Unit-VI

LIQUID CRYSTALS AND THEIR APPLICATIONS Introduction: The study of liquid crystals began with an observation made by Austrian botanist, Freindrich Reinitzer in 1888. e observed that solid cholesteryl benzoate on heating becomes a turbid liquid at 1!" #$ which on further heating turns into a clear, trans%arent liquid at 1&8#$. The above changes are reversed on cooling. The changes are generally re%resented as
$holesteryl benzoate
'olid

1!"#$

$holeteryl benzoate
meso%hase

1&8#$

$holesteryl benzoate

$holesteryl benzoate is said to e(it a liquid crystal between 1!" #$ and 1&8#$. The first tem%erature at which solid changes into turbid liquid is )nown as transition point and second tem%erature at which turbid liquid changes in to clear liquid is )nown as !"tin# point$ Thus, liquid crystal is a distinct %hase observed between crystalline solid state and isotro%ic liquid state. D!%inition: Li&uid cr'sta"s may be described as a distinct state of matter in which the degrees of molecular ordering lie intermediate between the ordered crystalline state and the com%letely disordered isotro%ic liquid state. The liquid crystal state is also referred to as !sop(as!. The com%ounds which e(hibit meso%hase are also called !so#!ns. *iquid crystals e(hibit o%tical anisotro%y, i.e., they %ossess different o%tical %ro%erties when light is incident in different directions. *iquids, however, e(hibit o%tical isotro%y i.e., they e(hibit same o%tical %ro%erty irres%ective of the direction of incident light. Positiona" and ori!ntationa" ord!r: +ost liquid crystals are com%osed of organic molecules. ,n solid state, the molecules are highly ordered. -ach molecule occu%ies a definite %osition in a more or less rigid arrangement and is immobile. ,n solid state not only do the molecules occu%y s%ecific %ositions but also tend to orient in a %referred direction which is already e(isting. ,n liquid state, however, the molecules neither occu%y s%ecific %ositions nor remain oriented in a %articular manner. The molecules are somewhat free to move at random and collide with one another abru%tly changing their %ositions. ,ntermediate between the solid and the liquid crystal %hase, wherein the molecules free to move but are oriented in a %articular manner.

Fig.1 Re%resentation of solid, liquid crystal and liquid states .molecules are re%resented as thin lines/

Thus solid %hases %ossess %ositional order and orientational order. *iquid %hases %ossess neither %ositional nor orientational order while in liquid crystal %hase some orientational order is retained through there is a loss of %ositional order as shown in Fig.1 Dir!ctor: ,n a liquid crystal, the molecules %ossess orientational %rder i.e., the molecules tend to remain oriented in a %articular direction. The direction of %referred orientation in a liquid crystal is called dir!ctor and may be imagined to be directed towards the to% or bottom of the %age. 'ince the molecules are in constant motion, in liquid crystal %hase they s%end more time %ointing along the director than along any other direction. The e(tent of orientational order can be described by ta)ing the average. A sna%shot of the liquid crystal at any instant of time will give the angle made by each molecule with the director at any instant of time. ,f we consider a re%resentative grou% of molecules and measure the angles using the sna%shot, the average angle gives the measure of orientational order. An average of ## indicates %erfect orientation and can be e(%ected in solids. An average of greater than !"# indicates no orientational order a found in liquids. owever, in liquid crystals a smaller average angle with the director is observed which indicates some orientational order .Fig.0/.

Fig.0 A sna%shot showing the orientation of the molecules in the liquid crystal %hase as com%ared to its solid %hase. ,n the liquid crystal %hase, the molecules orient in a %referred direction along the director with an average angle of #. $hange in the %ositional order could be seen.

C"assi%ication o% "i&uid cr'sta"s: *iquid crystals are classified into two main categories, namely, 1. Thermotro%ic liquid crystals 0. *yotro%ic liquid crystals. )$ T(!r otropic "i&uid cr'sta"s: The class of com%ounds that e(hibit liquid crystalline behaviour on variation of tem%erature alone are referred to as thermotro%ic liquid crystals. The tem%erature range at which some liquid crystal are stable are given below1
0

'olid $holesteryl 2enzoate %3Azo(y%henetole %3Azo(yanisole 1!" 14&# 115#

#

*iquid crystal 1&8 15&# 14"#

#

*iquid

*$ L'otropic "i&uid cr'sta"s1 'ome com%ounds transform to a liquid crystal %hase when mi(ed with a solvent. They have a lyo%hilc and a lyobhobic end that is they are am%hi%hilic com%ounds. They are usually obtained by mi(ing the com%ound in a solvent and increasing the concentration of com%ound till liquid crystal %hase is observed. 'uch liquid crystals are called lyotro%ic liquid crystals. The formation of lyotro%ic meso%hases is de%endent on the concentration of either the com%onent or the solvent. 6ariation of tem%erature also affects the formation of these mesogens. -(am%les1 .i/ soa% .soa%3water mi(ture/ molecules .ii/ 7hos%holi%ids .biologically im%ortant molecules where each cell membrane owes its structure to the liquid crystalline nature of the %hos%holoi%id3water mi(ture/. *yotro%ic mesogens are ty%ically obtained from am%hilic com%ounds com%rising of both lyo%hilic .solvent attracting/ and lyobhobic .solvent re%elling/ %arts in the same molecule. ,n the %resence of solvent the lyo%hobic ends come together while the lyo%hilic ends directed towards water forming micelles. The formation of micelles ta)es %lace only beyond a %articular concentration of the solution called critical micelle concentration .$+$/. 8hen the concentration of the solution is increased .beyond cmc/ the micelles increase in size and eventually coalesce to form liquid crystalline %hase. +o"!cu"ar ord!rin# in "i&uid cr'sta"s ,T'p!s o% !sop(as!s-: ,)- N! atic p(as!: N! atic .9ree) nematos : thread li)e/ liquid crystals are formed by com%ounds that are o%tically inactive. The molecules have elongated sha%e and are a%%ro(imately %arallel to one another .Fig.4/. ;ematic %hase is characterized by the total loss of %ositional order and a near normal flow behaviour similar to its liquid %hase.

Fig.4 ;ematic liquid crystal

-(am%les1 .i/ %3azo(yanisole .115314"#/

<
H3CO N N OCH3

.ii/ %3azo(y%henetole .14&315&#$/

<
H3CH2CO N N OCH2CH3

.iii/ Anisaldine .15"318##$/

H3CO

$ :;3;:$

OCH3

.iv/ %3+etho(ycinnamic acid .1&#3185#$/

H3CO

$ :$ 3$<<

,*- C(ira" ,T.ist!d- N! atic P(as! ,/i#$0-: $hiral nematic liquid crystals, also referred to as cholesteric liquid crystals or twisted nematic liquid crystals .T;*$/, re formed from o%tically active com%ounds having chiral centres. =nli)e in a nematic %hase where all the molecules a%%ro(imately %arallel to one another, in chiral nematic %hase, the molecules arrange themselves in such a way that they form a helical structure. ,n this meso%hase, the director is therefore not fi(ed in s%ace as in s%ace as in a nematic %hase, but rotates throught the sam%le forming a helical %attern as it changes its direction >ust li)e the motion of a nut on a screw. The distance traveled by the director as it com%letes one full turn is called the %itch of the liquid crystal. ,n other words, the %itch length is the distance traveled

by the director when it gets turned by 45##$. The twisted %attern re%eats itself throught the liquid crystal %hase. The most stri)ing feature of choleteric meso%hase is its strong o%tical activity and selective light reflection, which are attributed to the twisted structure. The twist %resent in chiral nematic liquid crystal im%arts s%ectacular o%tical %ro%erties which are made used of as thermochromic materials. The %itch is also tem%erature de%endent and hence cholesterics are used in thermogra%hy. -(am%les1 .1/ $holesteryl benzoate .0/ $holesteryl myristate and .4/ $holesteryl formate etc.

.a/

.b/

Fig.!.a/ ,llustration of the twisted structure in a chiral nematic %hase of a liquid crystal as shown by the change in the direction of the director. Arrows show the orientation of the molecules. 7itch is shown as the distance traveled for the director to come bac) to its original direction. .b/ A nut moves a certain distance when it ma)es a full turn .one %itch/ and comes bac) to its original direction is as shown by the arrows.

,1- S !ctic !sop(as!: 'ubstances that form smectic %hases are soa%3li)e .in 9ree), smectos means soa%/. ,n fact, the soft substance that is left at the bottom of a soa% dish is a )ind of smectic liquid crystal %hase. ,n smectic meso%hase, there is a small amount of orientational order and also a small amount of %ositional order. The molecules tend to %oint along the director and arrange themselves in layers. A sna%shot would reveal that more number of molecules %osition in regularly s%aced %lanes and a few molecules lie between the %lanes .Fig."/. That is, any one molecule would s%end more time in these %lanes than between the %lanes. 2ased on the orientation of the director there are many ty%es of smectic %hases. ,f the director is %er%endicular to the %lanes it is called smectic A .Fig. "a/ and smectic $ if the director ma)es an angle other than ?# # .Fig."b/. ,n smectic 2 %hase, the director is %er%endicular to the %lane with the molecules arranging themselves into a networ) of he(agons within the layer.

"

.a/

.b/

Fig." 'chematic re%resentation of smectic meso%hase where molecules lie on regularly s%aced %lanes .in the form of layers/. .a/ 'mectic A where molecules is %er%endicular to the layer %lanes. .b/ 'mectic $ where the molecules are tilted with res%ect to the layer %lanes.

-(am%les1 !3n32utylo(ybenzylideneamino %ro%io%henone .smecti A/

H 9C 4 O

$ :;

COCH2CH3

Tere%hthalylidene3bis3!3n3butylaniline .smectic 2/
H9C4

;: $

$ :;

C4H9

!,!13di3n3 e%tylo(yazo(ybenzene .'mectic $/

<
H15C7O N N OC7H15

Discotic or Co"u nar Li&uid cr'sta""in! P(as!: *iquid crystals formed by molecules which have dis)3li)e or %late3li)e structure are referred to as discotic or columnar liquid crystals. The sim%lest discotic %hase is also called discotic nematic %hase because there is orientational order but no %ositional order .Fig.5a/. There is random motion of the molecules, but on an average, the a(is %er%endicular to the %lane of each molecule tends to orient along the director. ,n the discotic or columnar %hase, in addition to the orientational order %resent in the nematic discotic %hase, most of the molecules tend to %osition themselves in columns .Fig.5b/. The columns are arranged in a he(agonal lattice

resembling a set of coins stac)ed as shown below .note1 the coins in a stac) have a great deal of %ositional order i.e., the coins are equidistant whereas the molecules in a columnar %hase are stac)ed in random fashion/.

.a/

.b/

Fig.5 'chematic re%resentation of disc li)e molecules arranged in .a/ @iscotic nematic .b/ discotic columnar liquid crystal %hases

-(am%le1 2enzene3he(a3n3al)anoate
R R C O O C R O O C R O O O C R O O C O O C O R

Li&uid cr'sta""in! 2!(a3iour in (o o"o#ous s!ri!s: A series of com%ounds of the same ty%e in which all the members have the same functional grou% and molecular formulae of ad>acent members differ by $ 0 is called a homologous series. The thermal stability of a liquid crystal com%ound may be altered by altering the molecular structure e.g., by increasing its chain length as in homologues series. PAA ,p-a4o5'aniso"!- s!ri!s: The liquid crystal %hase of %3azo(yanisole .7AA/ is stable between 118#$ and 14"#$. 7AA has more than 10 homologues which are formed when A$ 0 grou%s are added to its side chain as shown below.
;o. of $3atoms in side chain
N OCH3

<
H3CO N

&

<
H 5 C 2O N N OC2H5

<
H 7 C 3O N N OC3H7

$ $ $
<
H13C6O N N OC6H13

12

A %lot of transition tem%eratures against number of carbon atoms for 7AA is as shown in Fig. &.a/

.a/

.b/

Fig.& 9ra%hical re%resentation of different %hases and transition tem%eratures of the homologous series of .a/ %3azo(yanisole .7AA/ and .b/ %3metho(ybenzylidine3%3n3butylaniline .+22A/

,t can be seen from Fig.&.a/ that, in general, the transition tem%erature of the liquid crystal, decreases with the increase in the number of carbon atoms in the side chain. The molecules with even number of carbon atoms generally have higher transition tem%erature than those having odd number of carbon atoms. 8hen the al)yl grou% .side chain/ contains 1 to 5 carbon atoms, liquid crystals show a nematic %hase and when the number of carbon atoms is greater than 5, smectic %hase is e(hibited. omologues containing & and 8 carbon atoms, however, show a transition from solid to smectic to nematic before melting to a liquid. +olecules with longer al)yl chains e(hibit smectic %hase. ,n 7AA series, the al)yl grou%s are lin)ed to benzene ring through an o(ygen atom. ,n addition, the transition tem%erature of the 7AA series ma)e them unsuitable for dis%lay a%%lications.
8

p-+!t(o5'2!n4'"id!n!-p-n-2ut'"ani"in! ,+66A- s!ri!s: The structure of which is given below

H3CO

$ :;

C4H 9

,t may be noted that there is direct lin)ing of al)yl chain to the benzene ring on one side .$! ?/ where as the other al)yl .$ 4/ is lin)ed through o(ygen to the benzene ring. The molecules with odd number of carbon atoms generally have higher transition tem%erature than those having even number of carbon atoms. The transition tem%erature .013&##$/ and various %hases of first five homologues of the +22A obtained by changing the length of the chain that does not contain o(ygen .i.e., $! ?/ is shown in Fig.&.b/. The members of +22A series do not e(hibit smectic %hase. All the members show transition from solid to nematic to isotro%ic liquid state. The transition tem%eratures of the com%ounds can thus be altered by changing the length of the fle(ible side chain at terminal %osition. 2i%henyl and ter%henyl systems carrying highly %olarizable grou%s such as nitro and cyano show lower transition tem%eratures. 'uch molecules with low transition tem%eratures have e(tensive a%%lications in liquid crystal dis%lay. E"!ctro-optic !%%!ct o% "i&uid cr'sta"s: ;ematic liquid crystals have rod li)e molecular structure and align themselves s%ontaneously along the director. ;ematic materials have two dielectric constants3 one in the direction %arallel to the director and the other %er%endicular to the director. @ielectric anisotro%y .BC/ is defined as the difference between the dielectric constants %arallel and %er%endicular to the director. 'imilarly, the optica" anisotrop' .Bn/ is defined as the refractive inde( %arallel to the director minus the refractive inde( %er%endicular to the director. These two %ro%erties are im%ortant for the electro3o%tic effects in liquid crystals. E%%!ct o% !"!ctric %i!"d: The director in a liquid crystal is free to %oint in any direction. 2ut when a film of liquid crystal is %laced between two %lates of certain materials, director is forced to %oint along a %articular direction when an electric field is a%%lied. For e(am%le, when a film of liquid is %laced between two s%ecially treated glass sheets .such as rubbing with a velvet cloth, or a%%lying a thin coat of a %olyamide followed by unidirectional rubbing with a roller/, the molecules close to the glass surfaces are forced to orient themselves %arallel to the surfaces of the glass sheets.

Fig.8 *iquid crystal film )e%t between two treated glass %lates .a/ in the field off state .below the threshold value/ all molecules and the director orient %arallel to the surface .b/ in the field on state .above the threshold value/ the molecules near the surface orient %arallel to the surface whereas in others it is deformed

,n the absence of an electric field, .below a threshold value/ the molecules at other layers are also aligned %arallel to the surfaces giving a homogeneous arrangement. 2ut when an electric field is a%%lied %er%endicular to the glass surface, molecules near the surface are aligned %arallel to the surface .%er%endicular to the a%%lied field/. The molecules near the centre of the liquid crystal layer .away from the surface/ are free to orient themselves along the a%%lied field. The crystal undergoes deformity .Fig. 8/. The deformity begins at a threshold value of the a%%lied field and increases with increase in the strength of the field. This transition .deformity/ is im%ortant in the o%eration of liquid crystal dis%lays .*$@/ because the transition brings about a significant change in the o%tical characteristics of the liquid crystal. E%%!ct o% "i#(t: 8hen light is incident on two crossed %olarizers, no light emerges because the light emerging from the first %olarizer id com%letely absorbed by the second %olarizer and hence a%%ears dar). 8hen a film of a liquid crystal is %laced between two %olarizers, only a %art of the light from first %olarizer is absorbed by the second %olarizer some light emerges giving bright a%%earance. A cell is assembled such that the direction of alignment at the to% surface is %er%endicular to that at the lower surface of the cell. Then it filled with a twisted nematic liquid crystal .T;*$/ having a %ositive dielectric anisotro%y .dielectric constant %arallel to the director is higher/. Twisted structure acts li)e a wave3guide and gradually rotates the %lane of %olarization of light by ?# #. ence a linearly %olarized light incident on the cell emerges linearly %olarized but in the an orthogonal direction resulting in a bright a%%earance .Fig. ?/.

1#

Fig.? 2right and dar) a%%earance when light is %assed through twisted nematic liquid crystal %laced between two crossed %olarizers .a/ a%%earance is bright in the absence of electric field .b/ a%%earance is dar) in the %resence of electric field.

The ?## twist in the cell is lost when a sufficiently strong electric field .03"6/ is a%%lied to the cell. ence the cell a%%ears dar) between two crossed %olarizers .Fig. 8b/. The following conditions, however should be met to see the electro3 o%tic effect. .i/ The %lane of %olarization of incident light should be %arallel or %er%endicular at the surface of the cell. .ii/ The %roduct of o%tical anisotro%y, Bn, .the difference in refractive indices %arallel and %er%endicular to the director/ and %itch 7 should be greater the wavelength of the incident light. Bn D 7 E F. App"ications o% "i&uid cr'sta"s in disp"a' s'st! s: The electro3o%tic effect of liquid crystals controls brightnessGdar)ness of the light emerging from its elements and is used in information dis%lays. ,nformation is %assed into the user using the liquid crystals which control the brightnessGdar)ness of the %arts of the dis%lay. ;umeric dis%lay has seven segments whereas al%habets are dis%layed using fourteen3segments. +ore com%le( gra%hic images are formed using %i(els .%icture elements/ which are closely %ac)ed array of dots in two dimensions. A numeric dis%lay consists of seven segments for each digit. *ight from the area of each of the seven segments of %i(els is controlled inde%endently and is used to create any one of the ten digits. 8hen an electric field is a%%lied to a segment, the liquid crystal in that segment undergoes deformation .is activated/ and when %olarized light is incident, the light is modulated de%ending on the deformation in that segment. A ty%ical liquid dis%lay cell .reflection mode/ is shown in Fig.?.

11

Fig.?. 'chematic re%resentation of a liquid crystal dis%lay .reflection mode %i(el/ where the liquid crystal is embedded between two glass %lates.

The seven3segment dis%lay shown in Fig.1# is used to dis%lay numbers in calculators and watches. The to% and bottom glass %lates of a dis%lay have electrode %atterns formed by etching a layer of indium tin o(ide using standard %hotolithogra%hic %rocess. All the seven segments in the bottom glass %late are interconnected as shown in Fig. 1#a to form a bac) %lane. $onnections to the segments a to g are brought out se%arately on the other glass %late as shown in Fig. 1#b. *iquid crystal mi(ture is filled in the cell formed by sealing the edges of the to% and bottom glass %lates. Area of intersection between the electrode %atterns on the to% and bottom glass %lates decides the sha%e of the segments in the dis%lay. The distance between the to% and bottom glass %late is called cell thic)ness. ,t is usually in the range ! to 8 Hm to ensure that dis%lay can switched in milliseconds. The quantity of liquid crystal mi(ture used in a dis%lay is small. Figure 1#c shows a 4 digit numeric dis%lay. A%%lication of a voltage between the bac) %lane and the corres%onding electrode on the to% %late turns <; a segment. For e(am%le the segment b is turned <; by a%%lying a voltage about 4 volts between the bac) %lane and the electrode b on the to% %late. The ac waveforms a%%lied to the bac) %lane, an <; segment and an <FF segment are as shown in Fig.1#d.

10

Fig.1#. 'even segment liquid crystal dis%lay used to dis%lay numbers in calculators

@yes used in liquid crystal dis%lays are called dichroic dyes and give desired colours to the dis%lays with a good contrast. *iquid crystal dis%lays o%erate at low voltages .a few volts/ and consume less %ower as com%ared to other dis%lay. Us!s: a/ 8atches, calculators, mobile tele%hones, la%to% com%uter and related electronic gadgets. b/ ,ndicators used in automobile dashboards, air%lane coc)%its, traffic signals, advertisement boards and %etrol %um% indicators. c/ 2lood %ressure instruments, digital thermometers and T6 channel indicators. d/ % meters, conductometers, colorimeters, %otentiometers and other analytical instruments.

14

INSTRU+ENTAL +ETHODS O/ ANALYSIS

,)- COLORI+ETRY The variation of the color of a solution with change in concentration of some solute com%onent in the solution forms the basis of colorimetry. T(o!r': 8hen a monochromatic light of intensity , # is incident on a trans%arent medium, a %art of light is absorbed by the media .,a/, a %art of light is reflected .,r/ and the remaining %art of light is transmitted .,t/, i.e., ,# : ,a I ,r I ,t For a glass3air interface, ,r is negligible Therefore ,# : ,a I ,t The investigations on the change of absor%tion of light with thic)ness of the medium were carried out by *ambert. 2eer later a%%lied similar e(%eriments to solutions of different concentrations. Two se%arate laws governing absor%tions are )nown as *ambertJs law and 2eerJs law. ,n the combined form, they are referred to as *ambert32eer law. La 2!rt7s "a.: ,t states that Kwhen monochromatic light %asses through a trans%arent medium, the rate of decrease in intensity with thic)ness of the medium is %ro%ortional to the intensity of the lightL i.e., 3 d,Gdt : ), MMMMMMMMM...1/ 8here , is the intensity of the intensity of the incident light, l is the thic)ness of the medium and ) is a %ro%ortionality factor. <n rearranging .1/, 3d,G,: 3)dtMMMMMMMMMM.0/ ,ntegrating .0/ between the limits, , : ,# when l : #, and , : ,t at l ln.,#G,t/ : )t ,t : ,#e3)t MMMMMMMMMM...4/ 8here ,# is the intensity of the incident light falling u%on an absorbing medium of thic)ness l, ,t is the intensity of the transmitted light and ) is a constant for the absorbing medium. The equation indicates that the intensity of the emitted light decreases e(%onentially as the thic)ness of the absorbing medium increases arithmetically. 2y changing into common logarithms, we get1 ,t : ,# 1#3NtMMMMMMMMMM. .!/ 8here, N : )G0.4#4, and is termed as absor%tion coefficient. ,tG,# : 1#3Nt MMMMMMMMMM.."/

1!

The ratio ,tG,# is the fraction of the fraction of the incident light transmitted by a thic)ness t of the medium and is termed the trans ittanc!8 T$ ,ts reci%rocal, ,tG,# is the o%tical density .o%acity/. Therefore, A2sor2anc! A : log .,#G,t/ : NtMMM.5/ 6!!r7s "a.: ,t states that Kwhen monochromatic light %asses through a solution, the rate of decrease in intensity with concentration of the light absorbing s%ecies is %ro%ortional to the intensity of the light.L i.e. 3 d,Gdc : )1, MMMMMMMMM...&/. 8here OcJ is the concentration of the light absorbing s%ecies in the solution and ) 1 is %ro%ortionality constant. <n rearranging and integrating between the limits, , : , # at c : #, and , : , t at c, ,t : ,# e3)c log .,#G,t/ : N1c MMMMMMMMM..8/ 8here N1 : )1G0.4#4. La 2!rt-6!!r "a.: ,t states that Kwhen monochromatic light %asses through a solution, the rate of decrease in intensity with thic)ness of the medium is %ro%ortional to the intensity of incident radiation as well as to the concentration of the solution.L i.e., 3 d,Gdt : ) , c MMMMMMMMM..?/ 8here , is the intensity of the intensity of the incident light, t is the thic)ness, c is the concentration of the medium and ) is a %ro%ortionality factor. <n rearranging and integrating between the limits, , : , # at l : #, and , : ,t at l, ,t : ,# e3)tc MMMMMMMM..1#/. ,tG,# : e3)tc ,tG,# : 1# 3Ntc : TMMMMMM.11/ T is the transmittance of light absorbing medium. ,nversing the above ratio and ta)ing log we get, log .,#G,t/ : Ntc : A MMMM...10/ A is called absorbance .or o%tical density/ of the light absorbing trans%arent solution. Therefore if absorbance of a series of solutions are %lotted versus their concentrations, a straight line %assing through origin results .Fig. 1/

1"

P(oto!"!ctric co"ori !t!r: The essential %arts of a %hotoelectric colorimeter are a light source, a light filter, a container for the solution, a %hotocell to receive the transmitted light and means for measuring the res%onse of the %hotocell. The bloc) diagram is shown in Fig.0.

The function of the filters is to isolate any desired s%ectral region by filtering off the undesired radiations. <%tical filters consist of either thin films of gelatin containing different dyes or colored glass. The filter allows radiations of definite wavelength range to %ass through it and reach the sam%le. App"ications: .i/ ,n quantitative analysis1 A large numbers of metal ions, anions and organic com%ounds can be determined by colorimetry. .ii/ 7hotometric titrations1 $olorimetric measurements have also been used in locating the equivalence %oint in a titration. .iii/ @etermination of the com%osition of a colored com%le(. ,*- POTENTIO+ETRY 7otentiometry is an electroanalytical technique in which the amount of a substance in solution is determined, either directly or indirectly, from measurement of the emf between two electrodes that are di%%ed into the solution. 8hen a metal + is immersed in a solution containing its own ions, +nI, the electrode %otential is given by ;ernst equation. - : -# I .0.4#4RTGnF/ log P+nIQ - can be measured by combining the electrode with a reference electrode and measuring the emf of the cell. The concentration can be calculated, %rovided - # of the electrode is )nown. The %rocedure of using single measurement of electrode %otential to determine the concentration of an ionic s%ecies in solution is referred to as direct %otentiometry. The electrode, whose %otential is de%endent u%on the concentration of the ion to be determined, is termed as the indicator electrode. The indicator electrode res%onds to the change in concentration of the analyte s%ecies %resent in the solution, in which it is in contact with. +easurement of % and measurement
15

of ion concentrations using ion selective electrodes are the e(am%les for direct %otentiometry. ,t requires accurate measurement of the emf. A %otentiometer is used to measure the emf of the cell and emf is measure when no current %asses through the circuit, i.e., when neither current is drawn from the cell nor it %asses through the cell. Instru !ntation: 7otentiometer consists of a reference electrode, an indicator electrode and a %otential measuring device. The indicator electrode res%onds ra%idly to the changes in the concentration of the analyte i.e. the solution under study. A sim%le arrangement of %otentiomeytric titration is de%icted in Fig.4. A is reference electrode .say saturated calomel electrode, '$-/, 6 is the indicator electrode .say %latinum electrode/ and $ is a mechanical stirrer. The solution to be titrated .to be estimated/ is ta)en in the bea)er. A )nown volume of analyte is ta)en and its %otential is determined. The titrant is added in increments of 1 ml and emf is measure each time. At the a%%roach of equivalence %oint, the e.m.f. tends to increase ra%idly. At this %oint, small increments, say, #.1ml of titrant are added. A few readings are ta)en beyond the end %oint. Thus the changes in %otential at different volumes are recorded.

Fig.4. 7otentiometric titration unit

Location o% !nd point: The im%ortant factor in a titration is the recognition of the %oint at which the quantities of the reacting s%ecies are %resent in equivalent amounts3 the equivalence %oint or end %oint of a titration. ,n %otentiometric titrations, the end %oint can be fi(ed by e(amination of the titration curves, including derivative curves. The titration curve can be obtained by %lotting emf readings obtained with the reference electrode3indicator electrode %air against volume of the titrant added. .Fig. !/

1&

Fig.!. 7otentiometric titration curve

<ver most of the titration ranges, the cell emf varies gradually, but near the end %oint, the cell emf changes very abru%tly as the logarithm of the concentration changes ra%idly. The resulting titration curve will be a '3sha%ed curve as shown in the figure. The end %oint can be located on the stee%ly rising %ortion of the curve, at the %oint of inflection, the %oint which corres%onds to the ma(imum rate of change of cell emf %er volume of the titrant added. 8hen the curve shows a very clearly mar)ed stee% %ortion, one can give an a%%ro(imate value of the end %oint as being mid way along the stee% %ortion of the curve. The end %oint can be located more %recisely by em%loying derivative methods in which the first derivative curve . -G 6/ against 6 .Fig. "a/ or second derivative curve . 0-G 60/ against 6 .Fig. "b/ are %lotted.

Fig.".@erivative curves for %otentiometric titration

The first derivative curve gives a ma(imum at the %oint of inflection of the titration curve, i.e., at the end %oint. ,n the second derivative curve, is zero at the %oint of inflection or at the end %oint. App"ications: ,i- Acid 2as! titrations1 For an acid base titration, the indicator electrode has to be a % sensitive or I sensitive electrode as it has to res%ond the change in % during the titration. Therefore, glass electrode is most commonly used as the indicator electrode. 'aturated calomel electrode is generally em%loyed as the reference electrode.
18

The accuracy of the method de%ends u%on the magnitude of the change in emf in the neighbourhood of the equivalence %oint, and this de%ends u%on the concentration and strength of the acid and al)ali. The method may be used to titrate a mi(ture of acids which differ greatly in their strengths. ,ii- O5idation r!duction titrations: <(idation reduction titration can conveniently be carried out as %otentiometric titrations. For e(am%le, in the titration of +ohrJs salt solution with %otassium dichromate solution, calomel electrode is used as the reference and an inert %latinum foil is used to %ic) u% the %otential of indicator electrode, which is actually the o(idation reduction electrode involving the redo( s%ecies %resent in the solution. 2efore the titration is started, the solution contains only ferrous ions in the solution. 8hen a small volume of the dichromate solution is assed, equivalent small quantity of Fe0I ions are converted into Fe4I ions. ,n the %rocess, the $r5I ion in dichromate is reduced to $r4I ion.
3 Fe2+ + Cr6+ 3 Fe3+ + Cr3+

The %resence of Fe0I and Fe4I ions in the solution gives rise to an o(idation reduction electrode, the %otential of which can be %ic)ed u% by the %latinum electrode di%%ed in the solution .7t G Fe 4I, Fe0I/. The electrode %otential of the so formed electrode is given by, - : -# A #.#"?1log RPFe0IQ G PFe4IQS at 0?8N The electrode %otential of the indicator electrode de%ends u%on the ratio of the concentrations of reduced and o(idized s%ecies in the solution. As the titration %roceeds, the concentration of Fe4I goes on increasing and that of Fe 0I goes on decreasing. As a result, the ratio in the e(%ression for electrode %otential goes on increasing and the increase in the value of the ratio becomes very large near the end %oint. This results in the large in the electrode %otential and in turn, in the measured emf of the cell. At the equivalence %oint, all the Fe 0I ions are converted into Fe 4I ions, the 7t G Fe4I, Fe0I electrode ceases to e(ist. 2ut addition of a slight e(cess of dichromate solution introduces $r5I ions into the solution, which along with the $r4I ions in the solution .formed during the o(idation of Fe 0I/ form a new o(idation reduction electrode, 7t G $r5I, $r4I. This change over of indicator electrode at the end %oint also contributes to the large increase in %otential at the end %oint, as -# of the two electrodes differ by a large value. After the end %oint, therefore it is 7t G $r5I, $r4I acting as the indicator electrode.

1?

,1- CONDUCTO+ETRY ,n this method, an alternating voltage is a%%lied across two electrodes immersed in the same solution. The a%%lied voltage causes a current to flow. The magnitude of current de%ends on the conductivity of the solution and com%osition of the sam%le is deduced from the measurement of the conductivity. Princip"!: E"!ctro"'tic conducti3it': -lectrolytic conductivity is a measure of the ability of a solution to carry an electric current. -lectrolytic solutions conduct current by the migration of ions under the influence of an electric field. *i)e a metallic conductor, they obey <hmJs law, - : ,R 8here, - is the a%%lied %otential, , is the current and R is the resistance, which is the measure of the hindrance caused for the flow of current under the %otential a%%lied. The reci%rocal of the resistance is called the conductance, $ : 1GR ,t is e(%ressed in ohm31, mhos or 'iemen .'/ in ', units. The resistance of any conductor is directly %ro%ortional to the length and inversely %ro%ortional to the area of cross section of the conductor. R : ' .lGa/, where ' is s%ecific resistance or resistivity of the conductor. Therefore, conductance, $ : 1GR : .1G'/..aGl/ 9 T. .aGl/ 8here, T is the s%ecific conductance or conductivity of the electrolytic solution. 8hen a : 1and l :1, $ : T <r, sp!ci%ic conductanc! is the conductance of an electrolyte solution )e%t between two electrodes of 1m 0 cross sectional area at 1 m a%art. ,t is the conductance of a meter cube of the solution. The unit of T in ', units is '.m31 ,n electrolytic solutions, the ion concentration is an im%ortant variable. ,t is usual to relate the electrolyte conductance in terms of equivalent conductance or molar conductance. E&ui3a"!nt conducti3it' is defined as the conductance of a solution containing one gram equivalent weight of the electrolyte. +o"ar conductanc! is defined as the conductance of a solution containing one mole of an electrolyte. Instru !ntation: $onductometer consists of two %latinum electrodes and a conductance measuring device. The two electrodes have unit area of cross section and are %laced unit distance a%art. The assembly res%onds ra%idly to the changes in the concentration of the analyte .the solution under study/. A sim%le arrangement of

0#

conductometric titration is de%icted in Fig.5. The solution to be titrated .to be estimated/ is ta)en in the bea)er.

Fig.5. conductometric titration unit

Conducto !tric titrations: $onductometric titration is a method of volumetric analysis based on the change in conductance of the solution, at the equivalence %oint .or end %oint/ during titration. This method is based on the fact that conductance of an aqueous solution, containing an electrolyte, de%ends u%on, .i/ the number of free ions in the solution .concentration of the solution/, .ii/ the charges on the free ions, and .iii/ mobility .or s%eed/ of the ions. @uring the course of titration .i.e., addition of one electrolytic solution to that of another/, the number of free ions in the solution changes. ;ot only that, even the identity of the ions also changes. As a result of this, conductance of the solution .contained in cell/ also undergoes a change. Acid-2as! titrations: (a) Titration of a strong acid (like HCl) with a strong base (like NaOH)( Fig.7): 2efore base is added, the conductivity of acid solution is high .mainly due to the %resence of highly mobile I ions/. This is re%resented by %oint A on the curve. <n gradual addition of ;a< from the burette, highly mobile I ions .of the acid/ are removed by the added < 3 ions to form nearly non3conducting water molecules.
H+Cl- + Na+OHAcid Base Na+Cl- + H2O Salt Water (N !-c !d"cti!#$

ence, the conductivity of the solution decreases %rogressively, till the equivalence %oint 2 is reached. <n further addition of ;a< , the conductivity of the solution will rise along the curve 2$ .due to the addition of highly mobile < 3 ions to the solution/. Thus, the descending branch of the curve .i.e A2/ give the conductance of a mi(ture of an acid and salt, and the ascending branch .i.e., 2$/ gives the conductance of mi(ture of salt and e(cess base. At the minimum %oint 2, there is no e(cess of either acid or base and hence, it corres%onds to the equivalence %oint.

01

(b) Titration of a weak acid (say CH 3COOH) and a strong base (like NaOH) ( Fig. &): The titration curve has the form of A121$1. Acetic acid .a wea) acid/ has low conductivity, as re%resented by A1. As ;a< is added, the %oorly conducting acid is converted into highly ionized salt, $ 4$<<;a, and $ 4$<< I ;a< $ 4$<<3;aI I 0< consequently, the conductivity goes u% along A 121. 8hen the acid is neutralized, further addition of al)ali causes a shar% rise in conductance along 2 1$1 .due to addition of more conducting < 3 ions/. The intersection of A121 and 21$1, therefore, re%resents the equivalence %oint.

Fig.&. $onductometric titration curves. .a/ A2$3strong acid vs. strong base. .b/ A 121$13 wea) acid vs. strong base.

.c/ In the titration of a i!t"re of strong acid (HCl) and a weak acid (CH 3COOH) with a strong base (NaOH) .Fig. 8/, the conductance decreases u%on addition of ;a< to acid mi(ture .due to highly mobile I are removed by the added < 3 ions/.This trend continues till all the I ions of $l re%laced. $ontinued addition of ;a< rises the conductance moderately .due to %oorly conducting acid is converted into highly ionized salt, $ 4$<<;a/. Further addition of ;a< increases the conductance stee%ly due to the %resence of free < 3 ions. The titration curves in the gra%h given de%ict the location of the equivalence %oints.

Fig.8.$onductometric titration of mi(ture of a strong acid and a wea) acid with a strong base. MMMMMMMMMMMMMMMMMMMMMM

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