Option A Modern Analytical Techniques

Modern Analytical Chemistry

OPTION A
A1 Analytical Techniques (SL/HL)
Analytical techniques are an important and useful tool for the following reasons:
a) They allow the exact composition of substances/compounds/elements to be determined.
b) The formula of the compounds can be deried.
c) They allow a detailed structure to be deduced.
d) They are able to determine the purity of the substances inestigated.
The composition of substances can be determined by separation techniques such as chromatography.
!"aper# thin layer# column !$%/&%)# gas'liquid# high performance liquid !&%).
The concentration of substances can be deduced by process such as atomic absorption !AA)
spectroscopy !$%/&%)# () and isible spectroscopy !&%).
The formula of a compound can be determined from a ariety of techniques.
*. Chemical tests will determine the functional groups present.
+. mpirical formula can be wor,ed out by combustion with oxygen and then determining the mass
of -O+ and &+O gien.
The structure of a compound requires a com!ination of modern instrumental methods.
1" Mass Spectrometry"
+. #nfra $ed Spectroscopy" !../.)
0. %uclear Magnetic $esonance !1M/)
Option A Modern Analytical Techniques
A& 'rinciples of Spectroscopy (SL/HL)
lectromagnetic Spectrum
/adiation is related by the equation c2 3f. The greater the energy# the higher the frequency# the lower the
waelength.
%abel the main regions of the spectrum and the waelengths/frequencies.
T()* &ow is the electromagnetic spectrum used to transfer information4 5iscuss how using this energy has
affected our lies. 6hat are the limits to its usefulness# if any4
A!sorption and mission Spectra
7mission $pectroscopy inoles analysis of light gien out by atoms/molecules as they return to their
ground state.
Absorption $pectroscopy inoles energy being absorbed by the atoms/molecules to promote into excited
states.
The energy absorbed/emitted is characteristic to the atom/molecule inoled.
The most energetic absorptions inole electron transitions. These ta,e place in the 8'ray# 9'ray# () and
isible regions# depending on which electrons moe.
Option A Modern Analytical Techniques
Molecular ibrations !stretching and bending) cause less energetic absorptions. These occur in the ./
region.
Molecular rotations occur in the microwae region. The wea,est transitions inole nuclear spin. These
occur in the radio wae region !see nmr).
%abel the electromagnetic spectrum aboe with the types of transition that causes absorption.
A+ #nfra $ed Spectroscopy (SL/HL)
(sed to determine which !onds are present in the molecule.
.f an un,nown organic molecule is sub:ected to ../. energy# its bonds will a!sor! some of the radiation
causing them to bend# stretch and ibrate.
5ifferent bonds will absorb the radiation at different ,a-elengths of radiation allowing them to be
identified.
Absorptions are measured as ,a-enum!ers (1/,a-elength)
6ea,er bonds require less energy and so absorption occurs at a lower waenumber.
(perating 'rinciples
An infrared source produces radiation of the required frequency range.
A rotating mirror alternately passes the radiation through the sample and then through a reference.
A photomultiplier then conerts these photons of light into an electrical current.
The spectrum is generated by a comparison between the sample and reference beams. This is called a
dou!le !eam spectrometer.
5raw and label a simple diagram:
Option A Modern Analytical Techniques
Types of .i!ration
Only ibrations that inole a change in polarity will absorb infrared radiation.
Molecules that are perfectly non/polar !O+# &+ etc.) 6ill not therefore gie absorptions.
6ith non'polar molecules that contain polar bonds !-O+# --l;) the type of ibration is important.
Symmetrical stretching would not cause absorption since the dipoles would cancel. Asymmetrical
stretching would cause absorption# as would any type of !ending of the bonds.
7.g. -O+ symmetrical stretch asymmetrical stretch bending
7.g. $O+
7.g. &+O
7xtension: 5raw out some of the possible bending and stretching ibrations in <-&+'
1ote: There are lots of types of bending ibrations such as scissoring# roc,ing# twisting and wagging.
Option A Modern Analytical Techniques
Analysing #$ Spectra
Mainly used to identify functional groups.
*.
(H !ond in carboxylic acids 2 0+0='0>>= cm
'*
!waenumber)
+.
(H !ond in alcohols 2+>=='00== cm
'*

0.
C0( !ond 2 *?@='*A>= cm
'*
;.
C0C !ond 2 *?*='*?@= cm
'*
>.
1ingerprint region" 2 ;=='*;== cm
'*

This region is too complicated to analyse# but since each molecule will gie a characteristic pattern# it can be
used to positiely identify a compound by comparison with other ,nown spectra.
A2 Mass Spectrometry (SL/HL)
Brom Topic +
*.)aporisation
+..onisation
0.Acceleration
;.5eflection
>.5etection
.n addition to determining the molar mass of the substance# mass spectrometry will gie some information of the
structure of the molecule.
Option A Modern Analytical Techniques
The Molecular #on
The ionised molecule is detected as the molecular ion (M
3
) with the largest mass and this determines the
molar mass of the molecule.
1ragments
.onisation of the molecule will often lead to the molecular ion splitting into fragments. These fragments
gie clues its structure.
7.g. A difference in mass between + fragments of CC
14 suggests the loss of a <CH+ group.
15/16 the loss of a <(H/H group.
&7 the loss of CH+CH& or <CH0(
+1 the loss of <(CH+
24 the loss of <C((H
A4
1
H %M$ Spectroscopy (Lo, resolution) (SL/HL)
This gies information about the Hydrogen atoms in the molecule.
The nuclei of hydrogen atoms can spin in opposite directions. 6hen a strong magnetic field is
applied they may s,ap the direction in ,hich they are spinning"
This causes them to a!sor! a small amount of energy in the radio region of the spectrum.
5ifferent groups of hydrogen atoms absorb slightly different amounts of energy depending on the
chemical en-ironment in which they are# causing them to appear at different positions on the
spectrum.
Option A Modern Analytical Techniques
$ome of the most common positions are:
& atoms -hemical shift
'-&0 2 =.D
'-&+' 2 *.0
'-&' 2 +.=
-&0'-2O 2 +.*
'O& 2 ;.>
-?&? 2 A.0
&-2O 2 D.A
&O'-2O 2 **.A
Eenerally# the more electronegatie the chemical enironment# the greater the chemical shift.
The num!er of hydrogen atoms can be determined by the area under each pea, on the spectrum.
This is useful information as it shows how many hydrogen atoms are experiencing the same chemical
enironment.
8ses of %M$ Spectroscopy in 9ody Scanners
1M/ has some ery important medical applications. One reason is that the low energy radio waes used
are harmless and hae no ,nown side effects.
M/. !magnetic resonance imaging) is one application that can monitor and ealuate arious medical
conditions.
.t inoles the whole body of the patient being placed inside the magnet of a large 1M/ machine.
The protons !&Fs) in water# lipids# carbohydrates etc in the body gie different signals that allow an
accurate 05 image of the body to be obtained.
Option A Modern Analytical Techniques
A7 %M$ Spectroscopy (High $esolution) (HL (%L:)
Tetramethylsilane (TMS)
This is used as a reference sample for the following reasons.
.t is non toxic and unreactie.
.t produces a ery clear single pea, since all *+ &Fs are equialent.
.t is ery unpolar and so occurs upfield# well away from any other possible pea,s.
.t has a ery low bp and so can therefore be easily remoed from the sample.
Splitting 'atterns
The absorption pea,s gien in
*
& spectra are influenced by ad:acent hydrogens.
These can be analysed when using high resolution 1M/ to show a pea, splitting patterns.
$inglet: .f there are no ad:acent &Fs.
5oublet: .f there is one & atom on an ad:acent carbon.
Triplet: .f there are two & atoms on ad:acent carbons.
Guartet: .f there are 0 &Fs on ad:acent &Fs.
This is called spin'spin coupling. 7xact details of how these patterns arise is not required.

Option A Modern Analytical Techniques
A; Atomic A!sorption Spectroscopy (AA) (SL/HL)
8ses of AA Spectroscopy
AA measures the amount of energy that is absorbed by electrons as they are promoted from lower to
higher energy leels.
.t is the reerse of emission spectra that measure the energy released when electrons drop down into
lower energy leels and gie rise to characteristic colours of flames in the isible region !potassium 2 lilac)
A light source of a particular frequency/waelength is selected to complement the colour of the sample.
(sing the amount of energy absorbed# the concentration of the sample can be accurately determined.
.t can therefore be used to determine the concentration of metal ions in samples such as water# blood#
food# soils etc.
'rinciples of AA Spectroscopy
AA machines wor, on the same double beam principle outlines for ./ spectra.
5raw a simplified labelled diagram:
The sample is turned into a fine mist and then burnt in a fuel/air mixture. This happens in the atomiHer.
A monochromatic light source is then passed through the resulting flame. The light source needs to contain
the metal under inestigation so that the correct frequency of light will be used.
The amount of light absorbed by the atoms in the sample is detected and conerted into an electrical
signal.
Iy changing the light source# the concentration of different metals in the same sample can be determined.
Option A Modern Analytical Techniques
1inding Concentrations
The amount of light absorbed by a sample !Absorbance) is directly proportional to the concentration of
metal ions in the sample.
This is called the Ieer %ambert %aw.
A 2 J-l
A 2 Absorbance J 2 molar absorbtiity coefficient !constant)
- 2 concentration l 2 path length of sample cell.
7.g. A metal solution in a cell of length * cm. The absorbance of the solution at a particular waelength is *.D+.
The molar absorptiity is *D;== for that waelength. !from a data boo,)
Cali!ration Cur-es
(sing this relationship# if a calibration cure is determined for a particular metal using arious ,nown
concentrations# the concentration of an un,nown solution of that metal can be easily determined.
Absorbance
-oncentration
1ote: The calibration cure and Ieer %ambert %aw becomes less linear at higher concentrations of solution.
Option A Modern Analytical Techniques
A5 Chromatography
8ses of Chromatography
-hromatography can be used to separate mixtures containing ery small amounts of substances.
.t can be used to identify how pure a substance is.
Iy comparisons to ,nown samples it can be used to identify components and also determine the
concentration/amount present.
'rinciples of Chromatography
All types of chromatography inole separation inoling two phases. The stationary phase stays fixed.
The mo!ile phase moes.
$eparation occurs due to the difference in tendency to absorb onto the stationary phase compared to its
solubility in the mobile phase.
Adsorption inoles a solid stationary phase and a liquid mo!ile phase. The distance a solute moes
depends on the relationship between how quic,ly it absorbs onto the solid phase compared to its solubility
in the liquid phase.
The faster it absorbs# the less distance it moes.
'artition inoles a liquid stationary phase and a liquid/gas mo!ile phase" .f the mobile phase is a
liquid# the distance moed by the solute depends upon its difference in solubility in the two phases. .f the
mobile phase is a gas it depends on the olatility of the solute.
The more soluble/olatile# the greater distance moed.
Option A Modern Analytical Techniques
<ifferent Types of Chromatography
a) 'aper Chromatography"
"aper consists mainly of cellulose that consists of a large number of O& groups.
6ater can &'bond to these polar groups in the paper so that KdryF paper still consists of about *=L water.
.t is this water that is KtrappedF in the paper that acts as the stationary phase.
The mo!ile phase is a solent !eluent). 7.g. water itself# ethanol etc.
The mixture is spotted on the paper about *cm from the base. This is mar,ed with a pencil line.
The paper is placed in a small olume of water below the pencil line.
A lid is put on the container to saturate the atmosphere.
The solent rises up the paper and the arious components separate between the two phases according to
their relatie solubility.
The final distance that the solent rises is also measured !solent front).
After drying# if required the components can be stained by a dye !deeloped) to ma,e them isible# and
then the distance moed can be measured.
This is used to calculate the retention factor ($f) and these can be compared to ,nown alues to deduce
the identity of the arious components.
/etention factor !/f) 2 5istance moed by solute !cm)
5istance moed by solent !cm)
!) Column Chromatography (LC)
This is used to separate components in a mixture rather than identify them.
This consists of a long column pac,ed with a solid stationary phase !7.g. silica gel)
The column is saturated with solent.
The mixture is poured in the top and separates the arious components according to their solubility in the
solent.
.f necessary# another solent can be then introduced to dissole and separate other components that are
still held in the column.
Option A Modern Analytical Techniques
c) Thin Layer Chromatography (TLC)
This wor,s by the same principle as paper chromatography# except instead of the paper# a thin layer of
solid !silica) is used.
.n the same way# water acts as the stationary phase and the mobile phase is another solent.
T%- allows the component to be scraped off at the end and re'dissoled. This method is used for some
pregnancy sets.
d) =as/Liquid Chromatography (=LC) HL (%L:
This technique is used to analyse a mixture of -olatile liquids.
The liquids need to be stable at temperatures close to the boiling point.
The stationary phase consists of a liquid suspended on a solid in a long thin tube.
The mobile phase is an inert gas such as helium or nitrogen.
The sample is in:ected and then aporised by heat.
The arious components in the aporiHed mixture are then carried through the column by the inert gas.
5epending on the solubility in the stationary solent# the components hae different retention times and
therefore reach the detector at different times.
This method also allows the measurement of the relatie concentrations using the area under the pea,s.
This allows for use in detecting the alcohol leel in blood during drin, driing tests.
e) High 'erformance Liquid Chromatography (H'LC) HL (%L:
This method wor,s in a ery similar way to E%-. .nstead of allowing graity to moe the components
through the column# they are forced through much faster under pressure.
This means that the column used doesnFt hae to be as long as the process is ery efficient.
As well as separation# &"%- can also be used for identification of the components present.
&"%- is used for non -olatile su!stances# and also for -olatile su!stances that tend to decompose
near to their !oiling points. .t can also be used to separate and identify optically acti-e compounds if
the column is prepared using another optically actie stationery phase.
Other uses include pollutants# food# alcoholic drin,s# insecticides/herbicides# biochemical research and
pharmaceuticals.
Option A Modern Analytical Techniques
A6 .isi!le and 8ltra-iolet Spectroscopy (HL (%L:)
Transition Metal Comple> Colours
Transition metals hae incomplete d shells. This is the main reason why they form coloured compounds.
6hat colour are -u
M
# $c
0M
and Nn
+M
4
The different colours obsered by arious transition metal compounds depends on ; factors.
*. The type of transition metal.
6hat are the electron configurations of Mn
+M
and Be
0M
4 6hat are the colours4
+. The oxidation state of the transition metal.
6hat is the electron configuration of Be
+M
4 &ow does the colour compare to Be
0M
4
0. The type of ligand.
6hat colours is O-u!&+O)?P
+M
compared to O-u!1&0);P
+M
compared to O-u!-l);P
+'
4
6hat colour is O-o!&+O)?P
+M
compared to O-o!1&0)?P
+M
4
;. The shape of the complex.
6hat shape is OBe!&+O)?P
+M
4 6hat shape are O-u!-l);P
+'
and OAg!1&0)+P
M
4
Splitting of d (r!itals in Transition Metal Comple>es
There are > d orbitals of equal energy but different shapes# aligned along different axis. $,etch and label
below.
5uring complex formation# the non'bonding electrons on the ligand are donated into empty d'orbitals.
.n an octahedral complex# the ? ligands approach the metal ion along the x# y and H axis.
6hich + of the d orbitals are arranged on these axix4
The extra repulsion between the non bonding electrons in the ligands and these electron orbitals causes
two of the d orbitals to split to a higher energy. 5raw out the d orbital split for an aqueous Be+M
%ight can be absorbed by these complexes causing electron transition from the lower to the higher energy
d orbital energies.
Option A Modern Analytical Techniques
%abel the amount of splitting as Q7. This amount of energy can be affected by the type of ligand# the
oxidation state of the metal# the type of metal ion and the shape of the complex.
1&0 liagnds cause more splitting than &+O# -l
'
cause een less.
The colour seen is the complementary colour to the one absorbed. 7.g. O-u!&+O)?P
+M
absorbs

red/orange
light and so appears light blue. 6hen some of the ligands are replaced by 1&0 to gie O-u!1&0); !&+O)+P
+M
the

splitting increases and the complex absorbs energy in the yellow region. This causes the colour to
appear iolet/blue.
8./.is Spectroscopy in (rganic Molecules
Organic molecules containing alternate double bonds are able to absorb energy in the isible and ()
range. These include long chain al,enes and arenes.
7xamples include retinal !itamin A) chlorophyll and I carotene. 5raw out the structure of one of these.
This type of structure is said to contain con?ugation.
The part of the molecule where con:ugation occurs is called the chromophore. %abel the chromophore on
the molecule aboe.
%ight energy can be absorbed causing the pi electrons to become delocaliHed and moe to different
orbitals. The amount of energy absorbed depends on the amount of con:ugation in the molecule.
More con:ugation# more delocaliHation# the less the amount of energy required to excite the
electrons. This means that absorption is more li,ely to occur in the isible region.
7.g. Al,enes hae only * double bond# no con:ugation or delocaliHation. The energy required to excite the
electrons into unfilled !molecular) orbitals is greater leading to absorption in the u part of the spectrum.
This is why al,enes appear colourless. !As do aldehydes and ,etones).
Option A Modern Analytical Techniques
6hat colour is chlorophyll or I carotene4 5o they absorb u or isible light4 6hat about their structure
allows this to happen4 7xtension: 6hat actual !complementary) colour must they absorb4
5raw out the dissociation of the wea, acid phenolphthalein.
7xplain why in acid it is colourless# but in al,ali it becomes a colourful pin,.
One of the main ingredients in suntan lotions is ;'aminobenHoic acid. 5raw the structure below.
7xplain why this molecule is able to absorb harmful high energy u light.
8sing the 9eer Lam!ert La, to 1orm Cali!ration Cur-es
The amount of light absorbed by a sample !Absorbance) is directly proportional to the concentration of
metal ions in the sample.
This is called the Ieer %ambert %aw.
A 2 J-l
Option A Modern Analytical Techniques
.f seeral samples of transition of arying concentration are prepared# the absorbance can be measured
using a spectrometer/colorimeter.
Measurements are made using !3max) by selecting the waelength of light that is the complementary colour
using an appropriate filter.
"lotting absorbance against concentration will gie a straight line graph.
This allows the concentration of an un,nown sample to be measured by recording the absorbance and
comparing to the graph.
7.g. .f a number of solutions of the compound are prepared of accurately ,nown concentration. Those
concentrations should brac,et the concentration to be determined.
Bor each solution# measure the absorbance at the waelength of strongest absorption !3max). Then plot a
graph of absorbance against concentration. This is a calibration cure.
According to the Ieer'%ambert %aw# absorbance is proportional to concentration# producing a straight line.
That is true as long as the solutions are dilute# but the %aw brea,s down for solutions of higher
concentration.
1o attempt is made to force the line bac, through the origin. .f the Ieer'%ambert %aw wor,ed perfectly# it
would pass through the origin# but this canRt be guaranteed for all concentrations.
Measure the absorbance of the solution with the un,nown concentration at the same waelength. .f# for
example# it had an absorbance of =.?==# record the corresponding concentration from the graph as shown.