Section 8
Complex-Formation
Titrations
Complex-Formation Titrations
General Principles
Most metal ions form coordination compounds with
electron-pair donors (ligands)
Mn+ + qLm- MLqn-mq
Kf = [MLqn-mq]/[Mn+][Lm-]q
The number of covalent bonds formed is called the
coordination number (e.g. 2,4,6)
e.g., Cu2+ has coordination number of 4
Cu2+ + 4 NH3 Cu(NH3)42+
Cu2+ + 4 Cl- Cu(Cl)42-
Complex-Formation Titrations
General Principles
Typical Inorganic Complex-Formation Titrations
Analyte
Titrant
Remarks
Hg(NO3)2
Br-, Cl-, SCN-, Products are neutral mercury(II)
CN-, thiourea complexes; various indicators used
AgNO3
CN-
Product is Ag(CN)2-; indicator is I-;
titrate to first turbidity of AgI
NiSO4
CN-
Product is Ni(CN)42-; indicator is
AgI; titrate to first tubidity of AgI
KCN
Cu2+, Hg2+,
Ni2+
Products are Cu(CN)42-, Hg(CN)42-,
Ni(CN)42-; various indicators used
Complex-Formation Titrations
General Principles
The most useful complex-formation reactions for
titrimetry involve chelate formation
A chelate is formed when a metal ion coordinates
with two of more donor groups of a single ligand
(forming a 5- or 6- membered heterocyclic ring)
Complex-Formation Titrations
General Principles
Chelate Formation Titrations
Ligands are classified regarding the number of donor groups
available:
e.g., NH3 = unidentate (one donor group)
Glycine = bidentate
(two donor groups)
(also, there are tridentate, tetradentate, pentadentate, and
hexadentate chelating agents)
Multidentate ligands (especially with 4 and 6 donors) are
preferred for titrimetry.
react more completely with metal ion
usually react in a single step
provide sharper end-points
Complex-Formation Titrations
General Principles
Aminopolycarboxylic acid ligands
The most useful reagents for complexometric titrations are
aminopolycarboxylic acids
(tertiary amines with carboxylic acid groups)
e.g., ethylenediaminetetraacetic acid (EDTA)
EDTA is a hexadentate ligand
EDTA forms stable chelates with most metal ions
Complex-Formation Titrations
Solution Chemistry of EDTA(H4Y)
EDTA has four acid dissociation steps
pKa1= 1.99, pKa2= 2.67, pKa3= 6,16, pKa4= 10.26
5 forms of EDTA, (H4Y, H3Y-, H2Y2-, HY3-, Y4-)
EDTA combines with all metal ions in 1:1 ratio
Ag+ + Y4- AgY3
Fe2+ + Y4- FeY2
Al3+ + Y4- AlY
KMY = [MYn-4]/[Mn+][Y4-]
Complex-Formation Titrations
Formation Constants for EDTA Complexes
Cation
KMY
Log KMY Cation
KMY
Log KMY
2.1 x 107
7.32
Cu2+
6.3 x 1018
18.80
Mg2+ 4.9 x 108
8.69
Zn2+
3.2 x 1016
16.50
Ag+
Ca2+
5.0 x 1010 10.70
Cd2+
2.9 x 1016
16.46
Sr2+
4.3 x 108
8.63
Hg2+
6.3 x 1021
21.80
Ba2+
5.8 x 107
7.76
Pb2+
1.1 x 1018
18.04
Mn2+ 6.2 x 1013 13.79
Al3+
1.3 x 1016
16.13
Fe2+
2.1 x 1014 14.33
Fe3+
1.3 x 1025
25.1
Co2+
2.0 x 1016 16.31
V3+
7.9 x 1025
25.9
Ni2+
4.2 x 1018 18.62
Th4+
1.6 x 1023
23.2
Complex-Formation Titrations
Equilibrium Calculations with EDTA
For Mn+ + Y4- MYn-4 KMY = [MYn-4]/[Mn+][[Y4-]
Need to know [Y4-], which is pH-dependent
pH dependence of Y4-:
Define: = [Y4-]/CT
CT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]
Conditional Formation Constant, KMY
[MYn-4]/[Mn+][[CT] = KMY
KMY = KMY = [MYn-4]/[Mn+][[CT]
Complex-Formation Titrations
Equilibrium Calculations with EDTA
Computing free metal ion concentrations:
Use conditional formation constants, KMY
values depend on pH
Thus, KMY are valid for specified pH only
values have been tabulated vs pH
YY4-4-complexes
complexeswith
withmetal
metalions,
ions,and
andso
sothe
thecomplexation
complexationequilibria
equilibriaare
arevery
verypH
pHdependent.
dependent.
22Only
Onlythe
thestrongest
strongestcomplexes
complexesform
formininacid
acidsolution,
solution,e.g.,
e.g.,HgY
HgY 2-; ; CaY
CaY2-forms
formsininalkaline
alkalinesolution.
solution.
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
Fig. 9.1. Fraction of EDTA species as a function of
KKf ==conditional
conditionalformation
formationconstant
constant==KKff4.4.
f
ItItisisused
usedatataafixed
fixedpH
pHfor
forequilibrium
equilibriumcalculations
calculations(but
(butvaries
varieswith
withpH
pHsince
since4 4does).
does).
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
Fig. 9.2. Effect of pH on Kf values for EDTA chelates.
Complex-Formation Titrations
Equilibrium Calculations with EDTA
Example: Add excess EDTA to Ni2+ solution at pH 3.0.
50.0 mL 0.0500M EDTA added to 50.0 mL 0.030M Ni2+
Assume very little Ni2+ is uncomplexed:
C(NiY ) = [NiY2-] = 50.0 mL x 0.030M/100.0mL = 0.015M
C(EDTA) = ((50.0 x 0.050) (50.0 x 0.030))/100.0 = 0.010 M
KMY = 4KMY = [NiY2-]/[Ni2+][0.010] =0.015/[Ni2+][0.010]
2-
KMY = 4.2 x 1018; 4 = 2.5 x 10-11 @ pH = 3.0
[Ni2+] = 1.4 x 10-8M
Complex-Formation Titrations
Metal-EDTA Titration Curves
Titration curve is: pM vs EDTA volume
Conditional Formation Constant, KMY for specific pH
e.g., 50.0mL 0.020M Ca2+ with 0.050M EDTA, pH 10.0
at pH 10.0, K(CaY ) = (4)(KCaY) = (0.35)(5.0 x 1010) = 1.75 x 1010
(a) pCa values before the equivalence point (10.0mL)
Ca2+ + Y4- CaY2assume: [CaY2-] = added EDTA dissociated chelate
[Ca2+] = unreacted Ca2+ + dissociated chelate
Dissociated chelate = CT << [Ca2+], [CaY2-]
[Ca2+] =((50.0 x 0.020) (10.0 x 0.050))/(60.0) = 0.0083M
pCa = 2.08 at 10.0mL EDTA
2-
Complex-Formation Titrations
Metal-EDTA Titration Curves
Titration curve is: pM vs EDTA volume
Conditional Formation Constant, KMY for specific pH
e.g., 50.0mL 0.020M Ca2+ with 0.050M EDTA, pH 10.0
at pH 10.0, K(CaY ) = (4)(KCaY) = (0.35)(5.0 x 1010) = 1.75 x 1010
2-
(b) pCa value at the equivalence point (20.0mL)
assume: [CaY2-] = added EDTA dissociated chelate
[Ca2+] = dissociated chelate = CT << [CaY2-]
[CaY2-] = ((20.0mL x 0.050M)/(70.0mL))-CT 0.0142M
K(CaY ) = [CaY2-] / [Ca2+] [CT] = (0.0142)/[Ca2+]2
[Ca2+] = ((0.0142)/(1.75 x 1010))1/2 = 9.0 x 10-7M;
pCa = 6.05 at 20.0mL EDTA
2-
Note: assumption (CT << [CaY2-]) is OK
Complex-Formation Titrations
Metal-EDTA Titration Curves
Titration curve is: pM vs EDTA volume
Conditional Formation Constant, KMY for specific pH
e.g., 50.0mL 0.020M Ca2+ with 0.050M EDTA, pH 10.0
at pH 10.0, K(CaY ) = (4)(KCaY) = (0.35)(5.0 x 1010) = 1.75 x 1010
2-
(c) pCa value after the equivalence point (25.0mL)
assume: [CaY2-] = stoichiometric amount [Ca2+]
CT = [excess EDTA] + [Ca2+] excess EDTA]
CT = ((25.0 x 0.050)-(50.0 x 0.020))/(75.0) = 0.0033M
[CaY2-] = ((50.0mL x 0.020M)/(75.0mL))-[Ca2+] 0.0133M
K(CaY ) = [CaY2-] / [Ca2+] [CT]; [Ca2+] = (0.0133)/(0.0033)(K(CaY ))
[Ca2+] = 2.30 x 10-10
pCa = 9.64 at 25.0mL EDTA
2-
Note: assumption ([Ca2+]<<CT << [CaY2-]) is OK
2-
As
Asthe
thepH
pHincreases,
increases,the
theequilibrium
equilibriumshifts
shiftsto
tothe
theright.
right.
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
Fig. 9.3. Titration curves for 100 mL 0.1 M Ca2+
versus 0.1 M Na2EDTA at pH 7 and 10.
The
Thepoints
pointsrepresent
representthe
thepH
pHat
atwhich
whichthe
theconditional
conditionalformation
formation
6
constant,
constant,KKf',',for
foreach
eachmetal
metalisis10
10,6,needed
neededfor
foraasharp
sharpend
endpoint.
point.
f
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
Fig. 9.4. Minimum pH for effective
titrations