PRECIPITATOMETRIC (PRECIPITATION) TITRATION

An application method of Inorganic Pharmaceutical Analysis

Lecturer : Dr. Tutus Gusdinar Pharmacochemistry Research Group School of Pharmacy INSTITUT TEKNOLOGI BANDUNG

Precipitatometric Titration
Compared to acid-base or reduction-oxidation titrations the precipitatometric titration has no much more methods Difficult to select a suitable indicator Difficult to obtain an accurate precipitate composition, the coprecipitation effect is oftenly occured. p p y

Solubility = a saturated concentration of analyte

(crysstaline or solid form) dissolved in solvent at a defined temperature.

BaSO4( ) 4(p)
(at equilibrium state)

Ba2+ + SO42Solubility product

Solubility Product Constant : Ksp = [Ba2+] [SO42-]

Saturated solution is occured when a continuous addition of a substance is performed into its solvent until dissolution precess is terminated or it can be terminated, achieved by increasing ionic concentration until the precipitate formation ntil formation. Solubility is influenced by temperature, solvent properties and other ions properties, existed in a solution.

Solubility y s Saturated

X( (concentration of ion) t ti fi )

Factors influencing the solubility

1. 2. 3. 4. 4 5. 6. 7. 8. Temperature Solvent properties Common ions Ionic activity pH Hydrolysis eta yd o yde Metal hydroxyde Complex compound formation

1. Temperature effect Most of inorganic salts increase its solubility by increasing temperature Its temperature. better to use hot/warm solution for filtering and washing precipitate. E d hi i it t Exception : ti precipitates which are slighty soluble in hot/warm solution (e.g. Hg2Cl2, g MgNH4PO4) could be filtered after previously stored in refrigerator.

2. Solvent effect
Most of inorganic salts dissolve in water but not in organic solvent. Water molecule has a higher dipole moment and could be attracted by cations or anions to form hydrate ions. ions Like hydrogen ion forming a hydrated ion H3O+, free ion,H energy released by ionsolvent interaction could increase attractive ionic force to precipitate more solid lattice. Crysstaline ions have no attractive force into organic solvents, its solubility is smaller than those in water. In y chemical analysis, solubility difference could be used as basic of separation of many compounds. Example : mixed of Ca(NO3)2 and S (NO3)2 can b separated i solvent f C (NO d Sr(NO be t d in l t mixture containing alcohol and eter, which yields a soluble Ca(NO3)2 and an insoluble Sr(NO3)2.

3. 3 Common ion effect

Precipitate dissolves more easily in water than in solution containing common i t i i ions. F example, i A Cl solubility For l in AgCl, l bilit product of [Ag+][Cl-] < its constant of solubility product (Ksp AgCl = 1x10-10) in pure water, where [Ag+]=[Cl-] = 1x10-5 M; water when AgNO3 is added upon [Ag+] = 1x10-4 M, the [Cl-] decreases into 1x10-6 M and reaction shifts to the right side M, AgCl as : Ag+ + ClThere is salt addition to the precipitate while concentration p p of Cl- decreases. This technique of common ion addition is oftenly used for : 1) completion of precipitation process 2) precipitate washing with a solution containing common ion effect

If there is exessed common ions in a solution, the precipitate solubility will be greater than estimated Ksp, then common ion addition must be limited up to 10%. Example : Calculate molar concentration of CaF2 dissolved in a) water; b) CaCl2 0,01 M; c) NaF 0,01 M. Ksp CaF2 = 4x10 11 Hydrolysis is 4 10-11. H d l i i neglected. l t d CaF2(p) Ca2+ + 2 Fa) Solubility s = [Ca2 ], then [F-] = 2s )S C 2+ [Ca2+][F-] = Ksp s . (2s)2 = 4x10-11, then s = 2,1 x 10-4 M b) [Ca2+] = (0,01+s) ; [F-] = 2s; then s = 3,2 x 10-5 M c) [Ca2+] = s ; [F-] = (0,01+s); then s = 4 x 10-7 M Common ions decrease precipitate solubility, [F-] effect is greater than [Ca2+] effect.

Solubility of Ag-halide in Na-halide at 18 oC

Solubility of AgX, M
1 10-2 10-4 AgBr g 10-6 AgI
8 10-8

AgCl

10-10 10-8 10-6 10-4 10-2 1

Concentration of NaX, M

4. Common i effect 4 C ion ff t

Most of precipitated compounds increase its solubility in a solution containing substance not reacted to precipitate ions. This phenomena is called as ionic activity effect or diverse ion effect or neutral salt effect. For example, solubility effect example of AgCl and BaSO4 in KNO3 solution.
[KNO3] (M) 0,000 (water) 0,001 0 001 0,005 0,010 0 010
5 [AgCl]x10-5 M 5 [BaSO4]x10-5 M

1,00 1,04 1 04 1,08 1,12 1 12 =12%

1,00 1,21 1 21 1,48 1,70 1 70 =70%

Molarity is an ionic activity occured in a high diluted solution, more concentrated solution decreases faster the activity coefficient (f), caused by greater different charge of attractive ionic force. The ionic effectivity (in equlibrium state) decreases as well, and addition of precipitate is required to recover ionic activity. aAg+ . aCl- = Kosp (Ksp at a defined state of ionic activity) fAg+[Ag+] . fCl- [Cl-] = Kosp [Ag+][Cl-] = Kosp / fAg+ . fCl- = Ksp The lower activity coefficient of both ion yields the greater molar concentration of product. Increased BaSO4 solubility is greater than solubility of AgCl, or ionic activity coefficient of divalent ion is smaller than those of univalent ion. In highly diluted solution the f = 1 and the Ksp = Kosp.

Relative augmentation of the solubility of AgCl and BaSO4 in KNO3 solution

s/so
1,7 1,6 16 1,5 1,4 1,3 13 1,2 1,1 1,0 10 0,001 0,005 0,01 KNO3, M AgCl BaSO4

Example : Calculate molar solubility of BaSO4 in KNO3 0,01 M solution using activity coefficient calculated by DebyeHuckel equation. Solution of KNO3 (1:1) has ionic strength equal to its molarity of 0,01M. Read from the table : fBa2+ = 0,667 ; fSO42- = 0,659. Ksp = 1,00 x 10-10 / 0,667 x 0,659 = 2,27 x 10-10 = s2 then s = 1,51 x 10-5 M. For its performed in neglected very low ionic solubility, the activity effect is not a serious problem in the chemical analysis. Precipitation process in high ionic concentration is quiet rare. Hence, ionic activity influence gives no significant error.

5. pH effect
Solubility of weak acid salt depends on pH of the solution. For example : oxalic, sulfide, hydroxyde, carbonate,phosphate. Proton reacts with the anion to form weak acid, and increases salt solubility. a) Monovalent salt : MA(p) M+ + AHA + H2O H3O+ + AAnalytical concentration Ca = [A-] + [HA] = [A-]{[H3O+]+Ka}/Ka Fraction of A- : [A-]/Ca = Ka / {[H3O+]+Ka = 1 [ ] {[ ] [A-] = 1 .Ca Substituted to the Ksp = [ +][A-] = [M+]. 1.Ca p [M ][ [ ] Ksp/1 = Keff = [M+].Ca Keff = Effective equilibrium constant, varied on the pH for pH depends to 1.

b) Divalent salt : MA2 H2A + 2 H2O

M2+ + 2 A22 H3O+ + A2-

Kef = Ksp/12 = [M2+] Ca2

[A2-] = 2 . Ca 2 = Ka1.Ka2 / { [H3O+]+[H3O+]Ka1+Ka1Ka2 }

Kef = Ksp/2 = [M2+] . Ca

Molar concentration of iron species in a ferric hydroxyde solution as function of pH in room temperature log C
-1 FeOH2+ -2 -3 -4 -5 -6 -7 0 1 Fe2(OH)24+ 2 3 4 5 Fe(OH)2+ Fe3+

[Fe3+][OH-]3 = Ksp = 2 x 10-39 [FeOH2+][H+]/[Fe3+] = 9 x 10-4 [Fe(OH)2+][H+]2/[Fe3+] = 5 x 10-7 [Fe2(OH)24+][H+]2/[Fe3+]2 = 1,1 x 10-3

pH

Solubility of HgS at 20 oC as function of pH in a solution containing total sulfide H2S + HSlog [Hg]total, log [Hg(HS)2], dst H2S -6 HSlog [H2S],log [HS-] -2

Hg total -7

-3

-4 4 -8 Hg(HS)2 7 8 9 10 -5

Hg.HS2-9 9 4 5 6

HgS22pH

6 yd o ys s effect 6. Hydrolysis e ect

A weak acid salt dissolved in water changes pH of the solution. MA M+ + AA- + H2O HA + OHA very weak acid HA has lower Ka and an insoluble MA has y lower Ksp. At a lower [A-] hydrolysis reaction is completed. Depend to the Ksp it should show two extreeme conditions : p p a) A very low solubility of precipitate where pH is not changed by hydrolysis reaction. b) A high solubility of precipitate where OH- ion produced from water molecule is neglected.

7. Metal hydroxyde effect

As occured by hydrolysis effect, when a metal hydroxyde dissolved in water the pH will be not changed water, changed. M2+ + 2 OHM(OH)2 OH- + H2O H3O+ + OH[M2+][OH-]2 = Ksp [H3O+][OH-] = Kw K Charge balance : 2 [M2+] + [H3O+] = [OH-] Molar l bilit M l solubility can b calculatd f be l l td from th these 3 equations. ti When M(OH)2 dissolved then [OH-] increases, this anion will shift water di hif dissociation reaction to the l f (H2O is f i i i h left i formed) : d) M(OH)2 (p) M2+ + 2 OH2H2O H3O+ + OH-

Depend to solubility of OH- it should show two extreeme conditions : a) A very low solubility of precipitate where pH is not changed by the reaction. [H3O+] = [OH-] = 1,0 x 10-7 10 Ksp = [M2+][OH-]2 s = Ksp / (1,0 x 10-7)2 (1 0 b) A high solubility of precipitate increases [OH-], but [H3O+] is very low (neglected). Charge balance of these equation is either 2[M2+] = [ [OH-] or [OH-] = 2s [ Ksp = [M2+][OH-]2 = s (2s)2
3

s=

Ksp/4

8. Complex compound formation effect

Slightly soluble salt solubility is influenced by a compound forming complex to the metal cation Complexing ion could be cation. an anion or a neutral molecule which is common or diverse to the precipitate; e.g. hydrolysis effect of complexing ion of OH-. eg Example : NH3 is used for separing Ag from Hg. Ag+ + NH3 Ag(NH3)+ K1 = 2,3 x 103 23 Ag(NH3)+ + NH3 Ag(NH3) 2 + K2 = 6,0 x 103 Non-complexed silver fraction (2) can be calculated as follow: 2 = 1 / { 1 + K1[NH3] + K1K2[NH3]2 } = [Ag+] / CAg Ksp = [Ag+][Cl-] = 2 CAg [Cl-] Ksp/2 = Kef = CAg [Cl-]

Example : Calculate molar solubility of AgCl in the solution of NH3 0 01 M (as a final concentration of free ammonia 0,01 solution). Ksp AgCl = 1,0 x 10-10. Stability constant K1 = 2,3 x 103 and K2 = 6,0 x 103. 2 = 1 / {1 + 2,3 + 103(10-2) + 1,4 x 107 (10-2)2 = 7,1 x 10-4 { , ( , ( , Keff = 1,0 x 10-10 / 7,1 x 10-4 = 1,4 x 10-7 s = CAg = [Cl-] [ s2 = 1,4 x 10-7 , and s = 3,4 x 10-4 M In existed precipitating ions, most of precipitate could form soluble complex compound. In the first step the solubility compound step, decreases into the minimum caused by common ion effect, but then it increases after formating complex compound in enough quantity.

AgCl forms soluble complex with Ag+ and Cl- : AgCl + ClAgCl2AgCl2- + ClAgCl32AgCl A Cl + Ag+ A Ag A 2Cl+
Curve C r e of AgCl solubility in sol tion of NaCl and AgNO3 sol bilit solution (AgCl is more soluble in AgNO3 0,1 M and NaCl 1 M than in water)
-1 log[Cl-] -2 -3 -4 -3 -4 -5 5 -6 log[Ag+] -7 log[Cl-] -4 -3 -2 -1 log[Ag+]

Titration Curve
In a titration of 50 ml of NaCl 0.10 M solution with a solution of AgNO3 0 10 M calculate chloride ion concentrations 0.10 M, during the titration and plot a titration curve of pCl vs ml of AgNO3. Ksp AgCl = 10 x 10-10. Condition before titration : [Cl-] = 0.10 M or pCl = 1.00 [ p After addition of 10 ml AgNO3 : g Ag+ + ClAgCl (p) initial 1.00 mmol 5.00 mmol change -1.0 mmol -1.0 mmol equilibrium 4.0 mmol [Cl-] = 4.00 mmol / 60.0 ml = 0.067 M or pCl = 1.17

After addition of 49.9 ml AgNO3 : Ag+ + ClAgCl (p) initial 4.99 mmol 5.00 mmol change h - 4 99 mmol - 4 99 mmol 4.99 l 4.99 l equilibrium 0.01 mmol 4 [Cl-] 0 01 [Cl ] = 0.01 mmol / 99 9 ml = 1 0 x 10-4 M or pCl = 4 00 l 99.9 l 1.0 Cl 4.00 At h Equivalent P i : A the E i l Point + ClAgCl (p) Ag+ initial 5.00 mmol 5.00 mmol change - 5.00 mmol - 5.00 mmol equilibrium [Ag+] = [Cl-] then [Ag+][Cl-] = Ksp = 1.0 x 10-10 [Cl-] = 1.0 x 10-5 or pCl = 5.00

After addition of 60 0 ml AgNO3 : 60.0 Ag+ + ClAgCl (p) initial 6.00 6 00 mmol 5 00 mmol 5.00 change - 5.00 mmol - 5.00 mmol equilibrium 1.00 1 00 mmol [Ag+] = 1.00 mmol / 110 ml = 9.1 x 10-3 M pAg = 2 04 or pCl = 10 00 2 04 = 7 96 2.04 10.00 2.04 7.96

Generally for halide salts : Ag A + + XAgX (p) A X( ) Equilibrium constant : K = 1 / [Ag+][X-] = 1 / Ksp Smaller th Ksp, hi h the K of a tit ti reaction. S ll the K higher th f titration ti

ARGENTOMETRIC TITRATION CURVES

AgI 13 11 pX 10 X 8 6 4 2 10 20 30 40 50 60 70 80 ml of AgNO3 Ksp AgCl = 1 x 10-10 12 KspAgBr = 2 x 10-12 KspAgI = 1 x 10-16 AgCl AgBr

Titration Feasibility
As in an acid-base titration, the feasible K value of precipitation reaction could be calculated from its ionic concentrations. Example : A solution of 50 ml of NaX 0.10 M is titrated with 50 ml of AgNO 0.10 M. Calculate the K and K of A X when A NO3 0 10 M C l l h d Ksp f AgX h addition of 49.95 ml of the titrant could achieve a completed stoichiometric ionic reaction where the pX changed in 2 00 reaction, 2.00 units at the addition of 2 drops (0,10 ml) of titrant solution. Consider NaX as a complete dissolved salt the reaction is : salt, Ag+ + XAgX (p) K = 1/Ksp An addition of one drop of titrant performed before 1/Ksp. the equivalent point consumes 4.995 mmol of Ag+, and dissolved Ag+ needed to reach the equivalent point is : (50 x 0.10) 4.995 mmol = 0.005 mmol.

[X-] = 0.005 mmol / 99.95 ml = 5 x 10-5 M or pX = 4,30 7 a) If pX = 2 00 then pX = 6 30 or [X-] = 5 x 10-7 M 2,00 6.30 The titration consumed 50.00 ml of titrant means one drop excess of silver i : f il ion [Ag+] = 0.05 x 0.10 mmol / 100.05 ml = 5 x 10-5 M. 5 7 K = 1 / {(5 x 10-5)(5 x 10-7)} = 4 x 1010 Ksp = 1 / (4 x 1010) = 2,5 x 10-11 M b) If we consider pX = 1.00 the K = 4 x 109 will be obtained.
In the titration of X- with Ag+ ions, the pX value at the equivalent point depends on the analyte and titrant concentrations concentrations. These phenomena are equal to those in acid-base titration. Before equivalent point : smaller the [X-], higher the pX. At the equivelent point : smaller the [X-], smaller the pX.

At a smaller titrant concentation, the lower , curve branchement after the equivelent point, point as well as the lower of pX at the equivalent point. To obtain a good feasible titration of Cl(analyte) with Ag+ (titrant) solutions, it is required both concentrations of analyte and titrant smaller than 0.10 M.

Methods in precipitatometric titration p p

Argentometric method Mercurimetric method Kolthoff titration

Argentometric titration

Argentometry is the most usefull method of precipitatometric titration, as it caused of very low solubility product of halide (or pseudohalide) salts i e salts,i.e.
Ksp AgCl = 1,82 . 10-10 Ksp AgCNS = 1,1 . 10-12 Ksp AgBr = 5,0 . 10-13 Ksp AgCN = 2,2 . 10-16 Ksp AgI = 8,3 . 10-17

There are 3 techniques of end point d Th h i f d i determination i i method of Mohr (indicator : chromic potassium) method of Volhard (indicator : ferric salt) method of Fajans (indicator : fluorosceince)

ARGENTOMETRY

MOHR

Mohr titration is used for determination of halide or pseudohalide in a solution Chromate ion (CrO42-) is solution. added to serve as indicator. At the end point the chromate ion is combined with silver ion to form the sparingly soluble, red, silver chromate, Ag2CrO4. Ksp Ag2CrO4 = 1,2 . 10-12 mol3.L-3 12 L Ksp AgCl = 1,82 . 10-10 mol2.L-2
[ Please consider the stoichiometric unit of these ionic reactions ]

Although the solubility product constant (Ksp) of AgCrO4 is close to the Ksp of silver (pseudo)halida, g ( ) these silver salts have different solubility.

Mohr titration has to be performed at a neutral or weak basic solution of pH 7-9 (or pH 6-10). In a lower pH (acid) solution the chromatedichromate equilibrium decreases the sensitivity of [CrO42-] then inhibits formation of Ag2CrO4 ], precipitate. 2 CrO42- + 2 H+ Cr2O72- + H2O
Chromate Dichromate

In a higher pH (basic) solution, Ag2O will be formed as a black precipitate.

Ag+ + ClAg+ + CrO42-

AgCl (p) Ag2CrO4 (p) red

Solubility of Ag2CrO4 > Solubility of AgCl (8.4 (8 4 x 10-5 M) (1.35 (1 35 x 10-5 M)

If Ag+ solution is added to a Cl- solution containing of small quantity of CrO42-, then AgCl will firstly precipitated, while Ag2CrO4 has not yet, and [Ag+] increases progressively until solubility product of the ions reach the value of Ksp Ag2CrO4 (2,0 x 10-12) to form red precipitate.

At the equivalent point : pAg = pCl = 5.00 th i l t i t A Cl 5 00

12 [Ag ][CrO 2- 2 00 [A +][C O42 ] = 2.00 x 10-12 Then [CrO42-] = 2.00x10-12 / (1.0x10-5)2 = 0.02 M

This chromate concentration is too high as yellow colour of CrO42 di t b visual ll l f C O 2- disturb i l observation of Ag2CrO4 (red). In laboratory work we use usually at 0.005 s/d 0 01 M f ll t 0 005 /d 0.01 for minimizing titration error. And it could be corrected by an indicator blank titration, or by t db i di t bl k tit ti b AgNO3 solution standized to a pure chloride salt (equal condition to the sample titration) . ( l diti t th l tit ti )

Mohr titration is limited at pH 6-10 (or pH 7-9). Ionic I i reaction in basic solution will be : ti i b i l ti ill b Ag+ + OH2AgOH Ag2O + H2O 2In acid sol tion [CrO42 ] will decrease until onl a solution, ill ntil only few of ionized HCrO4-, as the reaction will be followed with the dichromate formation : 2H+ + CrO422HCrO4Cr2O72- + H2O If is too low ( < 0,005 M) then the reaction needs excessive addition of [Ag+] to precipitate Ag2CrO4; this might be a titration error. error Dichromate ion, Cr2O72-, can not be used as indicator as Ag2Cr2O7 precipitate is easily dissolved in this ionic solution.
(chromate) the [CrO42-] (dichromate)

Mohr method can be used for determining Brg and CN- in a weak basic solution, but it is not feasible for I- and CNS- as of the salt precipitate adsorption. Ag+ can not be titrated with Cl- solution using indicator of CrO42-, because Ag2CrO4 will be g early obtained and slowly dissolves near the equivalent point. This shlould be overcome by q p y performing a back titration technique : to the solution of Ag+ we add standardized excessive g Cl- solution, then the excess of Cl- is titrated with standardized Ag+ using indicator of CrO42g g .

ARGENTOMETRY

- VOLHARD

Volhard titration is an indirect (back titration) technique which is used if reaction is too slow or if there is no appropriate indicator selected for determining the equivalent point. Titration principle :
Silver solution is added excessively to a (pseudo)halide

Br- + Ag+
excess

AgBr (precipitate)

After reaction has completed, the precipitate is filtered, then the filtrate is titrated with a standardized thiocyanate solution.

Ag+ +

SCN-

AgSCN (solution)

Fe(III) indicator reacts with thiocyanate ion to form a red colour solution : Fe3+ + SCN[Fe(SCN)]2+ The Th reaction requires acid condition, as i b i ti i id diti in basic solution the ferric ions form Fe(OH)3 precipitate. 39 3 Ksp Fe(OH)3 = 2.10-39 mol3L-3 ( [ 3+] = 10-2 M is usually used) [Fe y )
Example : A solution of KBr is titrated with Volhard procedure requires p p q addition of 100 ml of excessed AgNO3 0,095 M, then titrated with 18,3 ml of KSCN 0,100 M using a Fe3+ indicator. Calculate Br- concentration in the initial solution solution.

Volhard method is very common for ion determination based on Ag+ and Cl- reactions, as of very low precipitate salt solubility Acid condition is solubility. required to avoid hydrolysis of Fe3+ indicator. In a neutral solution, some of colour cations (H 2 , l l i f l i (Hg2+ Co2+, Ni2+, Cu2+) will precipitate and disturb the stoichiometric reaction. Volhard method can be used as a direct titration of Ag+ with CNS- as well as back titration of Cl-, Br- and I- d t determination. Th i ti These B - and I- can not be disturb Br d t b di t b by the CNS- as solubility of AgBr is equal to those of AgCNS, while solubility of AgI < solbility of AgCNS.

Titration error of Cl- determination would happen if AgCl reacts with CNS- : AgCl(s) + CNSAgCNS + ClSolubility of AgCNS < solubility of AgCl, then the reaction in above will shift to the left side of the reaction, and the result of Cl- analysis will be lower. lower But this could be prevented by filtering AgCl precipitate or nitrobenzen (poison !) addition before titration with CNS-. Nitrobenzen becomes a lipid layer between precipitate and CNS- solution.

ARGENTOMETRY

FAJANS

Fajans titration use adsorption indicators, i.e. organic compounds which is adsorbed into colloidal precipitate surface during the titration processes.
Example : Fluoresence in form of its fluorescenate (yellowish green) anion react with Ag+ to form an intensive red precipitate which is adsorbed to AgCl precipitate surface caused by ionic pair interaction. First t Fi t step of titration tit i f tit ti titrasi Final t Fi l step of titration : A +I df tit ti Ag Ind
Cl ClClClClCl AgCl ClClClClClAgCl Ag+ IndAg+ Ag+ IndAg+ Ag+ IndAg+ Ag+ Ind-

Adsorption of colour organic compound on a precipitate surface could induce intramolecular electronic shift then change solution colour shift, colour. This phenomenon is usually used for end titration detection of silver salt precipitation. d i f il l i i i Before Eq.Pt. :
(AgCl).ClPrimary layer M+ Secondary layer Excess of Cl-

After Eq.Pt. : q
(AgCl).Ag+ Primary layer y y XSecondary layer y y Excess of Ag+ g

A precipitate tends to adsorp easily ions formating slighty soluble salts with ions of the precipitate lattice. Then, Ag+ or Cl- could be more easily adsorb by AgCl p precipitate than by Na+ or NO3-. These anions in the p y solution will be attracted by the precipitate to form an ionic secondary layer layer.
Fluorescein is a weak organic acid, f Fl i i k i id forms a fl fluoresceinate i i t ion which is not adsorbed by colloidal AgCl precipitate during excess of Cl-. B t in th solution with more excess of Ag+ th f But i the l ti ith f A the fluoresceinate anion will be adsorbed to form a Ag+ shielding layer, f ll l followed b change th solution colour t pink. d by h the l ti l to i k

The factors that must be consider in choosing an adsorption indicator : 1) At the equivalent point dont let the AgCl point, don t precipitate grow too fast to form a big coagulant, for this could sharply decrease adsorptivity of the precipitate surface to indicator molecules. But if it was happened, we can overcome by happened addition of dextrin molecules (as a protective colloid) into the solution so that increase solution, particles dispersion, the colour change will be reversible and after equivalent point we can perform back titration using a standardized chloride (Cl-) solution (Cl ) solution.

2) Adsorption of indicator should be happen near and more fastly at the equivalent point. A bad indicator performance will result a too strong adsorption process resulting which can substitute ion adsorbed before the equivalent point. 3) The pH must be weel controlled for maintaining indication ionic concentration asam, in basic or acidic solution. For example, fluorescein (Ka = 10-7) in a solution having pH > 7 will release small quantity of fluoreseinate ion, hence we can not observe colour change of the indicator. Fluorescein is used feasibly in a solution of pH 7-10, difluorescein (Ka=10-4) is at pH 4-10.

4) It is recommended to choose ionic form of indicator with ionic charge in opposite of titrant ion. ion Adsorption of indicator can not happen before an excess of titrant ion. In tit ti I a titration of A + solution with Cl- methyl violet f Ag l ti ith th l i l t (as chloride salt of an organic base) could be used as an i di t of choice. d indicator f h i Before an excess of Cl- in the solution that resulting a negative charge on colloid layer, cation should not be adsorbed. For this condition, we can use dichlorofluorescein, but it must be added just close to the equivalent point.

Adsorption Indicators
INDICATOR ANALYTE TITRANT REACTION CONDITION pH = 4 pH = 7 8 pH = 2 pH = 1,5 3,5 pH = 4 5 acid solution HNO3 upto 0,3 M neutral 0,02 M soln t l 0 02 l solution of 0,1 M

Diklorofluorescein Fluorescein Eosin Thorin Bromcresol green Methyl violet Rhodamin 6G Orthochrome T O th h Bromphenol blue

ClClBr-, I-, SCNSO42SCNAg+ Ag+ Pb2+ Hg22+

Ag+ Ag+ Ag+ Ba2+ Ag+ ClBrCrO 2C O42 Cl-

List of Precipitation Titrations

ANALYTE Cl-, BrCl-,Br-,I-,SCNBr I SCN Br-,I-,SCN-,AsO43Cl-,CN-,CO32-,S2C2O42-,CrO42FSO42PO43CrO 2C O42 Ag+ Zn2+ Hg22+ TITRANT AgNO3 AgNO3 AgNO3 + KSCN AgNO3 + KSCN Th(IV) BaCl2 PbAc2 PbAc PbA 2 KSCN K4Fe(CN)6 NaCl INDICATOR K2CrO4 Adsorption Fe(III) Fe(III) METHOD Mohr Fajans Volhard (not filtered) Volhard (filtered) Fajans Fajans Fajans Fajans F j Volhard Fajans Fajans

Alizarin Tetrahydroxyquinoline Dibromofluorescein Fluorescein Fl i Fe(III) Diphenylamine Bromphenol blue

MERCURIMETRIC TITRATION
Hg2+ + 2 ClHgCl2 (as for other halides)

When halide ions is titrated with mercuric nitrate solution, [Hg2+] is not found at the equivalent point caused of precipitation of HgCl2 during the titration process. After equivalent point, [Hg2+] increases, react with indicator to form a Hg-indicator complex, e.g. Nitropruside form white precipitate, acid solution of diphenylcarbazide or diphenylcarbazon in forms intensive violet colour solution. Mercurimetric titration requires a blanc titration: 0,17 0 17 ml of Hg(NO3)2 0 1 N for 50 ml of HgCl2 0 05 N 0,1 0,05 N. This blanc titration volume varies as [HgCl2]EquivalentPoint For the excess of [Hg2+] reacts with HgCl2 : HgCl2 + Hg2+ 2 HgCl+

KOLTHOFF TITRATION
Determination of Zn2+ (as titrant) which is precipitated with standard solution of K-Ferrocyanide

2 K4Fe(CN)6 + 3 Zn2+ ( )
potassium ferro (II) cyanide

K2Zn3[Fe(CN)6]2 + 6 K+ [ ( )
potassium zink ferro (II) cyanide

Titration end point is detected by using external indicator such as uranylnitrate uranylnitrate, ammonium molybdate, FeCl3, etc, which needs a special technical skill. So it is better to use internal indicators such as diphenylamine, diphenylbenzidine, diphenylamine sulfonate etc sulfonate, etc. Fe3+ has rduction potential (at 30 oC) as follow : A redox reaction of Fe2+

E = Eo + 0,060 log [Fe(CN)63-] / [Fe(CN)64-]

Acidic solution of ferro-ferric cyanide has much lower reduction potential compared to those required to oxydize the indicator, forms intensive coloured of oxidized form. When Zn2+ is added to this solution then a Zn-ferrocyanide will be formed, followed with increasing reduction potential for Fe(CN)64- removed from ( ) p y , p the solution. After Fe(CN)64- completely reacted, a sharp increase of reduction potential which is followed by appearing blue colour of oxidized form of indicator, caused by excess of Zn2+.in the solution.

The END