Chapter 8

Complexometric (EDTA)
Titratioms
cactions involving complex ions or undissociated neutral molecules in solution fall under the class
Nof complexometric titrations. The basic requirement is that such a complex should be extremely
soluble. The complexes of metals with EDTA (disodium salt) fall into this category. In addition to
EDTA titration, titrations involving mercuric nitrate and silver cyanide are also known as complexometric
titrations.

8.1 EDTA AND THE COMPLEXONES

EDTA also called by several other names such as Versene, Complexone II, Sequesterene, Nullapon,
Trilon B, Idranat II. It has the structure as shown in Fig. 8.1.
HOOCCH, CH,COOH
N
-CH,CH,
HOOCCH, CH,COOH
Fig. 8.1 EDTA

CO
CO
H,c

CH,
Ca

H,C

CO

Fig. 8,2 Ca (NTA) complex

62 ANALYTICAL CHEMISTRY

It has both donor oxygen atoms and donor nitrogen atoms and it can form six (or
chelate rings simultaneously. Another agent is nitriliotriacetic acid N(CH,COOH),. five)
plex is shown (Fig. 8.2). Schwarzenbach exploited a number of amine carboxylic Its
acids as calciumemmbeCom-red
masking agents.
Flaschka reviewed its use as a masking agent. Several metals from complexes at titrating and
complexing action is proportional to the activity of the free anion y- (if acid is H,Y
constants pK, = 2.0, pK, =2.64, pK, =6.16, pK, =10.26) showing that activity of Y4- with
dif ering pH. The
1.0 to 10.0and universally changes as the square of [H"]in pH 3.0-6.0. The varies
complexes of
iofromnisatiophin
metals with
higher charge are more stable. Only Be?*; UO;" do not form complexes with EDTA. In addition
complexing agents are used in titrimetry (Fig. 8.3 and Fig. 8.4) are EGTA and CDTA. other
CH,-0-CH,CH,-N(CH,COOH),
CH,-0-Ch, -CH, -N(CH,COOH),
i.e. 1, 2-di (2-aminoethoxylethane)
NNNN (tetraacetic acid (EGTA)
Fig, 8.3 EGTA

CH,
CH, CH N(CH,COOH),.

CH, CH -N(CH,COOH),
CH,
i.e. 1, 2-di diaminocyclohexane
tetraacetic and (CDTA)
Fig. 8.4 CDTA
Similarly triethylene tramine (trien) is also used in titrations. H,Y or Na, H,Y
EDTA dissolves readily in water. It is available in high degree of are its formulat.
aprimary standard but due to an uncertain purity. The dihydrate can be used as
amount of water it is better to standardise it. Cadmium metal
is a good primary standard for such
standardisation.
8.2
COMPLEXOMETRIC TITRATION CURVES
EDTA is hexadentate, but in titration we use the
During the complexation reaction we have disodium salt hence it behaves as quadridentate,

M+R IMR'4)
IMR4)] so K,s absolutely stability constant
The fourdissociation constants of acid HR are as follows:
Case (i) H,R +H,0 H,0* +
H,R K=1.02x10
 ammonia
auxiliary
are
chelatine
They or
should
complex
Pthalein Thymolpthelin
RedErichrome
of and typeindicator
themselves.
themselves at
of effect CalceinZincon
concentration 8.4 sulphophthalem
pH Name Tiron
the Table The =
the
of K, as Structure
stability.definedZn]
has are
concentration the
reagents
in No. XV XVIXVIIXVII
alte XIX XX XXI
80 ammonia which shown log
EDTAequilibrium
i.e. complexuncomplexed
indicators
Metallochromic
M) vs affected. indicators
are i.e. uponcurve
60 Thus
(b). Red
Pyrocatechol
10 Zn different
from
colour SP
indicators
xEDTA(1for The the depends
the indicator Sulphon
BlackVaramine
Blue Patton
Reeder
Evennot or
curve
pH9.0.
8.6
INDICATORS
METALLOCHROMIC
8.3 with in
IDA-iminodiacetate (Total Calgmite
SPADNS
40
of Titration region. is inflection Structure Thorin
Name
10'M
=1x
a M used
10
b=1x ml Fig. C performed indicatormetal =(MZn)/MI
at (same of commonly 8.4
Table
20 8.6 EDTA point magnitude of of No. VIII IX X XI XII XIII XIV
Fig, an valueconstant
(6) are complexes
a
have
for equivalence of
M Most usefulness K,
titrations
curves
0.001 the are pM
CHEMiSTRY
ANALYOAL
68 at stability
16
12 4 0 indicators.
indicators Black Pyrecatechol
violet
Eriochrome Acid
chrome
Blue
twoand minimum, free Erichrome
Blue Xylénol
Orange
the complexometric
shows
(a) in The half apparent Murexide
and
metal
whose
8.6 pZn and
azocompounds.
metallochromic Structure
Name
8.6 (Fig. kept Most PAN
complexed
is
Fig. in is
(a) change
agent Most (XXI). Ky No. II V V VI VII
M in
69 so,Na
TITRATIONS
8.17. napthol
OH
to OH black OH black (pyridylazo)
(EDTA)8.7 -N=N
Figs. N=N Blue Chrome
OH
COMPLEXOMETAIC Erichrome
in Naso Acid
1.2
the OH N=N PAN
(IV)
in
shown
(II) so,Na (VI)
N
NaSO,
are
OH CH,COOHCH,COOH
indicators
CH,
metallochromic o CH,
N -so,H
OH 10.5)
5.0) 5.0)
8.0- OH
-N=N - 1.0
(pH OH 1.0
important (pH (pH
OH T
black violet NCH, orange
OH
of NO, Eriochrome Pyrocatechol Xylenol
structure
So,H
Naso, HO H,C
HOOC-H,C. (V)
HOOC-
H,C
)
The (II)
 T
SO,H the Black
B acidic
if
andbe Eriochrome blue
Varamine
(XII)
(VII)
ThorirOH SPADNS will
(X) the point
-N=N
titrant
uponequivalence
OH
thei.e.is:
depends -NH HCI
OH
HSO, EBTchange
of
HSO, HSO equivalence (orange)
point.
KZnthe colour
at In
of pM end
value The
equals
versus
the H,N
the on 11.5.Hln? (blue)
acids change
C=0 K,, error
=
-so;H log pk, so,Na
weakIf colour as
H N 13.0) 11.5) pH. cause 6.9,
H
OH
H, (purple)
In
-
6.0 are theof will=pk,
9.0 indicators
on curve N N Sulphon
black
(XI)
(pH (pH and indicator large, HO -N=N
so,Na
70
ANALYTIGAL
CHEMISTRY C= Murexide -N=N Calmagite the
reagent is
OH these small,pK,
of
(VII) (IX) amount
the its
all is acid
N N H CH, of indicator
Since
constants
largetribasic
so,Na
of A
71 pK,tooand
xylenol
TrranONS anda blocked
COOH
6.0 9.2 Sometimes
Red
Pyrocatehol
XIV) so, pH=
(EDTA) -OH is
pk, complex
Above
(XVII)
Zincon
Tiron
(XVI) HN pH.
CoNEOMETIHC C,H, 0,
OH OH 8.0.=
pK,neutral
strong
so,H 0,s <
-N N pH wherein
OH A
at effective
so,H region,titration.
inefficient
CH,COOH
CH,COOH pH indicators
direct
is broad
indicator
-CH, in
CH,N -OH EBT
a fluorescent
C=0 Na-so, has
COOH the Murexidewith
but formed
Dye Calceinred are
40 Reeders' (XV)
Phthelein
Complex blue
NN purple
indicator.
HO or is
calcein
N=N Solochrome complex
and NCH, is
OH Patton complex
an a
OH as and weak
(XII) HOOCH,C
HOOCH,C CH, (XVII) useless
HO metal Calcein
to0
is or
Theorange
10.5.srong
=
 andIndicator, V
Number XIIL, V, when
EBT is back II,
N X,
withsample
Reeder's -N=N-C=c
C=N Ind.
Metal II,
VI, saltis
Which
and
complexes
B
CH, red I
I, X calcium
the added
Eriochrome Th T, Zn
Zr EBT)
whenand V
is XV XVII a
metal Patton
EDTA XVIII
VIII,
XIX, with
analysis CH,COOHCH,COOH number
OH (XX) CH,COOH
CH,COOH Ind.
II,
Nunber I, complex
I, VI, complex
stabledoubt of
ahappens
water excess indicator I,
ThymolphthalexoneXIX,XIX, ofMg(EDTA),
form no Na'So,
in is then CH,N, CH,-N coloured
CH, with Metal Mg Mn Hg Ag Ni
Ni analysis
Co, weak, titration
XVIII a
Cu, reaction
water
is magnesium. (XXI)
XVII the forms
addition
e.g. complex Metal XVII
VII,
XIX, V,
HO turn
for
indicator
HO
(CH),CH: (CH,),CH Ind.
Metal
Number XII XII,
VI,
VII,
II,
8.6 II,
Suchindicator -OH XVI,I,
in
Table XVII XIX, (which
indicator
or OH Bromophyrogallol
(XIX)
red Substitution
titration
involves
metals. zinc Br II,
as
functioning
best Ch. CO Cu
72
CHEMISTRY
ANALYTICAL of Pb
OH Fe Mg
KCNThemetal
these solution
I,XVIII
XIX, free
maskcopper.
the OH Ind.
Metal
Number
II, V
XVII III,
XIX, XIII
I,VII,
and
from
if standard XV
I,
to contrary 0,S Ca(EDTA),
with
prevented Br.
nated Ba Bi Cd
thewith Al Ca
use