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.

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, to deduce relative atomic masses and to deduce molecular formulae. -ass spectrometry can also be used to determine the structure of organic molecules. 5n some respects molecules behave in a similar way to atoms in a mass spectrometer, but there are important differences$ 6hen a molecule is ionised, one electron is removed. As molecules generally contain paired electrons only, the result is the formation of a species with an unpaired electron, or a free radical. %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

or C02+ 7C02+89: 9 e The resulting species is thus a positi$ely c%arged ion and also a free radical. 5t is "nown as the molecular ion ;or parent ion4. Two possible things can happen to a molecular ion when it is formed$ it can pass intact through the mass spectrometer and onto the detector, being detected as having an m.< ratio of which < 1 / and m 1 relative mass of molecular ion. it can brea" up into two smaller, more stable species, one of which is a positively charged ion and one is a free radical. This is "nown as fragmentation. This will result in the detection of species with m.< ratios which are less than that of the molecular ion.

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.< ratio corresponds to the molecular ion, and this m.< ratio corresponds to the relative molecular mass of the molecule. the pea"s with smaller m.< ratios result from fragmentation of the molecular ion. These pea"s can be used to deduce more information regarding the structure of the molecule, because different molecules fragment in different ways and some fragments are more stable than others. %g mass spectrum of ethanol$

The mass spectrum of ethanol contains several pea"s$ the largest 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 &+. the other pea"s with smaller m.< ratios result from fragmentation of the ethanol molecule. The most abundant fragment ions appear to have relative masses of &) and */, and there are less abundant fragment ions with masses of 0, and 0=

&!

fragmentation

>uring fragmentation, the free radical molecular ion is bro"en up. As the molecular ion contains an odd number of electrons, one of the species into which it fragments will contain an even number of electrons ;this will be a positive ion4 and the other will contain an odd number of electrons ;this will be a free radical4. %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 ;not detected in mass spectrometer4

This species loses the electron and is a positively charged ion ;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. The process of fragmentation can thus be represented by the following general equation$ R'( ?9 9 @: A9: is the molecular ion and is detected ;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. The most stable cations are carbocations ;eg C2*9, C2*C209 and C2*C2C2*94 and acylium ions ;eg 2C39, C2*C39, C2*C20C394. These are thus the fragments most li"ely to be detected, and will give the most intense pea"s in a mass spectrum.

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. %g butanone$ C2*C20C3C2* %xpected in the mass spectrum of butanone would be$ m.< 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 &*, followed by ,0 and 0=. The pea"s at /) and ), can also be accounted for. ;5t is rarely possible to account for all the pea"s in a mass spectrum4

d!

using mass spectra to determine structure

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

Thus the presence ;or absence4 of specific fragments enables the structure to be determined.

N)M)R S"ECTROSCO"# a! Introduction

!ome nuclei have magnetic properties. 5f these nuclei are subEected to a strong magnetic field, they can either align themselves in the same direction as the magnetic field ;a low energy state4 or in the opposite direction ;a high energy state4. 6hen these nuclei are then subEected to radio waves with a range of frequencies, 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. The absorption can be detected and converted into a spectrum. The frequency of the radiation absorbed by the nuclei varies depending on the type of nucleus and the arrangement of electrons around that nucleus, and can thus be used to provide important structural information about the molecule. This technique for structure determination is "nown as nuclear magnetic resonance ;nmr4 spectroscopy. There are a number of different types of nmr spectroscopy, depending on the type of nucleus being investigated. Two techniques are required at A level$ proton nmr spectroscopy investigates the absorption of radiation by nuclei of hydrogen atoms ;/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 ;/*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 number of different pea"s, therefore, 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. The relative intensity of the pea"s is "nown as the integration factor and is generally given as a simplest whole number ratio ;as it is not always easy to see from the spectrum4

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

A typical proton nmr spectrum loo"s li"e this$

Irom this spectrum, it is clear that there are four pea"s. The chemical shift can be read from the hori<ontal axis, and the integration factor and splitting can be deduced by loo"ing at the si<e and shape of the pea"s ;computer techniques are usually required to wor" out the integration factor4. The four pea"s in the above spectra could be described as follows$ Chemical shift.ppm '.= /.+ 0.* *., !plitting triplet sextet singlet triplet 5ntegration Iactor * 0 / 0

The chemical shift, splitting and integration factor can all be used to deduce important information about the structure of the molecule in the sample. Bote that the integration factor ;the area under pea"4 is difficult to read directly. Ior this reason, the integration factor is indicated above the pea". Alternatively, pre integrated nmr spectra are often used. 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". 3ne example, showing both the integration line and the integration factor is shown below$

The shifts at each pea" are in the ratio /$0$*, and this ratio is the integration factor. @ou will need to deduce the integration factor of each pea" using only the integration line.

c!

car&on-*+ nmr spectroscopy

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

Irom this spectrum, it is clear that there are eight pea"s. This means that there are eight different types of carbon atom in the molecule, each with a different chemical shift. c! "reparing samples for proton nmr analysis

Kefore a spectrum can be analysed, 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. The problem with most solvents is that they themselves contain hydrogen atoms which absorb radiation, interfering with the spectrum produced by the sample. 5t is therefore necessary to use a solvent which contains no hydrogen atoms. The usual choices are CCl& and C>Cl*. > is the symbol for deuteriumF this is an isotope of hydrogen containing one neutron in its nucleus. 5t has no magnetic properties and does not interfere with a proton nmr spectrum. ii4 Choosing a standard

5n addition to the solvent, a standard ;or reference4 molecule must be added to calibrate the spectrum. The chemical shift is then measured relative to this standard as described above. The standard normally used is tetramethylsilane ;T.-.!.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, singlet pea" which is very intense ;there are /0 2 atoms, all identical4 which ma"es the pea" easy to identify. The 2 atoms are highly shielded ;as the !i is an electropositive atom, releasing electron density onto the 2 atoms4 so the pea" is generally at a significantly lower frequency than that found in most organic molecules, meaning that it does not interfere with the other pea"s and can be easily distinguished from them. 5t is cheap and non toxic. 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.

d!

Using proton nmr spectra in structure determination

Jroton nmr spectra are very useful for wor"ing out the structure of organic molecules, particularly if the molecular formula is "nown. 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. The number of pea"s therefore gives the number of types of hydrogen atom present. 5n some molecules, all the hydrogen atoms are identical. These molecules give only one pea" in the spectrum. %g ethane, propanone, 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

5n some molecules, there are two types of hydrogen atom. These molecules will give two pea"s in a proton nmr spectrum. %g butane, pentan * one, ethanal, methanol
H

H H C H

H C H

H C H

H C H H

O
CH3

C H

C H

OH

-ost molecules, however, 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

Kutanal gives four pea"s$

H H
C

%thanol gives three pea"s$

H H

H
C

O
C

C H

C H

OH

%ach of the 2 atoms within the same circle are identical and contribute towards the same pea". -ethylpropanal gives three pea"s$
this H atom is unique
H
C C

H H
C

O
C

H H

this H atom is unique

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, corresponding to a different distribution of 2 atoms in the molecule. %g. -ethylpropanal and butanone ;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 C H

O C

H C 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. The two molecules can thus be distinguished by their proton nmr spectra because the integration factors of the pea"s are different.

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. The nearer a hydrogen atom is to an electronegative atom, the more deshielded it will be and the greater the chemical shift. Ior example, 2 atoms in al"anes tend to have low chemical shifts ;G1 ' 04, but 2 atoms attached to 3 atoms in carboxylic acids tend to have high chemical shifts ;1 /' /04. All 2 atoms not within one carbon atom of a functional group will have a chemical shift between ' and 0 ppm. 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.ppm 0.' C 0.) *.* C &.' '.) C ).' &.+ C ).= = /' /' /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$ /.

The pea" at G 1 =., suggests an 2 atom in an aldehyde group. The pea" at G 1 0.) suggests 2 atoms on a C adEacent to a carbonyl group The pea" at G 1 /./ suggests 2 atoms on a C not adEacent to a functional group 5ntegration factors ;/ for G 1 =.,, 0 for G 1 0.), * for G 1 /./4 would suggest propanal$

H H
C

H
C

O
C

9.7 (1 H)

2.5 (2 H) 1.1 (3H) 0.

The pea" at G 1 *.+ suggests an 2 atom on a C adEacent to a C 3 bond The pea" at G 1 0.* suggests 2 atoms on a C adEacent to a carbonyl group, 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 /.+ suggests 2 atoms on a C not adEacent to a functional group The pea" at G 1 '.= suggests 2 atoms on a C not adEacent to a functional group 5ntegration factors ;0 for G 1 *.+, / for G 1 0.*, 0 for G 1 /.+ and * for G 1 '.=4 would suggest propan / ol$
H H C H H C H H C H 3.7 2H 1.! 2H O H 2.3 1H

".9 3H

Chemical shift data is thus useful for identifying functional groups and for deducing the position of other 2 atoms on the molecule. iv4 coupling

As was discussed earlier, the absorption of radiation by hydrogen atoms is affected by the presence of hydrogen atoms on adEacent carbon atoms ;provided they are not involved in hydrogen bonding4. These hydrogen atoms on adEacent carbon atoms cause a splitting of the pea" according to the ;n9/4 rule as described earlier. This is very useful for positioning the hydrogen atoms in different environments relative to each other.

Consider a C2* group. This will account for a pea" with integration factor *. The splitting of this pea", however, 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

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. This will account for a pea" with integration factor 0.
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.

%g Consider the following proton nmr spectrum$

The pea" at G 1 /.' is a triplet ;0 2 atoms on adEacent carbons4, with integration factor *. this suggests that it is caused by a C2* group adEacent to a C20 group The pea" at G 1 0.& is a singlet ;' 2 atoms on adEacent carbons4, with integration factor *. 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 *.* C &.' so it is probably caused by a C2* group attached to CC13 The pea" at G 1 0./ is a quartet ;* 2 atoms on adEacent carbons4, with integration factor 0. 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 *.* C &.' 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.% 3H n # " so it is a sin&let

1." 3H n # 2 so it is a tri$let

2.1 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 2.7 1H' sin&let

1.2 3H' tri$let

3.7 2H' quartet

The pea" at G 1 /.0 is a triplet, with integration factor *. 5t is the CC2* bonded to the C20 .

The pea" at G 1 *., is a quartet. 5t is the CC20 bonded to the CC2*. 5t does not couple with the 2 attached to the 3, even though it is on an adEacent carbon atom, because this 2 atom is involved in hydrogen bonding. The pea" at G 1 0., is a singlet, with integration factor /. 5t is the 2 bonded to the 3. 5t does not couple with the two CC20 hydrogen atoms because it is involved in hydrogen bonding. Two important general points in particular should be noted$ e! 5f a triplet with integration factor * and chemical shift ' 0 is present, as well as a quartet with integration factor 0, 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, particularly if the molecular formula is "nown. 2owever they give less information about a molecule than proton nmr spectra. 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, all the carbon atoms are identical. These molecules give only one pea" in the spectrum. %g ethane, methoxymethane, cyclohexane, ben<ene
H H C H O H C H H

methoxymethane

-ost organic molecules, however, give two or more pea"s as at least some of the carbon atoms are not identical$ Jropane and butane give two pea"s. Jentane and hexane give three pea"s. Jropene gives three pea"s. Kut 0 ene gives two pea"s. Kut / ene gives four pea"s.

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. The nearer a carbon atom is to an electronegative atom, the more deshielded it will be and the greater the chemical shift. Ior example, carbon atoms in al"anes tend to have low chemical shifts ;G 1 ' &'4, but carbon atoms attached to 3 atoms with a double bond tend to have high chemical shifts ;G 1 /+' 00'4. All carbon atoms not directly attached a functional group ;ie singly bonded to only carbon or hydrogen atoms4 will have a chemical shift between ' and &' ppm4. The nearer an electronegative atom, 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, ether, ester al"ene, arene carboxylic acid, ester Aldehyde, "etone Chemical shift.ppm )' =' =' /)' /+' /=' /=' 00'

%g consider the following carbon nmr spectrum of an alcohol with molecular formula C&2/'3$

The spectrum gives three pea"s, so there must be three different carbon atoms. As there are four carbon atoms in the molecule, two of them must be identical. 3f the possible isomers of C&2/'3$ Kutan / ol and butan 0 ol would give four pea"s ;all four C atoms are different4 -ethylpropan / ol would give three pea"s ;two of the C atoms are identical4 -ethylpropan 0 ol would give two pea"s ;three of the C atoms are identical4 The spectrum is therefore most li"ely to come from methylpropan / ol.

USIN- T.E ANA/#TICA/ TEC.NI0UES TO-ET.ER 5f all the different spectra are available, then the most effective analytical strategy is to use them together. There are a number of useful steps to deducing the structure$ 5f composition data is available$ /. 0. *. &. ). +. ,. D. #se the composition data to wor" out the empirical formula. #se the mass spectrum to deduce the relative molecular mass, and hence wor" out the molecular formula. #se the infra red spectrum to chec" for the presence of C13 and 3 2 bonds, and hence identify the functional group. -a"e a list of the possible isomers consistent with the molecular formula and functional group. #se the number of pea"s in the proton nmr spectrum to deduce the number of hydrogen environments. %liminate the isomers inconsistent with this number. #se the integration factors in the proton nmr spectrum to wor" out the number of hydrogen atoms in each environment. %liminate the isomers inconsistent with this distribution. Compare the splitting of the pea"s in the nmr spectrum with the expected splitting patterns of the remaining possible isomers. %liminate the isomers which do not give this splitting pattern. 5f necessary, compare the chemical shifts of the pea"s in the nmr spectrum with the expected values. %liminate the isomers which are inconsistent with the chemical shifts.

5f composition data is not available, the molecular formula must be found by a trial and error method. /. 0. *. &. >educe the relative molecular mass from the mass spectrum. >educe the functional groups present from the infra red spectrum and hence establish the li"ely number of oxygen atoms present. Add up the integration factors in the proton nmr spectra. The number of hydrogen atoms present is an integral multiple of this number. #se the relative molecular mass and the information on hydrogen and oxygen atoms to deduce the molecular formula.

A wor"ed example of combined analysis is given on the following page ;no composition data available4.

#se the following spectra to deduce the structure of A$ -ass spectrum$ Jroton nmr spectrum$

-olecular ion pea" 1 DD -ost intense fragments$ &*, 0=, &), +/, ,'

three pea"s$ G 1 /.*, triplet, integration factor * G 1 0.', singlet, integration factor * G 1 &./, quartet, integration factor 0

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

!o it cannot by methyl propanoate and therefore the structure is ethyl ethanoate. Iull explanation of spectra$ 5nfra red spectrum$
a(sor(s at 1715 cm)1

CH3

C O

CH2

CH3

Jroton nmr spectrum$

O

CH3

C O

1.3' 3H' tri$let

CH2 CH3

%.1' 2H' quartet 2."' 3H' sin&let

-ass spectrum$
sta(le ac-lium *ith m+, # %3
O

CH3

C O

CH2

CH3

sta(le car(ocations *ith m+, # 29 sta(le car(ocations *ith m+, # 15

7C2*C33C20C2*89: is the molecular ion pea" 7C2*C33C20C2*89: 7C2*C389 9 73C20C2*8: accounts for the pea" at m.< 1 &* 7C2*C33C20C2*89: 7C2*C2089 9 7C2*C338: accounts for the pea" at m.< 1 0= 7C2*C33C20C2*89: 7C2*89 9 7C2*C33C208: accounts for the pea" at m.< 1 /) 7C2*C33C20C2*89: 7C2*89 9 7C33C20C2*8: accounts for the pea" at m.< 1 /)

C.ROMATO-RA".# Chromatography is a technique by which different compounds in a mixture can be separated and then analysed. 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. The mixture is placed in a small area on the paper and allowed to flow up the paper with the solvent. >ifferent substances move at different speeds, and the distance travelled by that substance compared to the solvent can be used to identify the substance. gas-li3uid c%romatograp%y 5n gas liquid chromatography a gaseous mixture is allowed to flow through a column lined with a solid. Holatile liquids can also be vaporised and then allowed to flow through the column. >ifferent gases ta"e different amounts of time to flow through the column, and this can be used to identify the gas ;or volatile liquid4 The mixture of substances moving through the column ;or up the plate4 is called the mo&ile p%ase. The substance lining the column ;or the plate4 is "nown as the stationary p%ase. The speed at which each substance moves through the column or up the plate depends on its relative solubility in the two phases. 5n gas liquid chromatography, 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. 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.