Topic 4.

11 STRUCTURE DETERMINATION Mass Spectrometry Nmr Spectroscopy Chromatography

INTRODUCTION TO STRUCTURE DETERMINATION There are so many organic compounds in existence that it can be difficult to establish exactly what compounds, or what combinations of compounds, are present in a given sample. Chemical tests can be used to distinguish between different functional groups, and melting point and boiling point data can provide some further information as to the identity and purity of a compound, but they can generally only confirm suspected structures and can not usually be used to identify new compounds. Chemical techniques also require fairly large quantities of sample and are not always effective at distinguishing between similar compounds. Chemists have developed a number of other, more precise, analytical techniques to determine the exact structure of organic compounds. Knowledge of three of these techniques is required for AQA A level Chemistry. These are mass spectrometry, infrared spectroscopy and nuclear magnetic resonance nmr! spectroscopy. As infra red spectroscopy is covered at A! level, this topic is concerned with a more detailed consideration of mass spectrometry and nmr spectroscopy. At A level, these analytical techniques must be used to determine the structure of organic molecules containing carbon, hydrogen and oxygen only and generally containing no more than six carbon atoms. The molecule being analysed will be an al"ane, al"ene, alcohol, ether, carbonyl, carboxylic acid or ester. #sually, information is given which enables the empirical formula to be deduced before the analysis begins. This is usually given in the form of composition by mass$ %g A compound contains &'.'( carbon, )*.*( oxygen and +.,( hydrogen. -ole ratio$ C 2 3 &'./0 1 *.* +.,./ 1 +., )*.*./+ 1 *.* *.*.*.* 1 / +.,.*.* 1 0 *.*.*.* 1 /

!implest whole number ratio$ C 2 3

!o empirical formula 1 C203 The molecular formula of the molecule, and its structure, can then be deduced from one or more of the analytical techniques.

one electron is removed. Two possible things can happen to a molecular ion when it is formed$ it can pass intact through the mass spectrometer and onto the detector. the result is the formation of a species with an unpaired electron.< ratio of which < 1 / and m 1 relative mass of molecular ion. This will result in the detection of species with m. one of which is a positively charged ion and one is a free radical. being detected as having an m. 5n some respects molecules behave in a similar way to atoms in a mass spectrometer. more stable species. to deduce relative atomic masses and to deduce molecular formulae.MASS S"ECTROMETR# a4 5ntroduction The technique of mass spectrometry was used at A! level to determine the relative abundances of different isotopes in a sample of an element.or parent ion4.< ratios which are less than that of the molecular ion. but there are important differences$ 6hen a molecule is ionised. it can brea" up into two smaller. or a free radical. As molecules generally contain paired electrons only. 5t is "nown as the molecular ion . . This is "nown as fragmentation. -ass spectrometry can also be used to determine the structure of organic molecules. %g ethane$ H H xo ox x C x C x H o x o H xo xo H H H H xo ox x C x C x H o o H xo xo H H + x or C02+  7C02+89: 9 e The resulting species is thus a positi$ely c%arged ion and also a free radical.

< ratios result from fragmentation of the ethanol molecule. because different molecules fragment in different ways and some fragments are more stable than others. The most abundant fragment ions appear to have relative masses of &) and */. and this m.< ratio in the mass spectrum is &+. This is therefore the molecular ion pea" which means that the molecule has a relative molecular mass of &+.< ratio corresponds to the relative molecular mass of the molecule. and 0= . These pea"s can be used to deduce more information regarding the structure of the molecule.< ratio corresponds to the molecular ion.< ratios result from fragmentation of the molecular ion. and there are less abundant fragment ions with masses of 0. the pea"s with smaller m.The result is that a number of different pea"s are seen in the mass spectrum of an organic molecule$ the pea" with the largest m. %g mass spectrum of ethanol$ The mass spectrum of ethanol contains several pea"s$ the largest m. the other pea"s with smaller m.

the free radical molecular ion is bro"en up.assuming not all of them fragment4 ?9 is the fragment ion and is detected @: is the fragment radical and is not detected c! sta&le ions Bot all possible fragments are detected C some of the fragments form stable ions and these are more li"ely to be formed. C2*C209 and C2*C2C2*94 and acylium ions . As the molecular ion contains an odd number of electrons. The most stable cations are carbocations . C2*C39.detected in mass spectrometer4 This process can be represented by the equation$ 7C02+89:  7C2*8: 9 7C2*89 3nly the charged species is detected as the neutral free radical is neither accelerated nor deflected. These are thus the fragments most li"ely to be detected. and will give the most intense pea"s in a mass spectrum.eg C2*9. %g consider the case of ethane$ H H xo ox x C x C x H o o H xo xo H H H ox x C H o x xo H H xo x C o H xo H + This is the free radical molecular ion This species "eeps the unpaired electron and is an uncharged free radical . . C2*C20C394.this will be a positive ion4 and the other will contain an odd number of electrons .this will be a free radical4. one of the species into which it fragments will contain an even number of electrons .&! fragmentation >uring fragmentation.not detected in mass spectrometer4 This species loses the electron and is a positively charged ion .eg 2C39. The process of fragmentation can thus be represented by the following general equation$ R'(  ?9 9 @: A9: is the molecular ion and is detected .

%g butanone$ C2*C20C3C2* %xpected in the mass spectrum of butanone would be$ m.5t is rarely possible to account for all the pea"s in a mass spectrum4 .The main pea"s in the mass spectrum of an organic compound will thus be the molecular ion pea" and the pea"s corresponding to the most stable ions which can be formed from fragmentation of the molecular ion.< ratio .0 /) 0= ). . &* 5on responsible 7C2*C20C3C2*89: 7C2*89 7C2*C2089 7C2*C20C389 7C3C2*89 %quation to show formation of ion 7C2*C20C3C2*89:  7C2*89 9 7C20C3C2*8: 7C2*C20C3C2*89:  7C2*C2089 9 7C3C2*8: 7C2*C20C3C2*89:  7C2*C20C389 9 7C2*8: 7C2*C20C3C2*89:  7C3C2*89 9 7C2*C208: The real mass spectrum of butanone is shown below$ The most abundant pea" is &*.0 and 0=. can also be accounted for. followed by . The pea"s at /) and ).

. C2*C2C2*9 or C2*C39 A pea" at ).or not present4 in the molecule.no pea" at 0=4 ethanol gives pea"s at /). This is particularly useful for distinguishing between isomers$ %g C&2/' %g C*2+3 %g C02+3 butane gives pea"s at /). and hence the possible identities. &* and )D propanone gives pea"s at /). 0=. &* and )D only .no pea" at 0=4 propanal gives pea"s at /).or absence4 of specific fragments enables the structure to be determined. %g A pea" at 0= suggests the presence of C2*C209 A pea" at &* suggests the presence of C2*C20C209. 0= and &+ -ethoxymethane gives pea"s at /) and &+ .d! using mass spectra to determine structure The molecular ion pea" enables the relative molecular mass of the compound to be deduced.no pea" at 0=4 Thus the presence . of the fragments.or absence4 of these fragments gives important information as to which structural features are present . &* and )D methylpropane gives pea"s at /). The other pea"s give the masses. &* and )D only . 0=. suggests the presence of C2*C20C39 or C2*C3C209 The presence . These gives important clues to the structure of the unfragmented molecule.

Two techniques are required at A level$ proton nmr spectroscopy investigates the absorption of radiation by nuclei of hydrogen atoms . each nucleus can absorb the frequency which corresponds to the difference in energy between its low energy state and its high energy state and switch from one to the other.N)M)R S"ECTROSCO"# a! Introduction !ome nuclei have magnetic properties./*C4 and is thus a technique for obtaining information about the number and arrangement of carbon atoms in a molecule &! proton nmr spectroscopy A number of important pieces of information can be deduced from analysis of a proton nmr spectrum$ 5dentical hydrogen atoms all absorb radiation at the same frequency and so contribute to the same pea". The relative intensity of the pea"s is "nown as the integration factor and is generally given as a simplest whole number ratio . they can either align themselves in the same direction as the magnetic field . This technique for structure determination is "nown as nuclear magnetic resonance . and can thus be used to provide important structural information about the molecule./24 and is thus a technique for obtaining information about the number and arrangement of hydrogen atoms in a molecule car&on-*+ nmr spectroscopy investigates the absorption of radiation by nuclei of carbon /* atoms . The number of different pea"s. 5f these nuclei are subEected to a strong magnetic field. 6hen these nuclei are then subEected to radio waves with a range of frequencies.a high energy state4. therefore. There are a number of different types of nmr spectroscopy. depending on the type of nucleus being investigated.as it is not always easy to see from the spectrum4 . The absorption can be detected and converted into a spectrum. tells you the num&er of different en$ironments of %ydrogen atoms in the molecule. The area under each pea" is related to the intensity of the absorption and gives information about the num&er of %ydrogen atoms of t%at type in the molecule.nmr4 spectroscopy. The frequency of the radiation absorbed by the nuclei varies depending on the type of nucleus and the arrangement of electrons around that nucleus.a low energy state4 or in the opposite direction .

by definition4 a chemical shift of <ero. The pea"s are often not single pea"sF they are split into a number of pea"s very close together. 5f n 1 / the pea" will be split once and will thus appear as a doublet. The chemical shift is generally greater if the hydrogen atoms are closer to electronegative atoms. and hydrogen atoms with a low chemical shift are said to be s%ielded. The pea" resulting from the standard always has . The way in which each pea" is split depends on the total num&er of %ydrogen atoms on ad. expressed as a fraction of the frequency absorbed by the standard. 2ydrogen atoms with a large chemical shift are said to be des%ielded.The frequency of the radiation absorbed depends on the environment of the hydrogen atom and gives information about the position of t%ose %ydrogen atoms in t%e molecule relati$e to ot%er car&on atoms and functional groups. 5f a hydrogen atom is involved in hydrogen bonding.' ppm.n9/4. The names of the split pea"s are as follows$ Halue of n ' / 0 * & ) + Type of pea" !inglet >oublet Triplet Quartet Quintet !extet !eptet The splitting of the pea"s by adEacent hydrogen atoms in this way is "nown as coupling. G 1 f. where n 1 number of hydrogen atoms on adEacent atoms. its pea" will never be split . A hydrogen atom with no hydrogen atoms on adEacent carbon atoms will have no splitting and will give a single pea" "nown as a singlet.standard4 The value of G is generally very smallF typically / /' x /' +.it will always be a singlet4 and it will not contribute to the splitting of any other pea"s.sample4 C f.' x /' + is equivalent to 0. This fraction is "nown as the c%emical s%ift and is given the symbol G. The actual frequency of the absorption is difficult to measureF instead the frequency is measured relative to a standard. 6hat is measured is the difference between the frequency absorbed by the sample atoms and the frequency absorbed by the standard. . 5t is therefore expressed in parts per million C ie 0. The level of splitting of the pea"s is given by .acent atoms.standard4 f. but is also relatively high for hydrogen atoms close to al"ene and arene groups.

The chemical shift can be read from the hori<ontal axis. Ior this reason. the integration factor is indicated above the pea". The line above the spectrum shifts vertically when it passes each pea". The magnitude of the vertical shift is proportional to the integration factor of each pea". The four pea"s in the above spectra could be described as follows$ Chemical shift.computer techniques are usually required to wor" out the integration factor4. .A typical proton nmr spectrum loo"s li"e this$ Irom this spectrum. !plitting triplet sextet singlet triplet 5ntegration Iactor * 0 / 0 The chemical shift. Bote that the integration factor . and this ratio is the integration factor. it is clear that there are four pea"s.. pre integrated nmr spectra are often used. showing both the integration line and the integration factor is shown below$ The shifts at each pea" are in the ratio /$0$*. 3ne example.= /.ppm '. @ou will need to deduce the integration factor of each pea" using only the integration line. Alternatively.+ 0. splitting and integration factor can all be used to deduce important information about the structure of the molecule in the sample.the area under pea"4 is difficult to read directly. and the integration factor and splitting can be deduced by loo"ing at the si<e and shape of the pea"s .* *.

so it is not possible to deduce information about the number of adEacent carbon atoms in each carbon environment A typical carbon /* nmr spectrum loo"s li"e this$ . therefore. using c%emical s%ift. The frequency of the radiation absorbed depends on the environment of the carbon atom and gives information about the position of those carbon atoms in the molecule relative to other atoms and functional groups.c! car&on-*+ nmr spectroscopy Carbon /* nmr spectroscopy wor"s in a similar way to proton nmr spectroscopy. The number of different pea"s. but it is much simpler$ 5dentical carbon atoms all absorb radiation at the same frequency and so contribute to the same pea". so it is not possible to conclude the number of carbon atoms present in each environment. tells you the num&er of different en$ironments of car&on atoms in the molecule. Jea"s in the carbon /* nmr spectrum are not split. The area under the pea"s does not correspond exactly to the intensity of the absorptions. This is measured in the same way as in proton nmr spectra.

there are /0 2 atoms. 5t has no magnetic properties and does not interfere with a proton nmr spectrum. a standard .as the !i is an electropositive atom.or reference4 molecule must be added to calibrate the spectrum.-. The standard normally used is tetramethylsilane . 5t is cheap and non toxic. This means that there are eight different types of carbon atom in the molecule.!. it is clear that there are eight pea"s. c! "reparing samples for proton nmr analysis Kefore a spectrum can be analysed.4 which has the following structure$ H H C H H H C Si C H H H C H H H H This substance has a number of advantages as a standard$ 5t produces a single.T. The chemical shift is then measured relative to this standard as described above. 5t is therefore necessary to use a solvent which contains no hydrogen atoms. all identical4 which ma"es the pea" easy to identify. releasing electron density onto the 2 atoms4 so the pea" is generally at a significantly lower frequency than that found in most organic molecules. The large singlet which arises in proton nmr spectra at G 1 ' as a result of the T-! standard is usually erased from the spectra before it is produced .so you never see it4. The usual choices are CCl& and C>Cl*. each with a different chemical shift. .Irom this spectrum. The 2 atoms are highly shielded . meaning that it does not interfere with the other pea"s and can be easily distinguished from them. > is the symbol for deuteriumF this is an isotope of hydrogen containing one neutron in its nucleus. ii4 Choosing a standard 5n addition to the solvent. interfering with the spectrum produced by the sample. The problem with most solvents is that they themselves contain hydrogen atoms which absorb radiation. it is necessary to produce a spectrum and preparing a sample for proton nmr analysis requires some consideration$ i4 Choosing a suitable solvent 5t is necessary to dissolve the sample in a solvent before it can be analysed. singlet pea" which is very intense .

all the hydrogen atoms are identical. The number of pea"s therefore gives the number of types of hydrogen atom present.d! Using proton nmr spectra in structure determination Jroton nmr spectra are very useful for wor"ing out the structure of organic molecules. there are two types of hydrogen atom. These molecules give only one pea" in the spectrum. pentan * one. %g ethane. however. %g butane. particularly if the molecular formula is "nown. give more than two pea"s$ Kutanone gives three pea"s$ H H C H these H atoms are identical H C H O C H C H H these H atoms these H atoms are identical are identical . methoxymethane H H C H H C H H H H C O C H C H H H C H O H C H H H H 5n some molecules. The information from a spectrum can be bro"en down into four parts$ i4 the number of pea"s %ach pea" corresponds to one set of identical hydrogen atoms. methanol H H H C H H C H H C H H C H H O CH3 C H H C H OH -ost molecules. 5n some molecules. propanone. ethanal. These molecules will give two pea"s in a proton nmr spectrum.

%g.C&2D34 both give three pea"s in their proton nmr spectra$ H H C H C C O C H H H H H H C H O C H C H H H H C H these six H atoms are all identical 2owever the integration factors of the three pea"s in methylpropanal will be +$/$/. but in butanone they will be *$*$0.Kutanal gives four pea"s$ H H C %thanol gives three pea"s$ H H H C O C H C H H C H C H OH H H H %ach of the 2 atoms within the same circle are identical and contribute towards the same pea". -ethylpropanal and butanone . . -ethylpropanal gives three pea"s$ this H atom is unique H C C H H C O C H H H this H atom is unique H H these six H atoms are all identical ii4 integration factor The integration factor indicates the number of identical hydrogen atoms corresponding to that pea". -olecules which give the same number of pea"s can be distinguished because the integration factor of each pea" is different. The two molecules can thus be distinguished by their proton nmr spectra because the integration factors of the pea"s are different. corresponding to a different distribution of 2 atoms in the molecule.

the more deshielded it will be and the greater the chemical shift.' C 0.iii4 chemical shift The chemical shift depends on the environment around the 2 atomF in particular it is related to the proximity of electronegative atoms.' '.1 /' /04.. The pea" at G 1 0. The following table summarises the important chemical shifts for 2 atoms in common environments close to a functional group$ environment 2 C C13 2C3 32 2 C1C 2 C13 32 Type of molecule carbonyl alcohol or ether alcohol al"ene aldehyde acid Chemical shift.* C &.' &.) *. suggests an 2 atom in an aldehyde group. but 2 atoms attached to 3 atoms in carboxylic acids tend to have high chemical shifts ../4 would suggest propanal$ .G1 ' 04./ for G 1 =. 2 atoms in al"anes tend to have low chemical shifts . The nearer a hydrogen atom is to an electronegative atom.) suggests 2 atoms on a C adEacent to a carbonyl group The pea" at G 1 /. All 2 atoms not within one carbon atom of a functional group will have a chemical shift between ' and 0 ppm.) C ). 0 for G 1 0. The pea" at G 1 =. Ior example.).= = /' /' /0 The chemical shift data provides useful information in deducing the environments responsible for a particular pea" and identifying functional groups$ Consider the proton nmr spectra of two un"nown compounds$ /.ppm 0.+ C ).. * for G 1 /./ suggests 2 atoms on a C not adEacent to a functional group 5ntegration factors .

+ and * for G 1 '.9 3H Chemical shift data is thus useful for identifying functional groups and for deducing the position of other 2 atoms on the molecule.=4 would suggest propan / ol$ H H C H H C H H C H 3. The pea" at G 1 *.provided they are not involved in hydrogen bonding4. the absorption of radiation by hydrogen atoms is affected by the presence of hydrogen atoms on adEacent carbon atoms .+.H H C H C O C H H H 9.0 for G 1 *.7 (1 H) 2.+ suggests 2 atoms on a C not adEacent to a functional group The pea" at G 1 '.n9/4 rule as described earlier. / for G 1 0.7 2H 1. 0 for G 1 /.3 1H ".= suggests 2 atoms on a C not adEacent to a functional group 5ntegration factors . This is very useful for positioning the hydrogen atoms in different environments relative to each other.*.* suggests 2 atoms on a C adEacent to a carbonyl group. . These hydrogen atoms on adEacent carbon atoms cause a splitting of the pea" according to the . iv4 coupling As was discussed earlier.1 (3H) 0.! 2H O H 2.+ suggests an 2 atom on a C adEacent to a C 3 bond The pea" at G 1 0. but as this is inconsistent with the structure it could also suggest an 2 atom bonded to 3 in an alcohol The pea" at G 1 /.5 (2 H) 1.

%g Consider the following proton nmr spectrum$ . however. This will account for a pea" with integration factor *. H C C H H C H O C H C H H C H C O or O C H 2ere n 1 0 so a triplet will be observed H H C H H C H H C H H C H O or 2ere n 1 * so a quartet will be observed Thus the splitting of the pea"s gives much useful information about the splitting patterns in the molecule.Consider a C2* group. will depend on the hydrogen atoms on the adEacent carbon atom$ H H C H H C H 2ere n 1 0 so a triplet will be observed H O C H H H C H H C H C H O or O C C 2ere n 1 / so a doublet will be observed O H H C H H H C H or 2ere n 1 ' so a singlet will be observed Consider a C20 group. The splitting of this pea". This will account for a pea" with integration factor 0.

" 3H n # 2 so it is a tri$let 2.The pea" at G 1 /.% 3H n # " so it is a sin&let 1. 5t is the CC2* bonded to the C20 . .1 2H n # 3 so it is a quartet 2ydrogen bonded atoms do not contribute to coupling$ %g consider the proton nmr spectrum of ethanol$ H H C H H C H O H 2. this suggests that it is caused by a C20 group attached as C2* C20 C13 or C2* C20 3 but if it were attached to 3 it would have a chemical shift of *./ is a quartet .0 is a triplet.7 1H' sin&let 1. this suggests that it is caused by a C2* group attached to 3 or CC13 but if it were attached to 3 it would have a chemical shift of *.* 2 atoms on adEacent carbons4. with integration factor *. with integration factor *. with integration factor 0. with integration factor *.* C &.' 2 atoms on adEacent carbons4.* C &.7 2H' quartet The pea" at G 1 /.2 3H' tri$let 3.' is a triplet .0 2 atoms on adEacent carbons4.' so it is probably caused by a C2* group attached to CC13 The pea" at G 1 0.& is a singlet . this suggests that it is caused by a C2* group adEacent to a C20 group The pea" at G 1 0.' so it is probably caused by C2* C20 C13 !o the molecule is butanone$ H H C H H C H O C H C H H 2.

5t does not couple with the 2 attached to the 3. because this 2 atom is involved in hydrogen bonding. 2owever they give less information about a molecule than proton nmr spectra. Jentane and hexane give three pea"s. 5t is the CC20 bonded to the CC2*..The pea" at G 1 *. with integration factor /. methoxymethane. as well as a quartet with integration factor 0. The pea" at G 1 0. %g ethane. Jropene gives three pea"s. particularly if the molecular formula is "nown. ben<ene H H C H O H C H H methoxymethane -ost organic molecules. even though it is on an adEacent carbon atom. then C2*C20 is almost certainly present !inglet pea"s with integration factor / strongly suggest that an 3 2 bond is present Using car&on-*+ nmr spectra in structure determination Carbon /* nmr spectra are also useful for wor"ing out the structure of organic molecules. i4 the number of pea"s %ach pea" corresponds to one set of identical carbon atoms. The number of pea"s therefore gives the number of types of carbon atom present. 5n some molecules. is a quartet. 5t does not couple with the two CC20 hydrogen atoms because it is involved in hydrogen bonding. . give two or more pea"s as at least some of the carbon atoms are not identical$ Jropane and butane give two pea"s. all the carbon atoms are identical.. however. These molecules give only one pea" in the spectrum. Kut / ene gives four pea"s. Two important general points in particular should be noted$ • • e! 5f a triplet with integration factor * and chemical shift ' 0 is present. Kut 0 ene gives two pea"s. cyclohexane. is a singlet. 5t is the 2 bonded to the 3.

two of them must be identical. ether.ii4 chemical shift The chemical shift depends on the environment around the carbon atomF in particular it is related to the proximity of electronegative atoms. but carbon atoms attached to 3 atoms with a double bond tend to have high chemical shifts . arene carboxylic acid. the more deshielded it will be and the greater the chemical shift.all four C atoms are different4 -ethylpropan / ol would give three pea"s . so there must be three different carbon atoms.G 1 ' &'4.ppm )' =' =' /)' /+' /=' /=' 00' %g consider the following carbon nmr spectrum of an alcohol with molecular formula C&2/'3$ The spectrum gives three pea"s. the higher the chemical shift The following table summarises the important chemical shifts for 2 atoms in common environments close to a functional group$ environment C3 C1C C13 2 C1C Type of molecule alcohol. ester Aldehyde. ester al"ene. Ior example. As there are four carbon atoms in the molecule. "etone Chemical shift.G 1 /+' 00'4. . 3f the possible isomers of C&2/'3$ Kutan / ol and butan 0 ol would give four pea"s . The nearer an electronegative atom. All carbon atoms not directly attached a functional group .three of the C atoms are identical4 The spectrum is therefore most li"ely to come from methylpropan / ol. The nearer a carbon atom is to an electronegative atom. carbon atoms in al"anes tend to have low chemical shifts .ie singly bonded to only carbon or hydrogen atoms4 will have a chemical shift between ' and &' ppm4.two of the C atoms are identical4 -ethylpropan 0 ol would give two pea"s .

no composition data available4. *. /. #se the composition data to wor" out the empirical formula. %liminate the isomers inconsistent with this distribution. %liminate the isomers which are inconsistent with the chemical shifts. >educe the functional groups present from the infra red spectrum and hence establish the li"ely number of oxygen atoms present. &. D. Compare the splitting of the pea"s in the nmr spectrum with the expected splitting patterns of the remaining possible isomers. >educe the relative molecular mass from the mass spectrum. . 5f necessary. 0.T. Add up the integration factors in the proton nmr spectra. compare the chemical shifts of the pea"s in the nmr spectrum with the expected values. and hence identify the functional group. #se the integration factors in the proton nmr spectrum to wor" out the number of hydrogen atoms in each environment. #se the number of pea"s in the proton nmr spectrum to deduce the number of hydrogen environments. #se the mass spectrum to deduce the relative molecular mass. %liminate the isomers inconsistent with this number. &.E ANA/#TICA/ TEC. #se the infra red spectrum to chec" for the presence of C13 and 3 2 bonds. There are a number of useful steps to deducing the structure$ 5f composition data is available$ /. and hence wor" out the molecular formula. A wor"ed example of combined analysis is given on the following page . ). -a"e a list of the possible isomers consistent with the molecular formula and functional group. then the most effective analytical strategy is to use them together.NI0UES TO-ET. #se the relative molecular mass and the information on hydrogen and oxygen atoms to deduce the molecular formula. The number of hydrogen atoms present is an integral multiple of this number. the molecular formula must be found by a trial and error method. %liminate the isomers which do not give this splitting pattern. 5f composition data is not available. 0. +. ..USIN.ER 5f all the different spectra are available. *.

which is consistent with C2*C3 and not C2*3 . +/. 02 quartet. .#se the following spectra to deduce the structure of A$ -ass spectrum$ Jroton nmr spectrum$ -olecular ion pea" 1 DD -ost intense fragments$ &*././) cm /.which has &4./+.* C &. C13 present Irom proton nmr spectrum. remaining mass 1 +0 and cannot ma"e this using D./.*. integration factor 0 5nfra red spectrum$ sharp absorption at /. &).0& 2 atoms 5f two 3 atoms present.which has the ratio +$/$/4. 0=.*2 triplet. The coupling . *2 singlet4 is consistent with both remaining possible structures. which is consistent with C2*C203 and not C2*C20C3 . methylethyl methanoate Irom proton nmr spectrum$ There are * hydrogen environments so it cannot be propyl methanoate . The integration factors are *$*$0 so cannot be methylethyl methanoate .'. so it is not a carboxylic acid.' C 0.'4 The 02 quartet has a chemical shift of &. propyl methanoate. no broad absorptions between /)'' and *)'' cm / ANS1ER2 Irom mass spectrum. Kut the *2 singlet has a chemical shift of 0. quartet.' three pea"s$ G 1 /.for which the chemical shift would be 0. !o is probably an ester.'. singlet. integration factor * G 1 &. Irom infra red spectrum. Jossible structures$ -ethyl propanoate. sum of integration factors 1 D !o D. rmm 1 DD Irom infra red spectrum. remaining mass 1 )+F can ma"e this from & carbons and 2 hydrogens !o li"ely molecular formula 1 C&2D30. triplet. integration factor * G 1 0.)4 . ethyl ethanoate. /+ or 0& hydrogen atoms present and at least one oxygen 5f one 3 atom present.for which the chemical shift would be *. no 3 2 is present.

< 1 0= 7C2*C33C20C2*89:  7C2*89 9 7C2*C33C208: accounts for the pea" at m. # %3 O CH3 C O CH2 CH3 sta(le car(ocations *ith m+. Iull explanation of spectra$ 5nfra red spectrum$ a(sor(s at 1715 cm)1 O CH3 C O CH2 CH3 Jroton nmr spectrum$ O CH3 C O 1. # 15 7C2*C33C20C2*89: is the molecular ion pea" 7C2*C33C20C2*89:  7C2*C389 9 73C20C2*8: accounts for the pea" at m. # 29 sta(le car(ocations *ith m+.3' 3H' tri$let CH2 CH3 %."' 3H' sin&let -ass spectrum$ sta(le ac-lium *ith m+.< 1 /) 7C2*C33C20C2*89:  7C2*89 9 7C33C20C2*8: accounts for the pea" at m.!o it cannot by methyl propanoate and therefore the structure is ethyl ethanoate.< 1 &* 7C2*C33C20C2*89:  7C2*C2089 9 7C2*C338: accounts for the pea" at m.1' 2H' quartet 2.< 1 /) .

5n gas liquid chromatography.or up the plate4 is called the mo&ile p%ase. and the distance travelled by that substance compared to the solvent can be used to identify the substance. >ifferent gases ta"e different amounts of time to flow through the column.# Chromatography is a technique by which different compounds in a mixture can be separated and then analysed. >ifferent substances move at different speeds. a substance that is strongly attracted to the stationary phase will move slowly through the column and ta"e a long time to pass through the column. The mixture is placed in a small area on the paper and allowed to flow up the paper with the solvent. There are two main types of chromatography$ t%in-layer c%romatograp%y 5n thin layer chromatography a liquid solvent is allowed to flow up a piece of chromatography paper or a TLC plate.or volatile liquid4 The mixture of substances moving through the column .C.ROMATO-RA". gas-li3uid c%romatograp%y 5n gas liquid chromatography a gaseous mixture is allowed to flow through a column lined with a solid. and this can be used to identify the gas . The substance lining the column . A substance which is not strongly attracted to the stationary phase will move more quic"ly through the column and ta"e less time to pass through the column. . The speed at which each substance moves through the column or up the plate depends on its relative solubility in the two phases.or the plate4 is "nown as the stationary p%ase. Holatile liquids can also be vaporised and then allowed to flow through the column.