alkyne > alkene > alkane ‘The C-H stretching frequencies of these compounds are also in the same order : = nea Ld C=C—H Zen, mimi Yous 3300 em" 3300-3100 em 2800-3000 enr (i) Electronegativity of carbon of the C-H bonds in increasing order. (ii) Force constant is in decreasing order. (iii) Vjy4¢ 8 also in decreasing order. Inductive Effect A carbonyl compound may be considered as a resonance hybrid of the following structures R Re 0 Sco 6 rR“ Ray The stretching frequency of a carbonyl group decreases with increasing number of alkyl groups attached to carbonylcarbon. This is due to +1 effect ofalkyl groups which favours the structure (11) and lengthens (weakens) the carbon-oxygen double bond, and hence is force constant is decreased resulting in the lowering ofthe C =O stretching frequency. HL CH CH c=0 c=0 pero nH He CHy Vous 1750 ear? 1785 em! 1720 em (i) carbon-oxygen bond length in increasing order (structure II) (ji) force constant in decreasing order (iii) Vga: is decreasing order Similarly, when a group with-I effect is attached toa C= O groups, it favour the structure (1) and its stretching frequency is increased due to decrease in bond length or increase in the force constant of the carbon-oxygen double bond. For example, CH,COCH,, CH,COCF, and CF,COCF, shoW Ve ag bands at 1720, 1769 and 1810 cnr", respectively Resonance Effects Due to p- x and x~7 conjugation single bonds get partial double bond character and double bonds get partial single bond character. When a single bond acquires a partial double bond character through resonance, the vibrational frequency ofthe bond is expected to be greater than the normal value because of the shortening of bond length. On the other hand, when a double bond possesses a partial single bond character, the vibratioanl frequency is expected to be lower than the normal value because of the weakening of the bond strength though resonance. () C=O Stretching frequency of saturated and , B-unsaturated compounds. In ano, B-unsaturated carbonyl compound nn conjugation takes place. Due to this conjugation C=O group has a partial single bond character. Thus the C=O bond becomes longer than that in a saturated carbonyl compound; as a result the C = O bond strength decreases and its vibratianal freqeuncy becomes less than that of the C = O groups in the saturated carbonyl compound. Spectroscopy | 111NT-JAM/M.Sc. Entrance 0 f | NW Need ne aa i i whe coc 521705 en! : Vipul 725-170: 1685165 en (i) C=O stretching frequency of acid derivations | sam leis 1715 nr! The absorption frequency of saturated aliphatic keto group of a neat samp feat a : Replacement ofan alkyl group ofa saturated aliphatic ketone by a heteroatom (X) shifts the carbon, absorption. The direction of the shift depends on whether the inductive effect (a) or resonance effect (b) predominates, ‘The inductive effect reduce the length of C=O bond and thus increases its force constant and the frequency of the absorption. The resonance effect increases the C= O bond length and reduces its force constant and the frequency of absorption. x Table 1. The carbonyl absorption of rt=0 compounds x Vina C=O G tea Br 1812cm™ Inductive effect on | 1760em"! predominates OR | 1750-1735 em"! NH) | 1695-1650cm"! Resonance effect A lie predominates An NH, group has—T effect as wellas +R effect but the latter < Predominates, Due to the +R effect, the C=O group in an amide gets a partial single bond chara ca ter and possesses lower vibrational frequency (¥,,,,,C =O, 1650 cm7') than in the Corresponding ester (C= 0, 1750-1735 cm). Inthe case ofan ester the-1 eet ofthe alkoxy group predominates overits +R effet Illustration: effect. HC 112. | SpectroscopyCHEM ACADEMY oO 0 io CH (vy on 0.N HN vy PO=Ose (iid > Gi)> Gv) oO oO QO (> Gil) > Gil) oO Oo oO 0 C3 oC 3 WoO fA Gi)> > Gi) ° 9 9 9 0 C “9 (ii) c "9 (iy Ce oC} Oo Oo Z vi 7 Gi) > (> (> > G)> (WI. 0 Steric effects Steric effects such as steric inhibition of resonance, transannular effect, etc. influence stretching frequencies of bonds. For example, the-OH stretching (Vo, ) frequency of phenol is 3330 em This frequency is due to the intermolecular hydrogen bonding. In contrast to phenol2, 6-di-tert- buty! phenol, in which steric hindrance prevents intermolecular hydrogen bonding absorption band js obtained at 3600 cm. Similarly the C= Ostretching frequency of 2, 7-dimethylene~4, 5-benzo tropone is 1596 cm! where as tetramethylane ~4, 5-benzo tropone has a at 1724 cm. Ostretching (ve) Spectroscopy | 113NT-JAM/M.Sc. Entrance CH CI ff — CQ CH, 2,7-Dimethylene-4, 5-bezotropone cH ® Moy ———. oO Ci O CH I cH, CH; 2, 7-Tetramethylene-4, 5-bezotropone ut of the plane ofthe molecule and being non. Inthe latter compound, the C=O group is formed o1 ae planar, steric inhibition of resonance occurs and the compound shows normal value for v._, Whereas in the former case C-O double bond lengthens owing to conjugation of the C= Or bond with the rest ofthe molecule and as a consequence V¢_o comes down. Field effects Electrostatic or steric through space interaction between two groups within a molecule is called field effect. This field effect often influences the vibrational frequencies ofboth the groups. Ithas been observed that the v, is higher when the Cl atom of «-chldocyclonexamone occupies the equatorial position when itis in the axial position. In the equatorial position, the electron cloud ofthe Clatom and that of the oxygen atom experience electrostatic repulsion an as a result of which carbon-oxygen bond does not acquire a partial single bond character, ifit does so, it will have to face a greater repulsion. ie Gh Ae wee “OA Reputten & rt Sa A ° 8 Y oO xX Y H H re Br H Br Br Ring size Carbonyl stretching fequency in eyclic ketones having ring strain is shifted to higher value, The C- CO-C bond angle in strained rings is reduced below the normal value of 120° (acyclic and Si 114 | SpectroscopyCHEM ACADEMY membered cyclic ketones have the normal C-CO-C) angle of 120°C). This leads to an increase in s-character in the sp? orbital of carbon involved in the C =O bond. Hence, the C =O bond is shortened (strengthened) resulting in an increase in the (Vg. q) frequency. Ono On O Nostain Moderate sain ‘Highly stained Veo 181 ein! 1745 nt 1780 on! Vv, Nc=0 « cc ring stra = «ee ring strain Z Bond angle 0 L- ‘° =O Q=0=0 + CO L- 4 [=o increasing angle strain % s-character increase ¥, \ DC=O frequency increase Due to ring strain, bond strength of external double bond length increase. 1800} 1720] ring size Illustration: CH; 1? Cc As hE Q A @ (i) Gi) (vy) w) De=c® mri) Gid)> > O | | Spectroscopy | 115UT-JAM/M.Sc. Entrance Q cag (ii) (iii) << (it) > > goOn°¢ 4 Vo=c 1650cm- 1610. cm~—-1570em™ 1640 cm™ ine Similar to the ketones, as ring strain in lactones increases, the carbonyl stretching frequency also increases. 0 Oo © » No strain Moderate strain Highly strained S-valerolacione srbutyrotactone -Propiolactone (xo )1735 en 1770 em! 1800 cnr! ‘The C=O frequency in lactams too depends on the ring size. Similar to that ketones and lactones as the ring strain in lactams increases, the s-character of sp? carbon of C = O also increases and thus the carbonyl stretching freqeuncy also increases, da oo of S-valerolactoam +-butyrolactone B-Propiolactoam No strain Moderate strain Highly strained (ex) 1670 car! 1700 enr! 1745 cnr! Alkenes C=C stretching vibrations are moderate to weak absorptions at 1680 — 1620 cme! Vinyl group absorbs near 1640 cm! -~C=C-R. trans olefin absorbs at 1670 em-!, x \ 4 Pa, is olefinabsorbs at 1670 en \ Internal double bonds are less intense in IR then terminal bonds. Olefin; conjugated dienes without a centre of symmetry produce two C=C st shows absorption at 1650 cm! and 1600 em~!, Symmetrical 1, 3- 1625 em™!. Absorption frequency of > C = C is reduced by 30 Olefinic CH stretching vibrations above 3000 en! stretching. The most characteri ic bond stretching vibrationin retching bands. 1, 3-pentadiene enhanced olefic absorption near cm! when conjugated >C = 0. result from aromatic, acetylenic, or olefic C-H Of olefic are out ofplane C—H bending vibrations at 1000 ent! 116 | Spectroscopy(CHEM ACADEMY 650 cm"'. they are very strong bands. ‘Acetylenes have two stretching vibrations C = C stretching band occurs at 2260 cnr”. In monosubstituted acetylene R - C= CH, the C=C stretching occurs at 2140-2100 em-!. C—H stretching of R-C=C—H oceus at 3333~3267 ent, This is astrong band narrower than hydrogen bonded OH and NH bands, which occur in the same region. C—Hbending vibrations of acetylenes occurs at 700 — 610 ent! (strong band). ‘Aromatic hydrocarbons: The most prominent and most informative bands in the spectra of arom: compounds occur in the low frequency range between 900 ~ 675 cmr!. Aromatic C - C stretching bands occur between 3100 and 3000 cm. Alcohols and Phenols : © -H stretching and C —O stretching are characteristics of alcohols and phenols, IfOH is “free” (non-hydrogen bonded) then strong absorption occur at 3650—3580 cnr. Such sharp absorptions occur only in very dilute solutions ofaleohols in non-polar solvents. Intermolecular hydrogen bonding increases as the concentration of the solution increases and the O- H stretching frequency is shifted to lower values. 6 /\ fk ROH nd 0 en Fy Ho AR Strong intramolecualr hydrogen bonding occurs in orthohydroxy acetophenoneand here again the O— H stretching frequency is less than in free phenol. fo ‘CH Orhydroxyseetopophenone OH stretching absorption occurs at 3077 cnr!. This absorption is broad, shallow and independent of concentration. Concentration = 0.03 M of O-hydroxyacetophenone ‘Concentration = 1 M. oF Oshydroxyacetophenone = ‘Transmittance Transmittance BIS ear" 37S em v—> ves no~(O)-cocn shows free hydroxyl peak at 3600 em in dilute CCl, solution and braod strong, peak at 3100 cnr inthe neat sample (no solvent). This is due to intermolecular “Hl bonding inthe pure sample, R 1se-€-{O)-0-..0= ¢—~Op>e- noe bn, cut ©) o Spectroscopy | 117NT-JAM/M.Sc, Entrance Jin In2, 6-ditertiarylphenol, steric hindrance prevent H-bonding. Me. OH Me Z intermolecular wesc CMe bonding here Me’ Me retching vibrations in alcohols Non-bonded-OH stretching is observed inthis compound C—O st phenols produce a strong band in the 1260-1000 om, Ethers a ‘The characteristics of ethers inthe IR isthe C-O—C stretching vibrations ~it is 1150t0 1085 e ' for aliphatic ethers (e.g. (Or-o-cny) C-O-C asymmetric stretching occurs at 1275 1200 cm-! along with 1075 to 1020 em! and C=C stretching here isat higher intensity than inolefin This C=C stretching usually occurs asa double at 1620 cm! and 1640 cm™. Carbonyl compounds The absorption band for the carbonyl group (C =O) is very strong and sharp, hence easy to recognise A strong absorption in the region 1660 to 1850 cnr! generally points tothe carbonyl group is a obiquitous (ie. widespread) structural feature in organic compounds. (Though C=C occurs in the above frequency range, the intensity will be only moderate), The carbonyl group forms part of various functional groups such as aldehydes, ketones, acid chlorides, esters, acid amides and acid anhydrides frequency of absorption ofa neat sample ofa saturated ketone (aliphatic) viz. 1715 cm is taken as normal, (alphatic ketones : 1725 to 1700 cm~!; alkaryl: 1700 to 1680 cm-!; diarlyl: 1670 to 1660 c conjugation of C=O with C=C resulting resonance -c£0%c£b <> ~c-c=c-o It reduces double bond character between C and O of carbonyl group. Hence absorpton occurs as lower frequency (wave number). a ° I CH;—C—CH, CH,—C- > C0 steching occurs at 1725 ent C=O stretching occur 1683 en CH. oO 8 < — cue) of cnt) ate, | More canonical strucures are possible with single bond between “C” and “Or of carbonyl group. Absorption of> C=C Veymmetric Fermi Resonance “The energy resonance between fundamental band and adjecent over tone, due to this both band shifted from there original possition in which one goes to higher frequency and another goes to lower frequency and become almost same intensity this phenomena is known as fermi resonance. Fermi resonance was first observed was Enricho Fermi in CO, molecule Spectroscopy | 119UT-JAM/M.Sc. Entrance 0-C-0 ding Fundamental Bending _ symmetric sé7gen stretching First overtone 2.x 667.3 = 1334.6 cnr Fermi Resonance 1386.1 env . The intensity ofboth peak afler Ferns Resoranceisalimost same (1 :0.9) because after Fermi Resonance fundamental peak become partial over tone and over tone peak have partial fundamental charactor, Example: In aldehyde C-H stretching, two peak occur at 2720 cm” due to Fermi Resonance. Ilustration: Anorganic compound with molecular formula C,H,NO shows absorption data in the region 3415 (1m), 3236 (m), 3030 — 2899 (m), 1668 (3), 1635 (s) and 1460 cm (s). Give the probable structure of the compound. Solution: CH,CH,CONH, Mlustration: An organic compound A with molecular formula, C,H,N shows the following peaks in the infrared spectrum; (9) 3012 em! (an), (i) 3425 emt (5), (ii) 3236 cm (m), (iv) 1615 cm! (m). When the compound A is treated with nitrous acid, we obtain a compound B which showsa strong peak at 3430 cmr!. Identify A and B. Solution: (i) Two bands at 3425 cme! and 3236 cm are due to asymmetrical and symmetrical N-H stretching. Clearly, the compound contains -NH, group. (ii) The bands at 3012 cm? is dueto C-H str while the band at 1615 em” is due to N-H bending, The probable compound is CH,CH,CH,NH. When itis treated with nitrous acid, NH, is converted into OH group which shows a strong peak at 3430 emt. CH,CH,CH,NH, + HONO — CH,CH,CHOH (Propyl ale.) +N, + H,0 FREQUENCY (cm"!) 4000 2500 200018001650 1650 650 OH CH csc | very | coo | con FEW cei new cen | Banos a Cra ECaC) 7 ‘ e 55 64 WAVELENGTH (1) EIGURE The app aions where various common types of bonds ab btn gtr pd ne me a ating eres 120 | Spectroscopy(CHEM ACADEMY. — ow! —____» 18101800 17600-«1735—= 1725 t718S1710—SS 1690 Anhydride Acid, Anhydride Ester Adel i vaiverfe. Ack,, Aphydjide stor yde Ketone Carbgnyio Amide FIGURE Normal base values for the C=O stretching vibrations for carbonyl groups. NMR SPECTROSCOPY Introduction The nuclei of many elemental isotopes have a characteristic spin (1). Some nuclei have integral spins (e-g.1= 1,2, 3 ...), some have fractional spins (e.g. 1= 1/2, 3/2, 5/2 ...), and a few have no spin, I= 0 (eg. !C, 32C, !0, 328, etc). Nuclei with even atomic numbers and even mass numbers are invisible in NMR. Isotopes of paticular interest and use to organic chemists are 'H, '9C, !9F and *!P, all of which have a= 1/2. Essentials of an NMR spectrometer are a powerful magnet a radio-frequency generator, and a radio frequency detector. The sample is dissolved in a solvent, most commonly CDCI, or D,O and placed in a sample tube which is then suspended in the magnetic field and set spinning, Deuterated solvents are used to eliminate 'H signals from the solvent. Chemical Shift: Table of characteristic proton NMR chemical shifts Type of proton ‘Type of compound Chemical shift range, ppm RCH, 1° aliphatic 09 R,CH, 2° aliphatic 13 R, CH 3° aliphatic 15 vinylic 465.9 vinylic, conjugated 55-15 acetylenic 23 aromatic 68.5 benzylic 2.23 allylic. 7 fluorides 44,5 chlorides 34 bromides 25-4 iodides 24 alcohols 34-4 ethers 3.34 Spectroscopy | 121NT-JAM/M.Sc. Entrance 3.74.1 2. RCOO-CH esters HC-COOR esters 2-22 HC-COOH acids 2-26 HC-C=0 carbonyl compounds 2-27 RCHO aldehydic 910 ROH hydroxylic 24 ArOH phenolic 4-12 C=C-OH enolic 15-17 RCOOH carboxylic 10-13.2 HC-NHR amine 15-20 RNH, amino Ms RNHC(=0)R’ amides 5-8.5 + If we were dealing with nuclei isolated from other atoms and electrons, any combination of applied field and radiation that produces. signal for one nucleus would produce a signal for all identical nucle. + Hydrogen or carbon nuclei in organic molecules are not isolated from other atoms, theyare surrounded by electrons which are caused to circulate by the presence ofthe applied field. + The circulation of electrons around a nucleus inan applied field is called diamagnetic current and the nuclear shielding resulting from it iscalled diamagnetic shielding. + The difference in resonance frequencies among the various hydrogen or carbon nuclei withina molecule due to shielding or deshielding is generally very small. + Itiscustomary to measure the resonance frequency (signal) ofa reference compound. + Thereference compound now universally accepted is tetramethylsilane (TMS). i HsCSi—CHs CH, Chemical shift (s): The shift of an NMR signal from the signal of TMS. Normally given in parts permilion (PPM). 55 ~ Shift in frequeney from TMS (Hz) Frequency of spectrometer (Hz) NMR phenomenon A spining charge generates a magnetic feld. The resulting spin-magnet has a magnetic moment (H) proportional to the spin (I). Inthe presence ofan external magnetic field (By), two spin states are, +1/2 and—1/2. The magnetic ‘moment ofthe lower energy +1/2 state is aligned with the external field, but that of the higher energy, | 122 | Spectroscopy. (CHEM ACADEMY 2 spin state is opposed to the external field. The arrow representing the external field points North. i@¢ story Lor) 2 2 Spin Energy States The difference in energy between the two spins states is dependent on the external magnetic field strength, and is always very small. The following diagram illustrate that the two spin states have the same energy when the externla field is zero, but diverge as the field increases. 12 E ‘SE WB “2 By For NMR purpose, this small energy differnece (AE) is usualy given asa frequency in units of MHz (106 Hz), ranging from 20 to 900 MHz, depending on the magnetic field strength and the specific nucleus being studied. Chemical Shift + Theelectron (s) surrounding the proton in covalent compounds and ionsareresposnible for different NMR specrum for different compounds. Since electronsare charged particles, they move in response to the extenral magnetic field (B,) so as to generate a secondary field that opposes the much stronger applied field. This secondary field shields the nucleus from the applied so By must be increased in order to achieve resonance (absorption of RF energy). +The frequency ofan NMR transition depends on the local magnetic field experienced by the nucleus and is expressed in terms ofthe chemical shift, 6, the difference between the resonance frequency of nuclei in the sample and that ofa reference compounds : x108 ‘Acommon standard for 'H, °C or ?°Si spectra is Tetramethylsilane Si(CH,),, abbreviated as TMS. When 8 <0 the nucleus is said to be shielded relative to the standard; 8 > 0 corresponds to anucleus that is deshielded with respect to the reference. ‘The H chemical shift in CH, in only 0.1 because the H nuclei are in an environment similar to that in Tetramethylsilane, but the H chemical shift is5 = 3.1 for Hin GeH. Chemical shift are different for the same element in inequivalent positions within a molecule. Chemical Equivalence + Allthe protons found in chemically identical environments within a molecule are chemical equivalent and they often exhibit the same chemical shift. Thus all protons in trimethylslane (TMS), benzene, cyclopentane or acetone have same 6 value. + Protons that are chemically equivalent are also magnetically equivalent, however in cases. Protons Spectroscopy | 123HT-JAM/M,Sc, Entrance | jen. that are chemically equivalent are not magnetically equivalent perce by symmetry : Ea re a eg i ; all. + Molecules with one set ofequivalent atoms give one NMR sign: ” iT reach set. ‘Two or more sets of equivalent atoms give a different NMR signal for each CH, ci Ms H,c—C—cl Oe PO H H H 2'Hsignals 2'H signals 3'Hsignals 3 'H signals ‘Chemical shift depends on: + Electron density—> Induced magnetic field -> shielding and deshielding * Electron density depends on electronegativity of near by atoms hybridization of nearlby atoms magnetic induction within an adjacent x bond. Note: + Thenumber of signals shows how many different kinds of protons are present. The location of the signals shows how shielded or deshieled the proton is. The intensity of the signal shows the number of protons of that type. Signal splitting shows the number of proton on adjacent atoms. Magnetic equivalence: Magetically equivalent nuclei are isochronous have identical chemical shift and have equal coupling (J) to every other nuclei in the molecule, Similarly, iftwo nuclei are magnetically equivalent, they give a single signal and do not split oneanother. no, Chemically identical nuclei (H, and HY )is different to Hy, Integrals and Integration Inthe NMR spectrum, the area under each peak is proportionalto thé ‘number ofhydrogen generating that peak. Hence in phenyl acetone. The area ratio of the three peaks is $ 32:3, the same as the ratio of the numbe of the three types of hydrogen, ™ 124 | SpectroscopyCHEM ACADEMY Local Diamagnetic Shielding (A) Electronegativity effects (Electronegativity = E.N.) ENN. ¢, 84 (Electronegativity ofattached element increase, chemical shift increase) Electronegative substituents attached to a carbon atom, because of their electron withdrawing effects, reduce the valence electron density around the proton attached to that carbon. ‘These electron shield the proton from applied magnetic field. This effect is called Local Diamagnetic Shielding. (B) Hybridization effect sp? Hydrogen iy ed C-C-H = C-C- I | c ce x >> Strained ring 2 1 05 sp? hydrogen in an sp? - 1s C-H bond, the carbon atom has more s character (33% s) which effectively renders it "more electronegative” then on sp? carbon. (25%). This result in less shielding for the H molecules than in an sp? - Is bond. Thus 8 for vinyl hydrogen > 5 - 6 ppm 8 for aromatic hydrogen—> 7 - 8 ppm (high value due to anomalously large chemical shift due to anisotropy) 3 for aldehyde proton ->9- 10 ppm (high 6 value due to anomalously large chemical shift due to anisotropy) sp hydrogen Acetylenic protons have greater 8 value than sp* carbon protons. (C) Influence of Hydrogen Bonding Proton that can exhibit hydrogen bonding exhibit extremely variable absorption positions over a wide range. The more hydrogen bonding that take place, the more deshielded a proton becomes. The amount of H-bonding is often function of concentration of temperature. ‘Athigh dilution (nOH bonding), hydroxyl protonaborb near 0.5-10 ppm. In concentration solution, their absorption is closer to 4-5 ppm. Ro . Ny ye te gk Free (iste rluion) Hydrogen donded(eoeented soaton MAGNETIC ANISOTROPY ‘When itis place in a magnetic field, the x electrons in the aromatic ring system are induced to circulate around the ring. This circulation is called a ring current. The moving electrons generate in a loop of wire Spectroscopy | 125IT-JAM/M.Sc. Entrance i through which a current is induced to flow. The magnetic field covers spatial volume seer it influences the shielding of the benzene hydrogens. Th hydroge elie by the diamagnetic anisotropy of the ring, All groups in a mo! secondary anisotropic fields. Inacetylene, the magnetic field gen electrons has a geometry such that the acetylenic hydrogens are sI have resonance at higher field than expected. e benzene a ~ 105m a HM chon or, 5 CH, CH acum fe aso aoe. v Shielded ott : VANE ch, ot ppm Ring current (10 w electrons) Ring curent (6 electrons) Fig. The effects of anisotropy in some actual molecules, SPIN-SPIN SPLITTING RULE In 1,1,2-trichloroethane there are two chemically distinct types of hydrogens: tee 126 | Spectroscopy Jecule that have 7 electrons generate erated by induced circulation ofthe x Shielded. Hence, acetylenic hydrogensCHEM ACADEMY On the basis of the information one would predict two resonance peaks in the NMR spectrum of 1,1,2-trichloroethane, with an area ratio (integral ratio) of 2:1. In reality, the high resolution NMR. spectrum of this compound has five peaks: a group of three peaks (called a triplet) at 5.77 ppmanda group of two peaks (called a doublet) at 3.95 ppm. The methine (CH) resonance (5.77 ppm) is said to be split into a triplet, and the methylene resonance (3.95 ppm) is spit intoa doublet. The area under the three triplet peaks is |, relative to an area of 2 under the two doublet peaks. This phenomenon, called spin-spin splitting, can be explained empirically by the so-called n + | Rule. Each type of proton “senses” the number of equivalent protons (n) on the carbon atom(s) next to the one to which it is bonded, and its resonance peak is split into (n+ 1) components. Equivalent protons behave as a group a ‘Two neighbors give a triplet One neighbor gives a doublet (n+1=3) (area=1) (4 1=2) (area =2) ert i Hee a HAH H ‘Three equivalent neighbors give a quartet “Two equivalent neighbors give a triplet (a+ 1=4) (acea=2) (n+ 1=3) (area=3) #H NO; One neighbor gives a doublet Six equivalent neighbors give a septet (n+ 1=2) (area=6) (n+1=7) (area=1) THE ORIGIN OF SPIN-SPIN SPLITTING Spin-spin splitting arises because hydrogens on adjacent carbon atoms can “sense” one another. The hydrogen on carbon A can sense the spin direction of the hydrogen on carbon B. Proton A is said to be coupled to proton B. Its magnetic environment is affected by whether proton B has a+% or a-¥ spin state. Thus, proton A absorbs at a slightly different chemical shift value in type X molecules thanin type Y molecules. In fact, in X-type molecules, proton A slightly deshielded because the field of protonB is aligned with the applied field, and its magnetic moment adds to the applied field. In Y-type molecuks, proton A is slightly shielded with respect to what its chemical shift would be in the absense of coupling, In this latter case, the field of proton B diminishes the effect of the applied fied on proton A. Spectroscopy | 127UT-JAM/M.Sc, Entrance He - He He +5 co th differign spin relationships between protons H, and Hy. Since ina given solution there are approximately equal numbers of X- and "type molecules atany given time, two absorptions of nearly equal intensity are observed for proton A. The resonance of proton A is said to have been split by proton B, and the general phenomenon is called spin-spin spliting Ofcourse, proton A also “splits” proton B since proton A can adopt two spin states as well. The final spectrum for this situation consists of two doublets: i see tT 1 REGIONS OF THE PROTON NMR SPECTRUM Fig. Two different molecules in a solution Chemical Shift (8) = ——“se« —Vsstee 19° py Operating frequency t+5=10 ™s ‘3(PPM) 10 3 0 ‘egions of the proton NMR spectrum MoS protons. on } protons on | protons.on | saturates saturated unsaturated | unsaturates | unsaturated | CH Che ‘carbons: carbons: ‘cerbons: cH, CH ‘next to benzene, alkenes cH cH oxygen: aromatic neat to een ‘aldehydes | hydrocarbons ongen Te 105 as 65 45 30° Siopm) 0.0 128 | SpectroscopyCHEM ACADEMY PROTONS ON SATURATED CARBON ATOMS, Chemical shift: Atom Electronegatlvity Compound u 1.0 CHs-Li si 19 CHs-SiMeg 00 N 3.0 CHs-NH2 2.41 ° 3.4 CHs-OH 3.50 F 40 CHF 4.27 CHCl CHaCla CHCl; HNMR shit, ppm. 306 5.30 7.27 Approximate chemical shifts for methyl groups No electron-withdrawing functional groups Less electron-withdrawing functional groups X More electron-withdrawing functional groups X Me at about 1 p.p.m. MeX at about 2 p.p.m. (Le. add 1 p.p.m.) aromatic rings, alkenes, alkynes nitrites (CN) amines (NHR) sulfides (SR) carbonyl groups: acids (CO2H), esters (COR), ketones (COR), MexX at about 3 p.p.m. (ie. add 2 p.p.m.) oxygen-based groups: ethers (OR), esters (OCOR) ‘amides (NHCOR) sulfones (SO2R) Chemical shifts of protons in CH, CH,, and CH, groups with no nearby electron-withdrawing groups CH group (CHa group CHg group 0.4 p.p.m. downfield 0.4 p.pum. downfield —_— <—_—_ 1.7 p.p.m. 1.3 ppm, 0.9 p.p.m. Number of NMR Signal Number of NMR signal tellus about how many different kind of proton are present in the molecule. + Chemically equivallent proton gives 1-NMR signal + Chemically non equivallent proton gives different NMR signal ‘Compound CH, CH,-CH, CH,=CH, CH,-CH,-Cl Hy Ha wey ‘Noumber of NMR signal 1 NMR signal 1 1 2 Spectroscopy | 129IT-JAM/M,Sc. Entrance © a2 = ©- NO, ©- COcH; 5O> Me CH3-CH,-OH py 0) H, H3;C—C;—CH,* Se cl Cl Here c & d are disteriotropic proton Me, 130 | Spectroscopy‘CHEM ACADEMY LT j (89°C) LZ 1 (Room temperature) Spleating of the Signal Spleating ofthe signal tellus about heigh bouring environment of the proton that is they give the information ofnumber of neighbouring proton in the molecule. * Due to spin-spin interaction with neighbouring proton NMr signal spleated according to (2NI + 1) rules N= number of neighbouring proton 1= nuclear spin quantum number of neighbouring proton. Example: Compound Signal 9 H Il 1, H3C—C -C—CH3 3 it 1 singlet 0 @ © 9, CH,-CH,-NH, ves 2 M = Multiplat| i 3. H3;C—C—NH 2 (Ss) (s) Hy H C-CH3 a oot 4. 5 HOH da dd ° H, Il 5. H;C—C —C—H 3 t dQ t NO, ™ H di 6. 5 aoe iocs Spectroscopy | 131ATJAM/M.Sc. Entrance x 5 Y 3 7 yar Frna Zz x Z Y A 3 a a 9% HAC a ‘ (aa) 7 10 oy 4 (cay Spleating / Coupling with hetro nucleia ya No spleating lo iH Spleating SNe anc No spleating HD Spleating ae —— < lo spleating D / = Spleati H-BC pleating \ a No spleating B ee HN Spleating Y p HONS pleating 132 | Spectroscopyu loys Cc NY PH PCH P-O-C-H P-C-C-H P-O-H 31p_nis 3'p-F Pcl Sips No spleating Spleating Spleating Spleating Spleating No spleating, Spleating Spleating No spleating No spleating ‘Uneven electron distribution in aromatic rings CHEM ACADEMY ‘The 'HNMR spectrum of this simple aromatic amine has three peaks in the ratio 1:2:2, which must correspond to 3H:6H:6H. The 6.38 ppm signal clearly belongs to the protons round the benzene ring, but whyare they at 6.38 and not at around 7.2 ppm? The solution to both these puzzlesis the distrbution ofelectrons in the aromatic ring, Nitrogen feeds electrons into the system, making it electron rich: the ring protons are more shielded and the nitrogen atom becomes positively charged and its methyl groups more deshielded. The peak at 2.89 ppm must belong to the NMe, group. lone pair in powital on nitrogen HC. -CHs 842.89 H H 846.38 HC CH; H 542.28 Hs + CHs N 4. H chs CH; Spectroscopy | 133NT-JAM/M.Sc. Entrance ical shifts How electron donation and withdrawn change chemical shifts electron-withdrawing groups iy inductive effect, conjugation by conga a tr Po Fo wo tt K BN 3 ¢ 8.07 7.78 Oh, 8.48. 810 8.10 i 4 H H ut a a « 0700 ‘OH tl ov “a F F N F ‘The largest shifts come fom groups that withdraw electrons by conjugation. Nitro is the most powerfi Then come the carbonyl and nitrile group followed by groups showing simple inductive withdrawal, CF, isan important example of this kind of group-three fluorine atoms combine to exert a powerful effect. In the middle of out sequence, around the position of benzene itself at 7.27 ppm, come the halogens, whose inductive electron withdrawal and lone pair donation are nearly balanced. electron-donating and -withdrawing groups balance between withdrawal by induethe effect and donation of lone pais by conjugation Gt Gt Gt Gt @ 4 7.40 H 7.32 H 7.24 H 7.00 ir a F Alkyl groups are weak inductive donators, but the groups which give the most shielding-perhaps surprisingly-are those containing the electronegative atoms and N. Despite being inductively electron withdrawing (the C-O and C-N o bonds are polarized with 8 + C), on balance conjugation of their lone pairs withthe ring makes them net electron donors. Theyincrease the shielding atthe ring hydrogens. ‘Amino groups are the best. Note that one nitrogen-based functional group (NO,) isthe best electron withdrawer while another (NH,) isthe best electron donor. electron-donating groups aan omare| (ane sina tycodae : es “acti TI 7 1 PD 200 hi fs bay a cis " Electron rich and electron-deficient alkenes A conjugating and electron-withdrawing group such asa ketone removes electrons from the double 134 | Spectroscopy‘CHEM ACADEMY bond asexpected, The nearer the C=O group is only slightly downfield from cyclohexene but the more distant one is over | ppm downfield. 727 568 Oc CC H 1a 508 , 6.0 465 4 i" u Ch 10 6.35 Oxygen a conjugating electron donor is even more dramatic. It shifts the proton next to it downfield by the inductive effect but pushes the more distant proton upfield a whole | ppm by donating electrons. ‘THE COUPLING CONSTANT ‘The distance between the peaks ina simple multiplet is called the coupling constant J. The coupling constant is a measure to how strongly a nucleus is affected by the spin states of its neighbour. The spacing between the multiplet peaks is measured on the same scale as the chemical shift, and the coupling constant is always expressed in Hertz (Hz). In ethyl iodide, for instance, the coupling constant Jis7.5 Hz. The spectrum in Figure was determined at 60 MHz; thus, each ppm of chemical shift (6 unit) represents 60 Hz. Inasmuch as there are 12 grid lines per ppm, each grid line represents (60 Hz)/ 12=5 Hz. Notice the top of the spectrum. It is calibrated in cycles per second (cps), which are the same as Hertz, and since there are 20 chart divisions per 100 cps, one division equals (100 cps)/20= 5 cps=5 Hz. Now examine the multiplets. The spacing between the component peaks is approximately 1.5 chart divisions, so 5 Hz J=15 divx 7.5Hz I div. That is, the coupling constant between the methyl and methylene protons is 7.5 Hz. When the protons interact, the magnitude (in ethyl iodide) is always of this same value, 7.5 Hz. The amount of coupling is constant, and hence J can be called a coupling constant. Spectroscopy | 135IT-JAM/M.Sc, Entrance 1. Geminal Coupling Constant ; Ifintereting nucleia are seprated by two o-bond than coupling is cal Taam depend on bond angle electro negativity and %s character led Geminal coupling, Jygn © E.N.cc bond angle c % S character CH,-H =~12.5 CPS 10.8 CPS| “J decreases 25° eps} 2. Vieinal Coupling Constant If intreating nuclei are seprated by three sigma bond than coupling is called vicinal coupling. ) c—C It HH vicinal coupling constant depend on dihydral angle and explation by karplus curve. Jy, = 8.5008" 0-0.28 (0 =0-90°) Jyiq = 9.5c0s” -0.28 (8= 90-180") Jani > Son > 7), ache a H (| 51.5 eps H ; ; - increasing ring size “Jincreased 1 1.5—3.7 eps H H il 5.1-7.0 eps H H ] 8,8—11.3 eps H H 9.0 - 12.6 eps On 136 | Spectroscopy(CHEM ACADEMY Coupling is a through bond effect Coupling is in fact a ‘through bond effect” because ofthe way coupling constants vary with the shape of the molecule. The most important case occurs when the protons are at either end of'a double bond. If the two hydrogens are cis, the coupling constant J is typically about 10 Hz, but ifthey are trans, J ismust larger, usually 15-18 Hz. These two chloro acids are good examples. I I Hatoms distant tyerogens re vans Hatome close ‘ora paratt sais Coupling constants depend on three factors rorogens as orbitals not paral, yeah Factors affecting coupling constants + Through bond distance between the protons. + Angle between the two C-H bonds. + Electronegative substituents. The coupling constants we have seen so far have all been between hydrogen atoms on neighbouring carbon atoms-in other words, the coupling is through three bonds (H-C-C-H) and is designated *J,4. ‘These coupling constants), ,, are usually about 7 Hz in an open-chain, freely rotating system such as we have in haptanone. Coupling (7J,,,;) across double bonds are usually larger than 7 Hz (11 Hzin cyclohexenone). *J,,,; couplings are called vicinal couplings because the protons concerned are on neighbouring carbon atoms. But across a double bond there is no rotation and the angle between the two C-H bonds is fixed: they are always in teh same plane. In the plane of the alkene, the C-H bonds are either at 60° (cis) or 180° (trans) to each other. Coupling constants in benzene rings are slightly less than those across cis alkenes because the bond is longer (bond order 1.5 rather than 2). 3.4; coupling constants Fehon Bees nee tcc feasted Fi nun 4 AY vs vs ‘ ( AY kh i feenen Cre eae ep rane foe foot jasspie The effect of the third factor, electronegativity, is easily seen in the comparison between ordinaryalkenes and alkenes with alkoxy substituents, known as enol ethers. One pair has a phenyl group at one end of the alkene and the other has an OPh group. For either pair, the trans coupling is larger than the cs, as. you would now expect. But ifyou compare the two pairs, the enol ethers have much smaller coupling ‘constants, The trans coupling for the enol ehters is only just larger than the cis coupling for the alkenes. The electronegative oxygen atom is with drawing electrons from the C-H bond in the enol ethers and weakening communication through the bonds. Spectroscopy | 137HT-JAM/M.Sc, Entrance 3 and enol ethers eee fect of el stive substituents on °JuH Mey = AL.5 HZ Vane = 16.0 Hz Baia = 6.0 Ht . it OPh ; = ; i Long-range coupling 5 Four bond coupling 4J, is usually zero. However, its seen in some special being meta coupling in aromatic rings and allylic coupling in alkenes. In both, the: ion. This arrangement looks two hydrogen atoms can line up in a zig-zag fashion to maximize interacti I cases, the most importan, h, the orbitals betweenthe rather like a letter ‘W’ and this sort of coupling is called W-coupling. Even with this advantage, values of #J,y, are usually small, about 1-3 Hz. ‘meta coupling SS 0 C=C>C=C (bt) C=C>C=C>C-C (© C-C>C=CCaC Ethanol and glycolin CCl, exhibit broad O—H str. near 3350 emt in IR spectra.On dilution with CC, the spectrum of glycos does not charge but that of ethanol exhibits a sharp band at 3600 ent in addition to band at 3350 cm because (a) Intermolecular H-bonding is concentration dependent (b) Intramolecular H-bonding is not affected on dilution (©) Botha and b (d) None Inthe IR spectrum ofaroyl chloride, a weak band near 1750 cm results from (@) inductive effect (b) Fermi resonance between C = © band and first overtone (©) conjugation effect (@Al Compound, C,H, shows absorption at 1380 em-!. It is | (a) Pentene (b)Cyclopentane (c) Pentyne (All Ketenes absorb in IR at a very high frequency (2150 cm!) because (a) The inner C is sp-hybridised (b) The more s character ina bond, the stronger it is (c) Inner C is sp” hybridised (d) Botha and b Ring strain in lactone (cyclic ester) ora lactam (cyclic amide) i (a) Increases carbonyl stretching frequency (b) Decreases carbonyl stretching frequency | (c) Increases C=C frequency (d) Decreases C=C frequency Inachaloketones (a) Two C=O stretching bands are observed (b) One band has normal frequency 142 | Spectroscopy19. 20. 21. 22. 24. 25. 27. ‘CHEM ACADEMY (c) Other band is at higher frequency due to eclipsed interaction between halogen atom and C=O group (d) Allstatements are correct A compound C,H, decolorises Br, in CCI, and gives a white precipitate with Tollen’s reagent. It has sharp band at 3300 cm! and weak bands at 3085, 2110 em”. Itis (a) Phenyl acetylene (b) Phenyl propylene (©) Phenyl ethylene (d) Octene ‘A.compound ofmolecular formula C,H, has strong infrared absorption band near 1690 em! The most likely structure for the compound is (a) CgH,CH,CHO (o) Hs cH (©) w0o-{ cH = CH) (d) CjH,COCH, ‘The wave number of IR absorption is .. the reduced mass. (a) directly proportional to (b) inversely proportional to (©) independent of (@) directly proportional to square of ‘The number of vibrational degrees of freedom in CH,CH, will be (@)39 (b) 15 (18 (40 Which of the following molecules will not show infrared spectrum? (aH, (HCI (CH, (@H,O ‘The phosphorescence spectrum of the excited species is due to (a) Singlet to triplet transitions (b) Triplet to singlet transitions. (6) Vibration modes (@) Electron spin transitions Among the isomers of C,H, given below, the compound which exhibits absorption band at 3300 cm 1 and 2220 cm”! inthe IR spectrum, is (a) 1,3-butadiene (b) I-butyne ——_(¢)2-butyne’ (d) cyclobutene Monomeric saturated aliphatic carboxylic acids show carbonyl stretching frequency near 1760 cm! while saturated aliphatic ketones near 1720 cm because (a) Mesomeric (M) effect is dominant in acids over the inductive (I) effect (b) effect is dominant in carboxylic acids over the mesomeric effect (c) L effect in ketones is dominant over the M effect. (d) Meffect in ketones is dominant ‘The exceptionally low carbonyl stretching frequency (1650 cn) in 2, 4, 6-cycloheptatrienone is due to (a) Conjugation effect (b) Steric effect (©) Field effect (@ Electronic effect Spectroscopy | 143IT-JAM/M.Sc. Entrance . in lefins is 4 following ole 28. The correct order of IR stretching frequeney of the C=C in the (0 Oe O- b= (dy i>t> I W>t>T c) >> Te tond iat ° ° stretching vibration is 9. ‘The bond that gives the most intense band in the infrared spectrum forts (@C-H (b)N-H (OH (SH 30. The IR stretching frequencies (cm!) forthe compound X are as follows: 3300-3500 (s, br); 3000 (m); 2225 (s); 1680 (s)- QO Co " NC ‘OH x The correct assignment of the absorption bands is (2) Yon = 3300-3500; ¥cy) = 3000; Ven) = 2225; Vico) = 1680 (b) Vony = 3000; Ycp) = 3300-3500; Yicny = 22255 Veco = 1680 (©) Voor = 3300-3500; Vicy1) = 3000; Vicyy = 1680; Vico) = 2225 (4) Yony = 3000; Vey) = 3300-3500; Vey) = 1680; Vycoy = 2225 1, Inthe IR spectrum of p-nitrophenyl acetate, the carbony! absorption band appears at (a) 1670cm —(b)1700em™! —(c) 1730em™ —(d). 1760. cme! 2. Inthe IR spectrum, carbonyl absorption band for the following compound appear at y we 8 H (a) 1810cm) —(b)1770em™!——() 1730cm™ ~—(d) 1690 cm 33. Arrange in the decreasing order of carbonyl frequency ° ° 0 0 od org a) ay am) (ly) (a) IV>1>1> Ib) 1>1V>1M>1@1V>1 I> 1 dy > 1V>1>0 NMR Spectroscopy 34. The "HNMR spectrum of CH,OCHCICH, Cl will exhibit (a) A three proton doublet. One proton singlet and a two proton doublet (b) A three proton singlet. One proton singlet and a two proton doublet (c) Athree proton singlet. One proton triplet and a two proton doublet 144 | Speetroscopy35. 36. 37. 38. ae 40. 41. 42, 43. 44. 45. 46. (CHEM ACADEMY (d)A three proton triplet. One proton triplet and a two proton triplet An organic compound with molecular formula CHCl, exhibits only one signal in the ‘HNMR spectrum. ‘The compound is (a) 2, 2-dichloropropane (b) 1, 2-dichloropropane (c) 1, 3-dichloropropane (d) 1, I-dichloropropane ‘H-NMR spectrum of compound with molecular formula C,HyNO, shows 6 5.30 (broad, 1H), 4.10 (q. 2H), 2.80 (d, 3H), 1.20 (t, 3H) ppm. The structure of the compound that is consistent with the above data is (a) CH;NHCOOCH,CH, (b) CH,CH,NHCOOCH, (c) CH,OCH,CONHCH, (4) CH,CH,OCH,CONH, Which of the following has three types of hydrogens in the following compounds (a) Br— CH=CH, () CH, - CH, -CH, (©) CgH,CH, () CH, - CH, - CH(CH,) NO, Only one signal is present in the PMR spectra of (CH, CH, (6) CyHy. CHj (6) CgHy gs CHO (AI How many Hertz does | ppm correspond to for an PMR spectrometer operating ata radiofrequency of 60 MHzand 100 MHz? (a)6Hz,10Hz —(b) 60 Hz, 100 Hz (c) 100 Hz, 60Hz (d) None Compound C,H ,0 gave PMR spectrum consisting oftwo groups of lines (multiplets) with relative intensities in the ratio 3 : 2. Other compound of the same formula exhibited two lines with relativearea of 9: 1. Compounds are ()Diethylether (b)t-Butylalcohol (c) Bothaandb (d) None Distance between the centres of the peaks of doublet is called (a) Coupling constant (b) Spin constant (c) Spin-spin coupling (d) None ‘The PMR spectra of H, CH,, C,H, and CoH, exhibit (@ Singlet (b) Doublet (c) Triplet (4) Quintet A proton H, is coupled to four equivalent protons H,. The multiplicity and the relative intensity of lines in the signal H, is (a) Doublet, 1:4 (b) Triplet 1:4:6 (c) Quintet, 1:4:6:4:1 (d) Quartet 1:4 ‘The peaks expected in low-resolution NMR spectrum of vinyl chloride and ethyl cyclopropane are (a) 3,5 (0) 5,3 (©)6,3 (4) 3,6 The NMR frequency in MHz of bare H! in a magnetic field of intensity 1.4092 tesla is (given gy = 5.585, fly = 5.05 x 10-27 JT!) (a) 60 MHz (b)120MHz = (c) 1OOMHz == (d) IS MHz, At room temperature, the number of singlet resonances observed in the 'H NMR spectrum of Me,CC(O)NMe, (N, N-dimethyl pivalamide) is, (3 (b)4 (5 (2 Spectroscopy | 145HT-JAM/M.Sc, Entr 7 Shonen harp singlet for one ofits proton arg, 47. 48. 49. 50. 51. 7 53. 146 | Which of the following compounds is expected to show as ppm in 'H NMR spectrum, given that this signal remains unaffected on shaking the solution {hroughy with D,0? (a) CH,CO,H (b) CH;CONHC,Hs (©) n-C,H,;C = CH (d) n-CgH, CHO 1H NMR spectrum of [18]-annulene shows (a) only one peak at 8 7.2 (18H) (b) only one peak at 6 5.0 (18 H) (c) two peaks at 6 9.0 (12 H) and 8—3.0 (6H) (d) two peaks at 8 9.0 (6 H) and §—3.0 (12 H) Compounds A and B exhibit, two singlets, cach in their 'H NMR spectra, The expected chemical shits are 9 -Me O. Me ‘0 2 TT A) SC ®) 0 Mee 0 ve (a) 6.9 and 2.1 for A; 7.7 and 3.9 for B(b) 7.7 and 39 for A; 6.9 and 2.1 for B (©) 6.9 and 3.9 for A; 7.7 and 2.1 for B(d) 7.7 and 2.1 for A; 6.9 and 3.9 for B An organic compound (MF; CH 90) exhibited the following 'H NMR special data: 82.5 (3H, s), 3.8 (3H, s), 6.8 (2H, d, J 8Hz), 7.2 (2H, d, J 8 Hz) ppm. The compound, among the choices, is (@)4-ethylphenol (b)2-ethylphenol _(c) 4-methylanisole (d) 4-methylbenzyl aleohol Appropriate 'H NMR chemical shifts (8) for the protons A-D for the following compounds are mee a ar HOH B A (a) A-6.8; B+ ;D-2.1 ppm (b) A-6.8; B-5.7; C-2.1; D-3.9 ppm (¢) A-5.7; B-6.8; C-3.9;D-2.1 ppm (d) A-5.7; B-6.8; C-2.1; D-3.9 ppm In400 MHz 'H NMR spectrum of organic compound exhibited a doublet the two times of the doublet are at § 2.35 and 2.38 ppm. The coupling constant (J) value is (a)3 Hz (b) 6 Hz (c)9 Hz (12H In NMR spectroscopy, the product of Nuclear *g” factor (gy), the nuclear magneton (By) and the magnetic field strength (Bp) gives the (a) energy of transition from o. to B state (b) chemical shift (©) spin-spin coupling constant (d) magnetogyric ratio Spectroscopy «i54. 55. 56. 57. 58. 59. 60. 61. 62. ‘CHEM ACADEMY ‘An organic compound having the molecular formulae C, gH, exhibited two singlets in the 'HNMR spectrum and three signals in the '3C NMR spectrum the compound is ‘The 'H'NMR spectrum of a dilute solution of'a mixture of acetone and dichloromethane in CDCI, exhibits two singlets of |: | intensity, Molar ratio of acetone to dichloromethane in the solution is (a)3:1 (b) 1:3 (c) 1:1 (@i:t No. of signals in 'H NMR in the given molecules are Hs CH, (a)3, 4,4, 3 respectively (b) 2, 6, 4, 2 respectively (©)2, 4,6, 2 respectively (d) 2, 4, 2, 6 respectively ‘What will be the change in value of y(gyromagnetic ratio) if we double the applied magnetic field (a) Itwill remain same (b) It will get doubled (©) Itwilbecome half (d) Itwill become fourtimes Chemical shift value of proton attached to hetero atom depends upon (A) Concentration (B) Temperature (C) Solvent (D) External applied magnetic field Which statement are correct (@) Both (A) and (B) (b) (A), (B) and (C) (©) (A), (B), (C) and (D) (d) (A), (C) and (D) only A PMR spectrometer operates at 300 MHz. Find the value of magnetic field. Given: g,, = 5.585 and By = 5.05 * 1077)”. (a) 7.05T (b) 6.38T (©) 7.58T (4)5.93T H!, C3, F!9, P3! have nuclear spin equal to (a) 1/2 (b)! ()0 (d) 3/2 In paxylene, the ratio of methyl protonsto ring protons is 6: 4 while for mesitylene, iis (a) 6:4 (b) 3:2 (0)9:3 (6:3 ‘A compound of molecular formula CH, ClO showsa romient band in its IR spectrum at 1690 ent! 1H NMR spectrum revealed only two major typ;es of protons in the ratio ofS: 2. Which one of the following structures best fits the above data? @) € prenicoa ©) a—€_ coc, Spectroscopy | 147NT-JAM/M.Sc. Entrance 63. 64. Carer © € proo-cntcl d) Mr An organic compound Q exhibited the following spectral data. TR: 1760 cm! "HNMR: 8(ppm): 7.2 (1H, d, J = 16.0 Hz), '3CNMR: &(ppm): 170 (carbonyl carbon). Compound Qis Ow Me O. Me ‘OMe o ST ol To fo S Me’ Me M 5.1 (IH, m), 2.1 3H, 8), 1-8 GH, d, J=7.0 Hy Me le The NMR spectrum ofa compound with molecular formulae CsH,0, is shown below. IR spectrum shows medium intensity band at 3270 and 2180 cm”, Draw structure of compound. 8 1.3GCH,0 5 2.8 (7H, s) 6 4.3 7H, oO 2 ° Il (a) CH;—CH,—C—O—C = C—-H (b) CH;—CH, —-O—C—C = C—H Ultraviolet Spectroscopy 65. 66. Compare solvent shift on then—> n* transition of acetone (a) H,0 = CH,OH = C,H,OH = CHCl = CoH) (b) H,0 > CH,OH > C,H,OH > CHCl, > CoH 4 (c) HO < CH,OH < C,H,0H CH,OH o* (2) Dimethyl ether (Qo>0" (3) Methyl vinyl ether (R)nom (4) Triethylamine (S)x >a" (5) Cyclohexane (Nnom &non* (6)Acetaldehyde (a) 1-P, 2-S, 3-T, 4-S, 5-Q, 6-T (b) 1-S, (c) 1-S, 2-P, 3-Q, 4-T, 5-Q, 6-P @t , 2-P, 3-T, 4-P, 5-Q, 6-T 2: , 4-P, 5-Q, 6-T EXERCISE - I One or More Than One Correct Type 9 Ope cry witaton (@) tautomerism (b)3 signals (©) IR frequency around 1715 cme (d) Nucleophilic substitution reaction ° ke will show HC ‘CH; (a) quartet (b) I doublet (c) triplet (d) 2 doublets HC, /PHCH2— OH will show HC (@triplet (b) septet (©) doublet (d)singlet Spectroscopy | 149IT-JAM/M.Sc. Entrance 4. ‘Two doublets are shown by ° Il _ 'H. @)CH,-COOCH,CH(CH), —_(b) CH, -0-C-CH, ~ CHC sa ? ois (©) H-O-C-CH,-CHE (4) CH, - CH, - CH CHF, EXERCISE - III Numerical Answer Type Total number of 1H NMR signals in the given compounds is, BS oO Total number of 'H NMR peaks in the given compound CLHC- CH (OCH,CHs), is__. Total number of 'H NMR peaks in the given compound is: OH Me Total number of deshielded electrons in the [18] annulene is : §,,(OH) value (in ppm) for different compounds A, B and C is 2.0, 5.0 and 11.0. The most acidic compound among A, B and C is that which has 8 value is Total number of 'H NMR signals in the diammonium EDTA is Total number of 'H Signals in the zwitterion form of glycine is The compound shows a proton-NMR peak at 240 Hz down field from the TMS peak in a spectrometer operating at 60 MHz. What are the value ofthe chemical shift 8 in the ppm relative to TMS? A proton has resonance 90 Hz downfield from TMS when the field strength is 1.41 Tesla (14,100 Gauss) and the osciollator frequency is 60 MHz. (a) What will be its shift in Hertz if the field strength is increased to 2.82 Tesla and the oscillator frequency to 120 MHz? (b) What will be its chemical shift in parts per million (8)? 150 | Spectroscopy10. CHEM ACADEMY The following compound, with he formula C,H,O,, isan ester. Give its structure and assign the chemical shift values. it at f fh ree Calculate A, for the following max. H H CH, H i. Nome” CH: c=C Ne’ ON : / a) C=C! ) Some’ @) Roe H 7 H H H cH, Ht cH. Gp ie © qd) ) (CHCH,O' (CHs / cH CHy ‘CH; Cty CH, ©) © CH;COO H,C” “COOH Calculate Aja, for the following 9 cu, c. PN a a/' @ Ne-é ‘o, CHy CH; Spectroscopy | 151IT-JAM/M.Sc. Entrance 152 CHs CH, Os 0: (©) Gd NA 8 Br cu ® Br CH (©) ) a ‘0 0 vey i HO. .C—OH (g) od OH EXERCISE - IV Previous Year Question The number of normal modes of vibration in naphthalene is (a) 55 (by 54 (48 (49 Ractive molecule(s) is/are (a) CO, (b) CS, (¢ ocs (@) NO, ‘The number of proton NMR signals for the compounds P and Q, respectively, is com We P (a) 3 and 4 (b) 3 and 5 (©) 4and 3 (a) 5 and 4 Atan operating frequency of350 MHz, the shift (in Hz) of resonance from'TMS (tetramethysitane) of a proton with chemical shift of 2 ppm is The CORRECT order of carbonyl stretching frequencies for the following compounds is ° 9 9° 0. - Oo orcra: oO I I u 1 Iv (a) II

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