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Complex-Formation Titrations
COMPLEX-FORMATION REACTIONS
H H
.. ..
OH
H2 C
2H+
Mn+
HO HO O
H2 .. .. C N C C N H2 H2 C H2
H2 O C OH C H2 OH O
O O O O M
N N
UNIVERSITY OF THE PHILIPPINES MANILA Complexometric titrimetry are titrimetric methods based on complex formation.
It is based upon a particular class of coordination compounds called chelates. A chelate is produced when a metal ion coordinates with two (or more) donor groups of a single ligand to form a five- or six-membered heterocyclic ring. Multidentate ligands, particularly those having four or six donor groups, have two advantages over the unidentate ones. 1) react more completely with cations and thus provide sharper end points 2) react with metal ions in a single-step process
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pM
10
Much sharper end point is obtained with a reaction that takes place in a single step
EP 0 Volume of Titrant
0
H 4Y
2
H2Y2-
3
HY3-
4
Y4-
0.5
0 0
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H3Y-
6 pH
10
12
14
UNIVERSITY OF THE PHILIPPINES MANILA It is apparent that the H2Y2- predominates in moderately acidic media (pH 3 to 6). Only at a pH values greater than 10 does Y4- become a major component of solutions.
COMPLEXES OF EDTA AND METAL IONS
EDTA reagent combines with metal ions in a 1:1 ratio regardless of the charge on the cation.
AgY3AlYM : EDTA
Billones Lecture Notes
H N C C N H H2 H2 -OOC COO-
H 4Y
H2Y-2
-OOC
H N C C N H H2 H2 -OOC COOH
COO-
-OOC
H N C C N H2 H2 -OOC
COOCOO-
H3Y-
-OOC -OOC ..
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..
N C C N H2 H2
..
..
..
HY-3
COOCOO..
Billones Lecture Notes
Y-4
UNIVERSITY OF THE PHILIPPINES MANILA The dissociation constants for the acidic constants for the acidic groups in EDTA are K1 = 1.02 x 10-2 K2 = 2.14 x 10-3 K3 = 6.92 x 10-7 K4 = 5.50 x 10-11 Formation constants KMY for common EDTA complexes
The constant refers to the equilibrium involving the deprotonated species Y4- with the metal ion:
MY(n-4)
logKMY
Cation
KMY
6.3 x 1018 3.2 x 1016 2.9 x 1016 6.3 x 1021 1.1 x 1018 1.3 x 1016 1.3 x 1025 7.9 x1025 1.6 x 1023
logKMY
4 = [Y4-] cT
[Y4-] = 4cT
Mn+
MY(n-4)
UNIVERSITY OF THE PHILIPPINES MANILA Combining the two constants yields a new constant KMY
KMY = [MY(n-4)+] = 4KMY [Mn+]cT KMY = 4KMY
KMY describes equilibrium relationships only at the pH for which 4 is applicable.
4 =
HY3-
4 at Selected pH Values
pH 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0
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4
3.7 x 10-14 2.5 x 10-11 3.6 x 10-9 3.5 x 10-7 2.2 x 10-5 4.8 x 10-4 5.4 x 10-3 5.2 x 10-2 3.5 x 10-1 8.5 x 10-1 9.8 x `10-1
Example
Calculate 4 and the mole percent of Y4- in a solution of EDTA that is buffered to pH 10.20. [H+] = antilog (-10.20) = 6.31 x 10-11
From the values for the dissociation constants for H4Y, we obtain
K1 = 1.02 x 10-2 K1K2 = 2.18 x 10-5 K1K2K3 = 1.51 x 10-11
signicant conguration
At low pH values, in contrast, only the first two or three terms are important
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UNIVERSITY OF THE PHILIPPINES MANILA Calculation of the Cation Concentration in EDTA Solutions
Calculate the equilibrium concentration of Ni2+ in a solution with an analytical NiY2- concentration of 0.0150 M at a pH (a) 3.0 and (b) 8.0.
Ni2+ + Y4-
NiY2-
NiY2-
Ni2+ + Y4-
Kinstab =
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1 KMY
very small
Billones Lecture Notes
UNIVERSITY OF THE PHILIPPINES MANILA [NiY2-] = 0.0150 [Ni2+] 0.0150 because Kinstab is small
Since the complex is the only source of both Ni2+ and the EDTA species,
[Ni2+] = cT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y] Substitution of this equality gives KMY = 4KMY = [NiY2-] = [NiY2-] [Ni2+]cT [Ni2+]2 (a) 4 is 2.5 x 10-11 at pH 3.0. Substitution of this value and the concentration of NiY2- into the equation for KMY gives KMY = 0.0150 = 4KMY = 2.5 x 10-11 x 4.2 x 1018 = 1.05 x 108 [Ni2+]2
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Calculate the concentration of Ni2+ in a solution that is prepared by mixing 50.0 mL of 0.0300 M Ni2+ with 50.0 mL of 0.500 M EDTA. The mixture was buffered to a pH of 3.00.
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Here, the solution has an excess of EDTA, and the analytical concentration of the complex is determined by the amount of Ni2+ (limiting reagent) originally present. Thus,
cT = 0.0100 M
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Derive a curve (pCa as a function of volume of EDTA) for the titration of 50.0 mL of 0.00500 M Ca2+ with 0.0100 M EDTA in a solution buffered to a constant pH of 10.0.
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At EP,
[Ca2+] = cT
UNIVERSITY OF THE PHILIPPINES MANILA [Ca2+] = sqrt(0.00333 / 1.75 x 1010) = 4.36 x 10-7 M
pCa = -log (4.36 x 10-7) = 6.36 Postequivalence-Point pCa
Beyond the equivalence point, analytical concentrations of CaY2and EDTA are obtained directly from the stoichiometric data.
cCaY2- = 50.0 x 0.00500 = 2.94 x 10-3 M 50.0 + 35.0 the complex is diluted cEDTA = 35.0 x 0.0100 50.0 x 0.00500 = 1.18 x 10-3 85.0 As an approximation, we can write [CaY2-] = 2.94 x 10-3 [Ca2+] 2.94 x 10-3
from ionization
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KCaY = [Ca2+] =
2.94 x 10-3 = 1.75 x 1010 [Ca2+] x 1.18 x 10-3 2.94 x 10-3 = 1.42 x 10-10 1.18 x 10-3 x 1.75 x 1010
pCa = -log (1.42 x 10-10) = 9.85 The approximation that [Ca2+] is small is clearly valid.
Curve A (red) in the following figure is a plot of the data for the Ca titration in the example.
Curve B is the titration curve for a solution of magnesium ion under identical conditions.
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pCa
pM
8 6
pMg
The shaded areas show the transition range for Eriochrome Black T (EBT).
CaIn- + HY3red
HIn2- + CaY2-
MgIn- + HY3red EP
HIn2- + MgY2blue
4 2
blue
25.0 mL
EP
35.0 mL
10 8
pH 12 pH 10
pH 8
pCa
6
pH 6
Smaller pM at e.p End points for EDTA titrations become less sharp as pH decreases because the complex formation reaction is less complete under these circumstances. Lower pH, smaller 4 Smaller 4, smaller KMY
pM 10
8 4 0 50.00 mL Volume of 0.0100 M EDTA
smaller KMY, smaller pM
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Cations with larger formation constants provide good end points even in acidic media.
Billones Lecture Notes
log KMY
pH
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Many cations form hydroxide precipitates when the pH is raised to the level required for their successful titration with EDTA.
When this problem is encountered, an auxiliary complexing agent is needed to keep the cation in solution.
For example, zinc(II) is ordinarily titrated in a medium that has fairly high concentrations of ammonia and ammonium chloride. These species buffer the solution to a pH that ensures complete reaction between cation and titrant In addition, ammonia forms ammine complexes with zinc(II) and prevents formation of the sparingly soluble zinc hydroxide.
Zn(NH3)42+
+ HY3-
The solution also contains such other zinc/ammonia species as Zn(NH3)32+, Zn(NH3)22+, and Zn(NH3)2+.
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Complexation of a cation by an auxiliary-complexing reagent causes preequivalence pM values to be larger than in a comparable solution with no such reagent.
14 12 Influence of ammonia concentration on the end point for the titration of 50.0 mL of 0.00500 M Zn2+.
pZn
10 8 6 4 0
cNH3 = 0.100
cNH3 = 0.010
25.0 mL
A quantitative description of the effects of an auxiliary complexing agent (ACA) can be derived by a procedure similar to that used to determine the influence of pH on EDTA titration curves.
M = [Mn+] cM
[Mn+] = McM
where cM is the sum of the concentrations of species containing the metal ion exclusive of that combined with EDTA. cM = [Zn2+] + [Zn(NH3)2+] + [Zn(NH3)22+] + [Zn(NH3)32+] + [Zn(NH3)42+]
The value of M can be expressed readily in terms of the ammonia concentration and the formation constants for the various ammine complexes.
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Similarly, it is readily shown that [Zn(NH3)22+] = K2[Zn2+][NH3]2 [Zn(NH3)32+] = K3[Zn2+][NH3]3 [Zn(NH3)42+] = K4[Zn2+][NH3]4 Substitution of these expressions into the cM equation gives
cM = [Zn2+](1 + K1[NH3] + K2[NH3]2 + K3[NH3]3 + K4[NH3]4)
Substituting this expression for cM (here, [Mn+] = [Zn2+]), leads to M = 1 1 + K1 [NH3] + K2[NH3]2 + K3[NH3]3 + K4[NH3]4
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Finally, a conditional constant for the equilibrium between EDTA and zinc(II) in an ammonia/ammonium chloride buffer is
Calculate the pZn for solutions prepared by adding 20.0, 25.0, and 30.0 mL of 0.0100 M EDTA to 50.0 mL of 0.00500 M Zn2+. Assume that both the Zn2+ and EDTA solutions are 0.100 M in NH3 and 0.175 M in NH4Cl to provide a constant pH of 9.0. The logarithms of the stepwise formation constants for the four zinc complexes with ammonia are 2.21, 2.29, 2.36, and 2.03. Thus,
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K2 = antilog (2.21 + 2.29) = 3.16 x 104 K3 = antilog (2.21 + 2.29 + 2.36) = 7.24 x 106 K4 = antilog (2.21 + 2.29 + 2.36 + 2.03) = 7.76 x 108
Calculation of Conditional Constant, K
A value of the M can be obtained by assuming that the equilibrium molar and the analytical concentrations of ammonia are essentially the same; thus, for [NH3] = 0.100,
M =
KZnY = 4 x M x KZnY
= 5.2 x 10-2 x 1.17 x 10-5 x 3.2 x 1016
At this point, only part of the zinc has been complexed by EDTA. The remainder is present as Zn2+ and the four ammine complexes. cM = 50.0 x 0.00500 20.0 x 0.0100 = 7.14 x 10-4 M 70.0
pZn = 8.08
Calculation of pZn after Addition of 25.0 mL of EDTA
At the equivalence point, the analytical concentration of ZnY2- is cZnY2- = 50.0 x 0.00500 = 3.33 x 10-3 M 50.0 + 25.0
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The sum of the concentrations of the various zinc species not combined with EDTA equals the sum of the concentrations of the uncomplexed EDTA species:
cM = cT
and
Substituting, we have
cM = 4.18 x 10-7 M
pZn = 11.31
Calculation of pZn after Addition of 30.0 mL of EDTA
cEDTA = cT = EDTA sample VT = 6.25 x 10-4 M and since essentially all of the original Zn2+ is now complexed, cZnY2- = [ZnY2-] = 50.0 x 0.00500 = 3.12 x 10-3 M 80.0 Rearranging KZnY = [ZnY2-] = 4MKZnY cMcT gives,
Billones Lecture Notes
From the equation [Mn+] = McM, [Zn2+] = cMM = (2.63 x 10-10)(1.17 x 10-5) = 3.07 x 10-15
pZn = 14.51
INDICATORS FOR EDTA TITRATION
Eriochrome Black T (EBT) is a typical metal-ion indicator that is used in the titration of several common cations. Its behavior as a weak acid is described by the equations:
H 2O + H2InRed HIn2blue + H3O+ K1 = 5 x 10-7
H 2O
HIn2blue
K2 = 2.8 x 10-12
Billones Lecture Notes
The metal complexes of Eriochrome Black T are generally red as in H2In-. Thus, for metal ion detection, it is necessary to adjust the pH to 7 or above so that the blue form of the species, HIn2-, predominates in the absence of a metal ion.
Until the equivalence point in a titration, the indicator complexes the excess metal ion, so the solution is red.
When the EDTA becomes present in slight excess, the solution turns blue as a consequence of the reaction
MInred
+ HY3-
HIn2- + MY2blue
Over 40 elements can be determined by direct titration with EDTA using metal ion indicators.
MgY-2 + Ca+2
(less stable)
CaY-2 + Mg+2
Mg(EBT) red MgY-2 + EBT
blue
Billones Lecture Notes
Back-Titration Methods
Back-titration is useful for the determination of the cations that form stable EDTA complexes and for which a satisfactory indicator is not available. The method is also useful for cations that react only slowly with EDTA.
A measured excess of standard EDTA solution is added to the analyte solution.
After the reaction is judged complete, the excess EDTA is back-titrated with a standard magnesium or zinc ion solution to an Eriochrome Black T or Calmagite end point.
M + Y(xs)
Y(unreacted) + Mg
MY + Y(unreacted)
MgY (should be less stable than MY)
Displacement Methods
An unmeasured excess of a solution containing the magnesium or zinc complex of EDTA is introduced into the analyte solution.
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If the analyte forms a more stable complex than that of magnesium or zinc, the following displacement reaction occurs: analyte The liberated cation is then titrated with the standard EDTA.
MgY2- + M2+
MY2-
+ Mg2+
Interference from a particular cation can sometimes be eliminated by adding a suitable masking agent, an auxiliary ligand that preferentially forms highly stable complexes with the potential interference. For example, cyanide ion is often employed as a masking agent to permit the titration of magnesium and calcium ions in the presence of ions such as cadmium, cobalt, copper, nickel, zinc, and palladium.
All of the latter form sufficiently stable cyanide complexes to prevent reaction with EDTA.
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Illustration Showing How Masking and Demasking Agents Can Be Used to Improve The Selectivity of EDTA Titrations
Lead, magnesium, and zinc can be determined on a single sample by two titrations with standard EDTA and one titration with standard Mg2+. The sample is first treated with an excess of NaCN, which masks Zn2+ and prevents it from reacting with EDTA.
Zn2+
+ 4CN-
Zn(CN)42-
1.
The Pb2+ and Mg2+ are then titrated with standard EDTA.
After the equivalence point has been reached, a solution of the complexing agent BAL (2-3-dimercapto-1-propanol, CH2SHCHSHCH2OH), which we will formulate R(SH)2, is added to the solution.
This bidentate ligand reacts selectively to form a complex with Pb2+ that is much more stable than PbY2-:
PbY2-
+ 2R(SH)2 Pb(RS2)22-
The liberated Y4- is then titrated with a standard solution of Mg2+. Finally, the zinc is demasked by adding formaldehyde.
Zn(CN)42- + 4HCHO + H2O Zn2+ + 4HOCH2CN + 4OH-
3.
The liberated Zn2+ is then titrated with the standard EDTA solution.
Example
Suppose the initial titration of Mg2+ and Pb2+ required 42.22 mL of 0.02064 M EDTA. Titration of the Y4- liberated by the BAL consumed 19.35 mL of 0.007657 M Mg2+. Finally, after addition of formaldehyde, the liberated Zn2+ was titrated with 28.63 mL of the EDTA. Calculate the percentages of the three elements in a 0.4085 g sample.
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The initial titration reveals the number of millimoles of Pb2+ and Mg2+ present.
no. mmol (Pb2+ + Mg2+) = 42.22 x 0.02064 = 0.87142 The second titration gives the number of millimoles of Pb2+. Thus, no. mmol Pb2+ = 19.35 x 0.007657 = 0.14816 no. mmol Mg2+ = 0.87142 0.14816 = 0.72326
To obtain the percentage, we write 0.14816 mmol Pb x 0.2072 g Pb / mmol x 100% = 7.515% Pb 0.4085 g sample
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Exercise
A 1.3174-g sample containing the chloride salts of magnesium, mercury(II), and zinc was dissolved in 250.0 mL of solution. A 50.00-mL aliquot was treated with 10 mL of an NH3/NH4Cl buffer at pH 10 followed by 25.00 mL of 0.05331 M EDTA. After a few minutes of mixing, the excess EDTA was back-titrated with 11.43 mL of 0.01816 M MgCl2. A second 50.00-mL aliquot was made basic and treated with excess NaCN, complexing both the mercury and the zinc. The magnesium in this sample required 16.83 mL of 0.005583 M EDTA for titration. The solution remaining at the end of this titration was treated with excess formaldehyde, which reacts with the free CN- and with Zn(CN)42-: CN- + HCHO +H2O H2C(OH)(CN) + OH-
The liberated Zn+2 required 28.47 mL of the EDTA for titration. Calculate the percentage of each metal in the sample.
Solution
mmol xs EDTA = 25.00 mL x 0.05331 M = 1.3328 mmol mmol unreacted EDTA = 11.43 mL x 0.01816 M = 0.20757 mmol mmol M+2 = 1.3328 mmol - 0.20757 mmol = 1.12523 mmol ABANGAN ...