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Terminologies
Standard solution (or standard titrant) is a reagent of known concentration that is used to carry out a titrimetric analysis.
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UNIVERSITY OF THE PHILIPPINES MANILA Equivalence point - the amount of added titrant is chemically equivalent to the amount of analyte in the sample.
End point - observable physical change associated with the condition of equivalence. Indicators - added to the analyte solution in order to give an observable physical change (the end point) at or near the equivalence point. Primary standard - highly purified compound that serves as a reference material in all titrimetric methods.
Desirable Properties of Standard Solution
! 1.058 7 mmolKMnO4
5mmolFe 2 amount Fe2+ ! 1.0587mmolKMnO4 x ! 5.2935 mmolFe 2 1mmolKMnO4 The Health Sciences Center Billones Lecture Notes
massFe
2
! 0.2956 3 gFe 2
%Fe 2 0.2956 3 gFe 2 ! x100 ! 36.77% 0.8040g
Therefore,
UNIVERSITY OF THE PHILIPPINES MANILA 0.02242mmolKMnO4 massFe3O4 ! 47.22mLKMnO4 x mLKMnO4 5mmolFe3O4 0.2315gFe3O4 x x ! 0.4085 4 gFe3O4 3mmolKMnO4 mmolFe3O4
Weight or gravimetric titrimetry differs from its volumetric counterpart in that the mass of titrant is measured rather than the volume. In a weight titration, a balance and a solution dispenser are substituted for a buret and its markings
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pX
sigmoidal curve
equivalence point
Voltitrant
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pH 1.00
pOH 13.00 12.00 11.00 10.00 9.00 8.00 7.00 6.00 5.00 4.00 3.00 2.00
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0.00 40.91 49.01 49.90 49.99 49.999 50.00 50.001 50.01 50.10 51.01 61.11
1.000 x 10-1 1.000 x 10-2 1.000 x 10-3 1.000 x 10-4 1.000 x 10-5 1.000 x 10-6 1.000 x 10-7 1.000 x 10-8 1.000 x 10-9 1.000 x 10-10 1.000 x 10-11 1.000 x 10-12 40.91 8.11 0.89 0.09 0.009 0.001 0.001 0.009 0.09 0.91 10.10
2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00
Important formulas:
Kw = [H3O+][OH-] -log Kw = -log [H3O+][OH-] = -log [H3O+] log[OH-] pKw = pH + pOH -log10-14 = 14.00 = pH + pOH pKw = pH + pOH = 14.00
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Example
Derive a curve for the titration of 50.00 mL of 0.0500 M HCI with 0.1000 M NaOH. Initial Point At the outset, the solution is 0.0500 M in H3O+ and pH = -log[H3O+] = -log 0.0500 = 1.30 After Addition of 10.00 mL of Reagent (Pre-equivalence) The hydronium ion concentration decreases as a result of both reaction with the base and dilution. Thus, the analytical concentration of HCI is
cHCl = no. mmol HCl remaining after addition of NaOH total volume solution
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= (2.500 mmol 1.000 mmol) = 2.500 x 10-2 M 60.00 mL +] = 2.50 x 10-2 [H3O and pH = -log [H3O+] = -log (2.500 x 10-2) = 1.602 Additional points defining the curve in the region before the equivalence point are obtained in the same way. Equivalence Point At the equivalence point, neither HCI or NaOH is in excess.
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Titration UNIVERSITY OF THE Strong Base MANILA Data for Strong Acid - PHILIPPINES Titration
pH Volume of NaOH, mL
0 10 20 24 24.9 25 (EP) 25.1 26 30
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50.00 mL of 0.000500 50.00 mL of 0.0500 M M HCl w/ 0.001000 M HCl w/ 0.1000 M NaOH NaOH
UNIVERSITY OF THE PHILIPPINES MANILA Titration Curves for the Data in the Table above.
14 12
10
dilute concentrated
0 10 20 24 24.9 25 25.1 26 30
Effect of Concentration on Indicator Choice Note that the pH break is narrower in dilute system. Only those indicators that change color in that narrow range can be used.
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UNIVERSITY OF THE PHILIPPINES MANILA The Titration of Strong Base and Strong Acid
Example Calculate the pH during the titration of 50.00 mL of 0.0500 M NaOH with 0.1000 M HCI after the addition of the following volumes of reagent: (a) 24.50 mL, (b) 25.00 mL and (c) 25.50 mL.
UNIVERSITY OF THE PHILIPPINES MANILA Equivalence point (sample = titrant; [H3O+] = [OH-])
[H3O+] = sqrt(Kw) = sqrt(1.00 x 10-14) = 1.00 x 10-7
concentrated dilute
Four distinctly different types of calculations are needed to derive a titration curve for a weak acid (or a weak base):
1. At the beginning, the solution contains only the solute acid or base.
The pH is calculated from the concentration of that solute and its dissociation constant.
2. After addition of titrant, before the equivalence point, the mixture is a buffer solution.
The pH of the buffer can be calculated from analytical concentrations of the conjugate base or acid and the residual concentrations of the weak acid or base.
3. At the equivalence point, the solution contains only the conjugate of the weak acid or base being titrated (that is, a salt).
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4. Beyond the equivalence point, the excess of strong acid or base titrant represses the acidic or basic character of the reaction product to such an extent that the pH is governed largely by the concentration of the excess titrant.
Example Derive a curve for the titration of 50.00 mL of 0.1000 M acetic acid (Ka = 1.75 x 10-5) with 0.1000 M sodium hydroxide.
Initial pH
Calculate the pH of a 0.1000 M solution of HOAc [H3O+] = sqrt(Ka.cHOAc) = sqrt(1.75 x 10-3 x 0.1000) = 1.32 x 10-3 pH = - log (1.32 x 10-3) = 2.88
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We substitute these concentrations into the dissociation constant expression for acetic acid and obtain Ka = [ H3O+](1.000/60.00) = 1.75 x 10-3 4.000/60.00
pH = 4.16
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HOAc + OH-
After addition of 50.10 mL of NaOH, both the excess base and the acetate ion are sources of hydroxide ion.
The contribution of the latter is small, however, because the excess of strong base represses the reaction. The hydroxide ion concentration is only 5.34 x 10-6 M at the equivalence point. Once an excess of strong base is added, the contribution from the reaction of the acetate is even smaller.
Thus,
[OH-] cNaOH = 50.10 mL x 0.1000 M 50.00 mL x 0.1000 M 100.1 mL [OH-] =1.00 x 10-4 M
TitrationUNIVERSITY OF THEStrong Base MANILA Data for Weak Acid - PHILIPPINES Titration
Volume of NaOH, mL
0.00 10.00 25.00 40.00 49.00 49.90 50.00 50.10 51.00 60.00 75.00
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pH
50.00 mL of 0.1000 M HAc 50.00 mL of 0.001000 M w/ 0.1000 M NaOH HAc w/ 0.001000 M NaOH
2.88 4.16 4.76 5.36 6.45 7.46 8.73 10.00 11.00 11.96 12.30
3.91 4.30 4.80 5.38 6.46 7.47 7.73 8.09 9.00 9.96 10.30
Billones Lecture Notes
14
pH
7
dilute
Basic pH at EP
concentrated
0 14
Ka = 10-9
pH
Basic pH at EP
Ka = 10-2
Example
A 50.00 mL aliquot of 0.0500 M NaCN is titrated with 0.1000 M HCl. Calculate the pH after the addition of (a) 0.00, (b.) 10.00, (c) 25.00, and (d) 26.00 mL of acid.
The reaction is
CN- + H3O+
HCN + H2O
[OH-] = sqrt(Kh cNaCN) = sqrt(1.61 x 10-5 x 0.0500) [OH-] = 8.97 x 10-4 pH = 14.00 (-log 8.97 x 10-4) = 10.95
(b). 10.00 mL of reagent (BUFFER) cNaCN = 50.00 x 0.0500 10.00 x 0.1000 = 1.500 M 60.0 60.00 cHCN = 10.00 x 0.1000 = 1.000 M 60.0 60.00
These values are then substituted into the expression for the acid dissociation constant of HCN to give [H3O+] directly:
UNIVERSITY OF THE PHILIPPINES MANILA [H3O+] = 6.2 x 10-10 x (1.000/60.00) = 4.13 x 10-10 1.500/60.00 pH = -log (4.13 x 10-10) = 9.38
(c) 25.00 mL of reagent (WEAK ACID)
Ka = [H3O+]2/cHCN [H3O+] = sqrt(Ka cHCN) = sqrt(6.2 x 10-10 x 0.03333) [H3O+] = 4.55 x 10-6
The excess of strong acid now represses the dissociation of the HCN to the point where its contribution to the pH is negligible. [H3O+] = cHCl = 26.00 x 0.1000 50.00 x 0.0500 = 1.32 x 10-3 76.00 pH = -log(1.32 x 10-3) = 2.88
14
Kb = 10-2
The smaller the Kb (the weaker the base) the narrower the pH break.
acidic pH at EP
pH
7
Kb = 10-9