PAPER OF ANALYTICAL CHEMISTRY 1

PRECIPITATION TITRATION

Written by : GROUP I 1. Aisah Ika Wardhani K3309006 2. Dino Prihantoro K3309032 3. Nirmala hayati K3309061 !.N"r"l Aini K330906! #. $arry $aras%aty K33090&3 6. $iti $olikah K33090&6 &. 'iandika Ditama K33090(3 Chemical Educati ! P" #"ammed $e%a"teme!t & Mathematic' a!d Natu"al Scie!ce Educati ! Facult( & Teache" T"ai!i!# a!d Educati ! Se)ela' Ma"et U!i*e"'it( +,1,

PRECIPITATION TITRATION

I- INTRO$UCTION
Tit"ati ! is a )ommon laboratory method o* +"antitati,e )hemi)al analysis that is "sed to determine the "nkno%n )on)entration o* a kno%n rea)tant. -e)a"se ,ol"me meas"rements .lay a key role in titration/ it is also kno%n as volumetric analysis. A rea0ent/ )alled the titrant or titrator/ o* a kno%n )on)entration 1a standard sol"tion2 and ,ol"me is "sed to rea)t %ith a sol"tion o* the analyte or titrand/ %hose )on)entration is not kno%n. 3sin0 a )alibrated b"rette or )hemistry .i.ettin0 syrin0e to add the titrant/ it is .ossible to determine the e4a)t amo"nt that has been )ons"med %hen the endpoint is rea)hed. 5he end.oint is the .oint at %hi)h the titration is )om.lete/ as determined by an indi)ator 1see belo%2. 5his is ideally the same ,ol"me as the e+"i,alen)e .oint6the ,ol"me o* added titrant at %hi)h the n"mber o* moles o* titrant is e+"al to the n"mber o* moles o* analyte/ or some m"lti.le thereo* 1as in .oly.roti) a)ids2. In the )lassi) stron0 a)id7stron0 base titration/ the end.oint o* a titration is the .oint at %hi)h the .8 o* the rea)tant is 9"st abo"t e+"al to &/ and o*ten %hen the sol"tion takes on a .ersistin0 solid )olor as in the .ink o* .henol.hthalein indi)ator. 5here are ho%e,er many di**erent ty.es o* titrations : A)id -ase titration :edo4 titration om.le4ometri) titration 5his .a.er/ .re)i.itation rea)tion -roadly s.eakin0/ this ty.e o* analysis is 0ro".ed into: analysis o* .hysi)al/ )hemi)al/ .hysi)o)hemi)al/ mi)robiolo0i)al/ or0anole.ti). 5he analysis is deri,ed *rom the ;atin meanin0 analysis release. In 0eneral/ the analysis )an be de*ined se.aration o* one b"siness "nit o* material into its )onstit"ent )om.onents so that it

In this .a.er/ %e 9"st dis)"ss abo"t Pre)i.itation 5itration.

)an be seen *"rther. 5he analysis )an also be 0ro".ed into t%o: +"alitati,e and +"antitati,e analysis. <"alitati,e analysis is an analysis in,ol,in0 the identi*i)ation o* s"bstan)es/ ie %hat elements or )om.o"nds that e4ist in a sam.le/ %hile +"antitati,e analysis is an analysis o* determinin0 ho% a .arti)"lar s"bstan)e is in an instan)e/ s.e)i*ied s"bstan)es are o*ten re*erred to as the desired s"bstan)e or analyte 1to )onsists o* a small or lar0e .art o* the analy=ed sam.les2. I* the analytes are more than 1> is )onsidered as the main )onstit"ent/ %hen totaled abo"t 0.01 to 1> is less im.ortant )onstit"en)ies/ %hile the n"mber is less than 0.01> is )onsidered as a tra)e )onstit"ent. 'ol"metri) analysis is .art o* the +"antitati,e analysis. 'ol"metri) analysis be)a"se the .ro)ess is also )alled titrimetri) analysis o* titration/ standard sol"tion 1rea0ent2 as a titrant %hi)h is .la)ed in the b"rette is "sed to titrate the sol"tion to be determined amo"nt the analite. While 0ra,imetry is one o* the main bran)h o* )hemi)al analysis. ?ra,imetry be)ome the )lassi) method is still *re+"ently "sed. ?ra,imetry is the determination o* the amo"nt o* s"bstan)e based on %ei0hin0. Wei0hin0 a rea)tion a*ter %ei0hin0 the res"lts o* the analy=ed s"bstan)es %ere rea)ted. 5he res"lt o* the rea)tion may be resid"al material or a 0as that o))"rs or a .re)i.itate *ormed *rom the analy=ed material. ?ra,imetry is the %ay o* analysis o* the oldest and least e4.ensi,e. @nly 0ra,imetri) re+"ire a relati,ely lon0 time and )an only be "sed *or a *airly lar0e )om.onent le,els. A small error/ %ill res"lt in relati,ely lar0e. Ne,ertheless 0ra,imetri) still bein0 "sed *or ."r.oses o* analysis be)a"se the .ro)ess is "nne)essarily time )ontin"o"sly done sin)e ea)h sta0e o* )onstr")tion analyst takes a lon0 time. Pre)i.itation titration is a titration in,ol,in0 the *ormation o* salt de.osits that are not easily sol"ble bet%een titrant and analyte. 5his basis is re+"ired *rom this ty.e o* titration is a)hie,ement o* a ra.id e+"ilibri"m *ormation e,ery time titrant added to the analyte/ the absen)e o* inter*eren)e that inter*ere %ith the titration/ end.oint titration and are easily obser,ed.

@ne ty.e o* .re)i.itation titration is a ,ery lon0 history in,ol,in0 .re)i.itation rea)tions bet%een halide ions 1 l7/ I7/ -r72 %ith sil,er ions A0 A. 5itration is "s"ally re*erred to as ar0entometry the titration determination o* analytes in the *orm o* halide ions 1in 0eneral2 by "sin0 a standard sol"tion o* sil,er nitrate A0N@ 3. 5itration ar0entometry not only )an be "sed to determine the halide ions b"t also )an be "sed to determine the mer)a.tan 1thioal)ohol2/ *atty a)ids/ and se,eral di,alent anions s")h as .hos.hate P@!37 ion and ion As@!37 arsenate.

-asi) titration ar0entometry is the *ormation o* de.osits that are not easily dissol,e bet%een the titrant to the analyte. Bor e4am.le the %idely "sed titration determination o* Na l in %hi)h the A0 *rom the analyte to *orm salts
A

ions *rom titrant %ill rea)t %ith are not easily sol"ble

l 7 ions A0 l.

that

A0 1N@32 1a+2 A Na l 1a+2

A0 l 1s2 A NaN@3 1a+2

A*ter all the )hloride ions in the analyte o"t the e4)ess sil,er ions %ill rea)t %ith the indi)ator. 5he indi)ator "sed is ty.i)ally the )hromate ion r@ !27 %here %ith this indi)ator o* sil,er ions %ill *orm a reddish bro%n .re)i.itate so that the end .oint o* titration )an be obser,ed. @ther iIndi)ator that )o"ld be "sed is tio)yanide and indi)ator adsor.tion. -ased on the ty.e o* indi)ator and titration te)hni+"es are "sed/ the titration )an be distin0"ished on ar0entometry "sin0 Cohr/ 'olhard/ or Ba9ans. -esides "sin0 the abo,e ty.es o* indi)ators %e )an also "se .otentiometri) method *or determinin0 the e+"i,alent .oint. A)"ity e+"i,alent .oint de.ends on the sol"bility o* .re)i.itate *ormed *rom the rea)tion bet%een the analyte and titrant. $ediment %ith a small sol"bility %ill res"lt in the titration )"r,e stee.ness ar0entometry %ho ha,e a hi0h so easy to determine the e+"i,alent .oint/ b"t the .re)i.itate %ith lo% sol"bility %ill res"lt in the titration )"r,e is slo.in0 so that the e+"i,alent .oint some%hat di**i)"lt to determine. 5his is analo0o"s to the titration )"r,e bet%een a stron0 a)id %ith stron0 base and bet%een %eak a)id %ith stron0 base.

-asi) o* .re)i.itaion titration is rea)tion *ormin0 )om.o"nd that di***i)"lt to sol"ble "ntil *ormed .re)i.itation. Pre)i.itation rea)tion standard "sed on is rea)tion bet%een sil,er ion 1ar0entometry2. Ar0entometry is titration as re0ard "sin0 A0N@ 3 sol"tion. 5he rea)tion : A0A 1a+2 A D7 1a+2

A0D 1s2

D E l/ -r/ N$/ $ N/ dan N.

-ased on indi)ator "sed/ to determinin0 the end .oint titration di,ided into :

P"eci%itati ! T(%e . M h"/' meth d

Indi)ator o* this method is K2 r@! %ith titran A0N@3 in ne"tral )ondition. In a)id )ondition It is done in ne"tral )ondition be)a"se in a)id )ondition/ )hromat )an be )han0ed into bi)hromat. han0e o* )hromat ion to be bi)hromat %ill di**i)"lty to kno% the end .oint o* titration be)a"se not *ormed red ..t *rom A0 r@ !/ so need e4)ess A0N@3 and )orr".t titration. And %hen done is base )ondition/ it *o"nd m")h @87 ion so/ %ith A0N@3 han0 loosely to be A02@ and 82@ so need more A0 ion )a"se error titration. hloride is titrated %ith A0N@3 sol"tion. A sol"ble )hromate salt is added as the indi)ator. 5his .rod")es a yello% )olor sol"tion. When the .re)i.itation o* the )hloride is )om.lete/ the *irst e4)ess o* A0 A rea)ts %ith the indi)ator to .re)i.itate red sil,er )hromate:

2 Ag (aq) + CrO
+

2 4

(aq)

Ag CrO (s)
2 4

Gello%

red ..t

5he Cohr method m"st be .er*ormed at a .8 abo"t (. 5his method is "se*"l *or determinin0 l7 in ne"tral or "nb"**ered sol"tions s")h as drinkin0 %ater. F Ad' "%ti ! 0 Fa1a!/' meth d

Indi)ator is one indi)ator o* adsor.tion a))ordin0 to the kinds o* anions are .re)i.itated by A0 A/ titrant A0N@3/ .8 de.endin0 on the kinds o* anions and indi)ators "sed. onsider the titration o* l7 %ith A0A. -e*ore the e+"i,alent .oint/ l7 is in e4)ess and the .rimary layer is l7 10o ba)k to .re)i.itation .ro)ess in 0ra,imetry2. 5his re."lses the indi)ator anionsH and the more loosely held the se)ondary 1)o"nter2 layer o* adsorbed ions is )ations/ s")h as NaA : A0 l : l7 : : NaA -eyond the e+"i,alent .oint 1end .oint as %ell2/ A0 A is in e4)ess and the s"r*a)e o* the .re)i.itate be)omes .ositi,ely )har0ed/ %ith the 1 layer bein0 A0A. 5his %ill no% attra)t the indi)ator anion and adsorb it in the 2 1)o"nter2 layer: A0 l : A0A : : indi)ator7 5he )olor o* the adsorbed indi)ator is di**erent *rom that o* the "n7adsorbed indi)ator/ and this di**eren)e si0nals the )om.letion o* the titration. 5he de0ree o* adsor.tion o* the indi)ator )an be de)reased by in)reasin0 the a)idity. 5he titration o* )hloride "sin0 this kind o* indi)ator is )alled Ba9anIs Cethod. Ba9anIs method is the most re)ent and most a))"rate sil,erhalide method. It is based on the adsor.tion o* di)hloro*l"ores)ein 1D B2 and *l"oresen on the s"r*a)e o* the .ositi,ely )har0ed sil,er )hloride .arti)les *ormed in the .re)i.itation titration 2he! A#3 i ! i' i! e4ce''.

5he

"se

o*

indi)ator

adsor.tion

18o%

Ba9ans2

Adsor.tion o* an or0ani) )om.onent in )olor on the s"r*a)e o* a sediment )an )a"se a shi*t in mole)"lar ele)troni)s that )han0e the )olor. 5his .henomenon )an be "sed to dete)t the titration end .oint o* the de.osition o* sil,er salts. While the )om.o"nd "sed *or
A

thin0s

like

this

as

an

indi)ator

adsorbs.

5he me)hanisms that a..ly to s")h indi)ators is des)ribed by Ba9ans as *ollo%s: In the titration %ith A0 ne0ati,ely )har0ed 1A0 l2. l7C A $e)ondary .rimary s"r.l"s l7 ions are adsorbed to *orm .rimer layer/ the res"ltin0 )olloidal .arti)les are ne0ati,ely )har0ed. 5hese .arti)les attra)t .ositi,e ions *rom sol"tion to *orm a se)ondary layer %ith loose sit"ation. @n to. o* the e+"i,alen)e .oint/ e4)ess A0 .rimary layer and the .arti)les
A

l7/ be*ore the e+"i,alen)e .oint o* the )olloidal .arti)les are A0 l/ d"e to l7 ion adsor.tion *rom sol"tion:

ions re.la)e

l7 ions *rom the )har0ed:

be)ome

.ositi,ely

A0A 1a+2 A l7 1a+2

A0 l 1s2

$e)ondary .rimary s"r.l"s Anions in sol"tion are interested to *orm a se)ondary layer. Bl"oros)ein is a *atty or0ani) a)id/ %hi)h )an be re*erred to the 8BI %hen *l"ores)ein is added into the titration bottle. BI7anions are not adsorbed by )olloidal sil,er )hloride immersion e4)ess )hloride ions. 8o%e,er/ %hen e4)ess sil,er ions/ the ions )an ."lled BI7 to the s"r*a)e o* the .arti)les are .ositi,ely )har0ed. 1A0 l2. A0 A BI7 5he res"ltin0 a00re0ate .ink and the )olor is stron0 eno"0h to be a ,is"al indi)ator. A n"mber o* *a)tors m"st be )onsidered in sele)tin0 a s"itable adsor.tion indi)ator *or .re)i.itation titration. 5hese *a)tors are s"mmari=ed as *ollo%s:

1. A0 l sho"ld not be allo%ed to )oa0"late into lar0e .arti)les at the e+"i,alen)e .oint as this %ill drasti)ally de)rease the s"r*a)e a,ailable *or adsor.tion o* the indi)ator. A .rote)ti,e )olloid s")h as de4trins sho"ld be added to kee. the sediment area. With de4trin a..ear dis)oloration to titrate ba)k %ith a standard )hloride sol"tion. 2. Adsor.tion o* the indi)ator sho"ld be startin0 be*ore the e+"i,alen)e .oint and in)rease ra.idly at the e+"i,alen)e .oint. $ome indi)ators that do not mat)h stron0ly adsorbed. Indi)ator is a)t"ally re.la)in0 the main ions adsorbed lon0 be*ore the e+"i,alen)e .oint %as rea)hed. 3. P8 titration o* the media m"st be )ontrolled to ens"re an ion )on)entration o* the indi)ator %eak a)id or %eak base is eno"0h. Bl"orosein *or e4am.le has a Ka o* abo"t 107& and the sol"tions are more a)idi) than .8 & the )on)entration o* ions is ,ery small7BI so that no )olor )han0e )an be obser,ed. Bl"orosein has a Ka o* abo"t 107! and )an be "sed on a s)ale o* !710 P8 !. 8i0hly re)ommended that the ions o..osite )har0ed ion indi)ators %ere added as a titrant. Adsor.tion o* the indi)ator then it %o"ld not ha..en "ntil there is e4)ess titrant. Bor the titration o* sil,er %ith )hloride/ ."r.le metal )hloride salt o* a or0ani) base/ )an be "sed. ations are not adsorbed "ntil e4)ess )hloride ions are .resent e4)essi,e and ne0ati,ely )har0ed )olloids. It is .ossible to "se di)hloro*l"orosein in this )ase/ b"t the indi)ator sho"ld be added 9"st be*ore the e+"i,alen)e .oint.

F " 'il*e" a!al('e' 05 lha"d meth d

Indi)ator o* this method is *erry ammoni"m s"l.hate in a)id )ondition %ith titran K$ N or N8!$ N. 5itran rea)ted %ith e4)ess standart sol"tion A0N@3. J4)ess o* sil,er ion added %ith thio)yanat ion. In this rea)tion need a)id )ondition be)a"se %hen in rea)t in base )ondition/ @87 %ill *orm Be1@823 red bro%nish/ and a,oid hydrolysis *erry ammoni"m *ormed ..t A01@823. 5his is an indire)t titration .ro)ed"re *or the determination o* anions that .re)i.itate %ith sil,er like l7/ -r7/ I7/ $ N7/ and it is .re*erred in a)id 18N@32

sol"tion. A meas"red e4)ess o* A0N@3 is added to ..t the anion/ and the e4)ess o* A0A is determined by ba)k titration %ith standard .otassi"m thio)yanate sol"tion:

A0 1a+2 A l 1a+2 K A0 l1s2 A e4)ess A0

A F

e4)ess A0 1a+2 A $ N 1a+2 K A0$ N1s2

A F

5he end .oint is dete)ted by addin0 iron III 1Be3A2 as *erri) ammoni"m s"l*ate %hi)h *orms a sol"ble red )om.le4 %ith the *irst e4)ess o* titrant.

Be

3A

1a+2

A $ N 1a+2 K LBe$ NM
F

2A

1a+2

5hese indi)ators m"st not *orm a )om.o"nd %ith the titrant that is more stable than the .re)i.itate or the )olor rea)tion %o"ld o))"r on addition o* the *irst dro. o* titrant.

A"#e!t met"( Tit"ati ! Cu"*e'

Ar0entometry titration )"r,es made %ith .lot bet%een )han0es in analyte )on)entration on the ordinate a4is and the ,ol"me o* titrant in %i)k a4is. In 0eneral/ the analyte )on)entration is e4.ressed in *"n)tion 1.2/ ie/ PD E7lo0 LDM %hile the titrant ,ol"me in "nits o* milliliters. 5itration )"r,e )an be di,ided into 3 .arts namely be*ore the e+"i,alent .oint/ at the e+"i,alent .oint and a*ter the e+"i,alent .oint. 5o dra% a titration )"r,e ar0entometry then )onsider the *ollo%in0 e4am.le: #0 m; o* 0.1 C Na l sol"tion titrated %ith 0.1 C sol"tion o* sil,er nitrate A0N@3/ then )al)"late the )on)entration o* l7 at the be0innin0 and at the time o* addition o* sil,er nitrate as m")h as 10 m;/ !9.9 m;/ #0 m;/ and 60 m; and "nkno%n Ks. A0 l 1/#6.10710 At the be0innin0 there has been no A0N@3 titration is added so that the )on)entration o* )hloride ions are as *ollo%s: L l7M E 0.1 C P l E7lo0 L l7M E7;o0 0.1

E1 5he rea)tion is: A0 A 1a+2 A l71a+2 A0 l 1s2

A

*rom the abo,e rea)tion is kno%n that the mole ratio bet%een A0 )on)entration. When the addition o* 10 m; o* 0.1 C A0N@3 L l7M E 1#0 N 0.12 7 110 N 0.12 O 1#0 A102 E 0.06& C P l E 7;o0 L l7M E 7;o0 0.06& E 1.1& When the addition o* !9.9 m; o* 0.1 C A0N@3 L l7M E 1#0 N 0.12 7 1!9.9 N 0.12 O 1#0 A!9.92 E 1.107! P l E 7;o0 L l7M E 7;o0 1.107! E! When the addition o* #0 m; o* 0.1 C

and l7 is

1:1 so that )om.arisons )an be "sed to determine )han0es in )hloride ion

A0N@3

Addin0 at this amo"nt then the titration %ill be at the e+"i,alent .oint o"t %here A0N@3 and Na l rea)t to *orm A0 l. At this time there are no ions A0 A and l7ions in sol"tion so that the )on)entration o* l is determined by "sin0 the ,al"e o* Ks.. A0 l 1s2 A0 A 1a+2 A l7 1a+2

Ks. E LA0 AM L l7M Ks. E $4$ Cemory ard Ks. E s2 s E Ks.1 O 2 s E 11/#6.107102 1 O 2 s E 1/2#.107# P l E 7;o0 L l7M E 7;o0 1/2#.107# E !.9 When the addition o* 60 m; o* 0.1 C A0N@3

at this time then there is e4)ess A0 A as m")h as 10 m;/ so no% %e )al)"late the amo"nt o* e4)ess A0 A )on)entration LA0 AM E 104 0.1 O 1#0 A602 E 9/1.1073 Pa0 E 7;o0 LA0 AM E 7;o0 9/1.1073 E 2.0! be)a"se P l A .a0 is 10 1*rom .ri)e Ks.2 then P l E 10 to 2.0! E &.96 And the titration )"r,e is as *ollo%s:

5he )"r,e is e**e)t to Ks. ,al"e )"r,e o* the titration )"r,e )an be seen *rom the .i)t"re belo%. Bi0"re belo% sho%s the titration )"r,e 2# m; sol"tion o* CD 1%here D is l7/ I7/ and -r72 %ith 0.0# C A0N@3. It )an be seen that the smaller the .ri)e Ks. *or A0I/ the )"r,e %ill 0et stee.er/ %hile the 0reater the .ri)e Ks. *or A0 l is in)reasin0ly slo.in0 )"r,e. @ne more thin0 is the bene*it o* the titration )"r,e than )an be "sed to sear)h *or a .oint e+"i,alent to the titration )"r,e )an also be "sed to sear)h *or the )ation and anion )on)entration at e,ery .oint %here the titration takes

.la)e.

Indicator table of adsorption Indicator Fluorescein %ic!lorofluorescein bro'cresol green +osin 'et!.l /iolet r!oda'in 0 1 Titration Cl Cl it! Ag Solution "! #-$ p& 4 p& 4-* p& 2 Acid &)O2 (3-24)

it! Ag

(C)

it! Ag

,r - I - (C)
-

it! Ag

Ag Ag

it! Cl

it! ,r-

5!orin bro'p!enol blue

(O4 &g

2-

it! ,a

2+

p& 6-*-2-* solution 3-6 4

2+

it! Cl-

II

CONCLUSION
Pre)i.itation titration is a titration in,ol,in0 the *ormation o* salt de.osits that are not easily sol"ble bet%een titrant and analyte. 5his basis is re+"ired *rom this ty.e o* titration is a)hie,ement o* a ra.id e+"ilibri"m *ormation e,ery time titrant added to the analyte/ the absen)e o* inter*eren)e that inter*ere %ith the titration/ end.oint titration and are easily obser,ed. method 5here are 3 methods in .re)i.itation titration : Pre)i.itation 5y.e 7 CohrIs method/ Adsor.tion F Ba9anIs method and Bor sil,er analyses F'olhard

III

6I6LIOGRAPHY
8ast"ti/ -"di. 2010. Cod"l Kimia Analitik Dasar 1K"antitati*2. 3N$. 3nder%ood. 2002. Analisis Kimia K"antitati*. Pakarta : Jrlan00a. htt.:OOhary,ed)a.%ord.ress.)omO2010O0(O31Omod"l7analisis7se)ara7

0ra,imetri7dan7titrimetriO 5his entry %as .osted on A"0"st 31/ 2010 at 1:19 am and is *iled "nder Pen0"9ian C"t". Go" )an *ollo% any res.onses to this entry thro"0h the :$$ 2.0 *eed. htt.:OOkimiaanalisa.%eb.idOtitrasi7.en0enda.an7ar0entometriO Posted by indi0omorie on De) 12th/ 2009 in 5itrasi Pen0enda.an htt.:OObta0allery.blo0s.ot.)omO2010O03Oanalisa7kadar7na)l7dalam7te."n07 htt.:OOen.%iki.edia.or0O%ikiO5itration ta.ioka.html Postin0 -y -ertha D9oelistee ? di 23.2& $elasa/ 02 Caret 2010