56 ANALYTICAL CHEMISTRY

7.3 TITRATIONS BY TURBIDITY WITHOUT AN INDICATOR

If NaCl is added to a solution containing silver, at first a suspension appears which
cOagulates. The speed at which coagulation takes place gives an indication of
cquivalence point. The addition of NaCl is continued till the end point is reached the
i.e.
formation of AgCl precipitate in the supernatant liquid. However slight excess of NaC
end point e.g. is
subsequety
nearuntilnessthere is
added at the
Ag]=lcirl=i.6x10-10 =1.2x10-15
The determination of Ag as AgCl can also be done by turbidmetric measurements by
light.
7.4 VOLHARD'S METHOD
Scateing of

The titration of Ag with NH,SCN with ferric alum as an indicator is an example of the
involving the formation of a coloured substance in the solution. During titration AgSCN class of titration
while at the end point excess NH,SCN reacts with Fe(II) to form deep red [Fe SCN]2*. is
formad
thiocyanate which will give a visible colour is very small. Thus the end point error is veryThe amount o
solution should be shaken vigorously at the end point as silver ions are absorbed on the small but tik
are then desorbed. In Volhard's method, one can easily determine chloride ions in acidic and precipitate
otherwise in basic media Fe* will hydrolyse. An excess of AgNO, is added to chloride s0lu solution,
part of it is unreacted. Ag solution is back titrated with ferric alum as indicator, but the methd
source of error. AgSCN is less soluble than AgCl (K = 1x10-12)
AgCl + SCN ’ AgSCN + CI; Fe* +SCN Fe(SCN)* (Red)
This will consume more NH,SCN and chloride content will appear lower (~2% error). This emvr
can be eliminated by filtering off AgCl precipitate before back titration or if a little nitrobenzene is
added, it will adhere to AgCl and protect it from reaction with thiocyanate, however, nitrobenzene slos
down the reaction. This can be avoided if Fe(NO,), and a small measured amount of NH, SCN ar
added to the chloride solution at the start with HNO, and the mixture titrated with AgNO, til the re
colour disappears.
7.5 MOHR'S METHOD
The titration of halides with AgNO, is
carried out with Na,CrO, as
atitration which proceeds with the formation an indicator. This is an example o
of a new coloured
Ag,Cro, ions precipitate as brick red Ag,CrO,. The solution shouldprecipitate.
be neutralAtor the end pout
slightly alkaline, bu
not too basic so as to precipitate Ag as Ag(OH),. Further, with too much acid the end pointwillie
delayed due to lowering of Cr0;
concentration as per reaction
Ag +Cl =AgC1 Ksp =1.8x10-10
White

2Ag* +Cr0 =Ag,CrO4 Kyp, =1.lx10-12

Yellow Red
 PRECIPITATION TITRATIONS 57

H+CO’HCO,.Under proper conditions Mohr's method is accurate and applicable at low CF

concentration.In titrations of this type the colour-indicating precipitate
must be more soluble than the
fornned during titration. Also it should not be so soluble as to need more reagent.
mainprecpitate reagents are used as indicators such as the one shown in Fig. 7.2. These are used in
Hence onganic
with end point by a precipitate red barium salt. This method is also used
sulphatetitration with BaCl,isopropylacohol is added: at 25°C. The colour change is, however, not very
analysis. At pH 8.0
inwater is essential to give adequate concentration of indicator anions without precipitat-
sharp. Control of pH used as indicators in certain
s the unwanted substances. Lake forming organic reagents are also
titrations e.g. titration of F ion with
) Th (NO,), with sodium alizarine sulphonate as an indicator. Thus
2.9-3.4. CH,CI COOH buffer is used
ThE, Drecipitates and at the end point a red lake appears at a pH
present.
if asmall amount of F is

-Co HO.
-ONat
2Na

0=CCONa* OH
Co

Na - rhodizonate Na-salt of tetra hydroxyquinone

Fig. 7.2 Organic adsorption indicators

7.6 ADSORPTION INDICATORS IN PRECIPITATION TITRATIONS

from light yellow to
If AgNO, is added to NaCl containing fluorescein at the end point colour changes
due to adsorp
rose pink. On standing, the precipitate appears coloured while the solution is colourlessadsorption on a
tion of ind -ator on the precipitate of AgCi. The colour of a substance is modified by
surface. The reaction is represented with an anionic indicator, like fluoroscine:
If excess Cl: (AgCl) CF + FL’ no reaction (If FL =CH0, ie. fluorocine)
Ifexcess CI: (AgCl)Ag* + FL ’ (AgCl) (AgFL) adsorption
In the case of a cationic indicator the reaction is:
If excess Cl: (AgCl) CI + (MV) ’ (AgCl) (CI MV)t adsorption
If excess Cl: (AgClI) Ag + (MV) ’ No action if MV = methyl violet

CO0
COOH
CI Cl

HO OH HO OH

Fig 7.3 Fluorescein Fig. 74 Dichlorofluoroscein

58 ANALYTICAL CHEMISTRY

The adsorptivity of fluoroscein anions by substitution with bromoriodo groups is greatly

as shown in Fig. 7.3 - 7.4.
This is because halogen atoms make these indicators more polarizable and therefore enhanced
strongly adsorbed. All adsorption indicators are ionic. In addition to these, adsorption they are more
zarin and thorin are also used as indicators in titration of SO with BaCIO, in organic insolvent
dicators, alk-
such as acetone as shown in Fig. 7.5 - 7.6. Eosine and Erythrosine (Fig. 7.7 - 7.8) are media also
adsorption indicators. effective
OH

OH As0,H, SC, Na*

-N=N
sa, Na

`so, Na
Fig. 7.5 Alizorine Fig. 7.6 Thorin

COO
COO
-I
Br Br

HO OH
HO OH
I
Fig. 7.7 Eosin Fig. 7.8 Erythrosin
In addition to the above adsorption indicators, other indicators used in precipitation titration are
chrysodine derivatives. They are acid base indicators and adsorption redox indicators (Fig. 7.9). They
give reversible colour.
NH,

cH,O-N=N -NH,

Fig. 7.9 Structure p-ethoxychrysodine

This is used for titration of iodine against Agt ions. It acts in the following manner:
(yellow in base)
(Agl) Agt + MH’ (Agl) Agt M+H (red in acid)
(Agl) M+ H* ’ (Aglyt (MH)
Congo red is another acid base indicator.
 PRECIPITATION TITRATIONS 59

and demerits of adsorption indicators can be summarised as: They give very small end
The merits
errors,the colour change with adsorption indicators are very sharp. Adsorption, being
a surface
point
phenomenon,these indicators are dest suited for precipitates having alarge surface area, adsorption
indicators losetheir value if the precipitate coagulates in the presence of highly charged ions e.g. we
n then for A () due to coagulation. Protective colloids can eliminate this problem, but their
use has
limitations for optimum control of pH, or concentration of precipitate, during adsorption and
desorption procedures.

77 MISCELLANEOUS INDICATORS, FORTITRATIONS

follows:
Zinc with K, Fe(CN), reacts as
2[Fe(CN) +3Zn* + 2K* -’ K,Zn,[Fe(CN)J,
Diphenylamine is used as indicator with K,[Fe (CN)Jas the titrant
[Fe(CN),J+e ’ [Fe (CN),J if [Fe (CN),I= Fe (CN)J
is high the indicator is oxidised to the blue
the indicator is colourless but if ferrocyanide concentration
titration the situation is different. Thus at the
form. At the end point and in the beginning of the potential is high, while at the end point a
beginning, ferrocyanide concentration is low and redox
the indicator changes from blue to colour
Sudden drop is observed as ferrocyanide accumulates and so mention the so called hydrolytic titration.
we
less. Cadmium, calcium can be titrated like zinc. Finally hydrolysis of the excess of reagent which in
the
Inthese titrations the end point is markedly shown by is a salt of a weak base or acid
indicator provided the reagent
turn causes a color change in the acid base the pH as
e.g. Ba against Na, CO, to give BaCO,; with excess of Na,CO, it hydrolyses and increases
bromophenol blue
Al with NaOH in excess of chloride with
noted by phenolphthalein as indicator, e.g.
indicator.
PROBLEMS

gram feldspar sample is dissolved to give a 0.1801 gram mixture of chlorides of sodium and
7.1 A 1.5 mixed with 50 ml of 0.08333N silver nitrate
to
potassium. The salts are laxivated with water, 0.IN
The excess silver nitrate is titrated against
precipitate chloride as insoluble silver chlorides. and
thiocyanate to give an end point at 16.47 ml. Calculate % of oxide of sodium
ammonium
potassium in the mixture.
NaCl
Answer: Let x = gram of KCI(0.1801 - ) = wt of
(0.1801 x)
Total meg. of mixed halides= NaCl/100
KCI/1000
(0.1801 x) =(50x0.08333) (16.47 x0.10) =2.52
0.0746 0.0585
- 01.52)
Therefore on solving we getx= 0.152 KCl, NaCI = (0.1801
factors for
= 0.0281 g NaCl. Conversion
2KCl=K,O is 0.528, 2 NaCl= Na,0is 0.53