C ompl exometri cti trati ons

Comr te-ometric Titrotiont

titration
The Principlebehinda complexometric
A complexometric titrationcanbe simplydefinedasa "volumetric analysis in whichthe formationof
a coloredcomplexis usedto indicate the endpointof a titration."[1-] lt involvesa reaction
b e t w e e na m e t a li o n ( C a 2 * , C u ' F ) d a l i g a n dw h i c hi s
* ,e ' * ,M n 2 * a n dC d 2 * a m o n g s t o t h e ras n
an electrondonor and bondsto the metal ion covalently.Ligandscan either be
m o n o d e n t a t eo, r m u l t i d e n t a t ea n d a f e w e x a m p l e si n c l u d eN H r ,C N - ,a n d
Ethylenediaminetetraaceticacid (EDTA).

T h e a i m o f t h i s t e c h n i q u ei s t o f o r m a c o m p l e xi o n w h i c hc a nt h e n b e u s e di n t h e a n a l y s i o
sf
pharmaceutical products;for exampleto determinethe metal contentof water (e.g.hard
w a t e r )o r t h e m e t a lc o n t e n to f a p h a r m a c e u t i c ap lr e p a r a t i o n .

W h e n a m e t a li o n i s i n s o l u t i o ni t i s s o l v a t e db y w a t e r m o l e c u l e sa, d d i t i o no f a l i g a n d( N H r ,
CN-,and EDTA)displaces the moleculesof water and bondswith the metal complex.A bond
w i t h a m e t a lc o m p l e xa n d a l i g a n di s a c o v a l e n b t o n d a n d i t c a n e i t h e rb e :

a) A coordinatecovalentbond - were the liganddonatestwo of its electronsand the

m e t a lp r o v i d e sa n e m p t y d - o r b i t a l .

Or

b) A basiccovalentbond - were both the ligandand the metal ion eachdonateone

e l e c t r o ni n t o t h e b o n d .

Forminga complexion can be illustratedby the equationbelow:

M + x MX

tzl

acid (EDTAI
Ethvlenediaminetetraacetic

EDTAis a multidentateligandthat can form more than one coordinate(covalent)bond with

a metal ion and becauseof this specialabilityit is then calleda chelatingagent.[2] lt is the
m o s t c o m m o nc h e l a t i n ga g e n ta n d I w i l l t h e r e f o r eu s ei t i n m y e x a m p l e sa n d d i s c u s s i o nt so
follow. lt is a hexaproticacid meaningit hassix protonsand theseionizeat differentpKa's.
t p o nt h e p H o f t h e s o l u t i o n
E D T Ae x i s t si n m a n yf o r m s i n a s o l u t i o na n d t h i s i s d e p e n d e n u
( E D T A = H o Y 2 * + H s Y * + H + Y + H : Y - + H z Y 2 - + H bYu3t-t+hY eam-o) s t d o m i n a n t f o r m o f E D T A l S
Ya-which exists between the p H range t}-t4. The fraction of EDTApresentas Ya-can be
calculatedusingthe equationbelow:
 C ompl exometritic trati ons

ctyo-=[a-1 /IEDTA]

EDTAis a water solublechelatingagentand is made up of four carboxylgroupsand two

aminegroups,[1] it forms 1:L complexeswith metal ions[3] below is the structureof EDTA-

o
ovoH tl
+oH
I I
\N,n--r *\

Ho)/
I
o/-oH
o t4l

f i g u r e 7 : S t r t i c t u r ec t JE D T A ,a d o p t e dJ r o n .
|t'!'L:.l.iP!))y_-']]l!-].t]ilj{t.':j.d.gltii;-t.!-!q,.|)!!i::|!||

pH of the solution and indicators.

Complextitrationshaveto be carriedout in an environmentthat hasa constantpH,the

form Ya-of EDTApredominatesbetweenpH of 10-14.To achievethis a bufferingagentthat
maintainsthis pH rangeis added.Thereis alwaysa challengefacedwhen one of the buffer
t u s t r e a c tw i t h
c o m p o n e n t si s a l i g a n dt h a t b i n d st o t h e m e t a li o n .A n e x a m p l ei s C d z * t h a m
EDTA;if a buffer containingN11o*/NH: is usedthe NHralsoforms strongstableCd2*-NH:
complex,but becauseEDTAforms strongercomplexwith Cd2*it will displaceNHr but the
stabilityof the Cd2*-EDTAcomplexdecreases.
[3J

ln order for the end point of a complextitrationto be determinedthere needsto be an

indicator;a chemicalthat is sensitiveto p H and changescolor in a very short p H range.The
indicatorneedsto be ableto form a poorlystablecomplexwith the metal that quickly
dissociates as the EDTAattachesand forms a more stablecomplex.lt alsoneedsform a
differentcolor when it complexeswith a metal ion and alsowhen it is free in a solution.
 Complexometric
titrations

/
Examplesof indicatorsusedin suchtitrationsincfudeAlizarinfluorineblue,Calcon
carboxylicacid,EriochromeblackTand Methyl blue amongstothers.

The stabilitvconstant(K'fl
K'risa constantvaluethat dependson the concentrationof EDTA[Y4-],
it is calculatedby
u s i n gt w o t a b l e so f v a l u e s[:5 ]

i. Tableof " Formulaconstantsfor metal-EDTA complexes"

ii. The "table of valuesof aya-forEDTAat 25 "C and F=0.10M"

T h ef o r m u l af o r c a l c u l a t i nK
g ' ri s [ 5 ]

' K'r=(ay4-1
(Kr)

Calculating
the titration curve
After a complextitration has beendone the resultsneedto be plottedon a graphso as to
assessthe helpfulness of EDTAas a titrant.The complextitrationgraphslightlydifferswith
the graphof acid/basetitrations,the curveshowsa changein p M [(-loeM) were M is the
metal ionl as a functionof the volumeof EDTA

When plottinga titration curve,the followingare needed

i. Thevolumeof the EDTAto be added

ii. T h e i n i t i a lp H o f t h e m e t a li o n .
iii. Calculations of p M beforeand after the equivalencepoint ( point at which [H.]=[OH-
1)

Calculationsteps [3]

1 ) W r i t e d o w n a b a l a n c e ds t o i c h i o m e t r iecq u a t i o n

2) Calculatethe conditionalformationconstantfor the metaI-EDTA

complex:Krw€re Kr

i s t h e c o n d i t i o n aflo r m a t i o nc o n s t a n o
t r t h e s t a b i l i t yc o n s t a n t .

3) Calculatethe volume of EDTAneededto reachthe equivalencepoint.

4
 Complexometric
titrations

I 4) Calculatep M valuesbeforethe equivalencepoint by determiningthe concentration

of the unreactedmetal.
p M v a l u ea t t h e e q u i v a l e n cpeo i n t u s i n gt h e c o n d i t i o n aflo r m a t i o n
5) Calculate

constant.

6) Calculatep M after the equivalencepoint usingthe conditionalformationconstant.

The following steps need to be taken when plotting the titration curve [3]

i. C a l c u l a t tei t r a t i o ne q u i v a l e n c pe o i n tv o l u m e .

ii. Draw axesplacingp M ( -logM)on the y-axisand the titrantsvolumeon the x-axis

iii. T o i n d i c a t et h e v o l u m en e e d e dt o g e t t o t h e e q u i v a l e n c pe o i n t ,a v e r t i c a l i n e

c o r r e s p o n d i ntgo t h e v o l u m eo f E D T Ai s d r a w n .

iv. p M a n d m a r kt w o p o i n t sb e f o r et h e p o i n to f e q u i v a l e n c e .
Calculate

v. p M a n d m a r kt h r e e p o i n t sa f t e r p o i n to f e q u i v a l e n c e .
Calculate

vi. n f t h e c u r v eu s i n gd a s h e d( - - - - - )l i n e s .
D r a wa p r e l i m i n a r ya p p r o x i m a t i o o

vii. n f t h e t i t r a t i o nc u r v eb y d r a w i n ga s m o o t hc u r v e .
D o t h e f i n a la p p r o x i m a t i o o

titration calculations
Exampleon complexometric tsl

Question

Calciumreactswith EDTAto form a L:l stablecomplex,the solutionwas bufferedto p.H 10

and Mordant blackil was the indicatorused(colorchangeRedto Blue). 40.00mL of CaClz

with a concentrationof 0.0300Mwas titrated with EDTAof concentration0.0700M.

l . W r i t e d o w n a b a l a n c e ds t o i c h i o m e t r iecq u a t i o n

2. Calculatethe stabilityconstantKr

3. Sketcha titration curveand distinctlymark 5 pointson the graph basedon the

c a l c u l a t i o ntsh a t y o u w o u l d h a v em a d e .

I ocknowledgethat t got the idea of this examplefrom the link belowand then modifiedit to the
bestof my obility.

hJtp:iiwww.chem.mun.calcourrseinfo/c3_10_0Alt
%ZaEAIM"ZQ!tratiorrs.pdf

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C*" f)
 C ompl exometri cti trati ons

[ 1 B . K I RUTH IG"AS, R MU n i v e rc acl h e m i s tr y:D epartmentof pharmaceuti cal

chemi stry,"l Onl i ne].
[A ccessed 29
I A v ailabl eh: ttp ://w w w .s rm u n i v .a c .i n / dow nl oads/C ompl exometri c-Ti trati on.pdf.
March 20f41.

c trati ons,"N ew D el hi ,l ndi a,2007.

[ 2 H. A , " T h e o re ti v abl a s i so f a n a l y s i sc: o mpl exometri ti
l
: h e mw i k i , " l O n l i n e ]A
[ 3 D . H a r v e y ", U C D a v i sC . vailable:
I http://chemwiki.ucdavis.edu/Analytical_Chemistry/Analytical-Chemistry-2.0/09-Titrimetric-Me
thods/9C-Complexation-Titrations. [Accessed29 March 2}t4l.
 I

C ompl exometritic trati ons

/
[4 [. EDTA,"Wikipedia,"20 OCTOBER 2OO5.lOnline].Available:
[Accessed29 March 2Ot4].
I http:/lpl.wikipedia.org/wiki/Plik:Ethylenediaminetetraacetic.png.

[5 H. L. G. Dr. G. Van Biesen,"Principlesand Techniques,"in AnalyticalChemistry,PrenticeHall,Inc,

I zOtI, p. chapter 11.

[5 C. Billing,"Wits University:Chemistrydepartment,Compfexometrictitrations notes," 2001".

. a i l a b l eh: ttp ://w w w .g h .w i ts.ac.za/chemnotes/chem2001-
I [ O nline] Av
2/ Caren_BiIIi nglComplexation%20Notes.pdf . [Accessed29 M arch 2OI4].