UNIVERSITY OF THE PHILIPPINES MANILA

TITRIMETRIC METHODS OF ANALYSIS

Titrimetric methods - quantitative procedures based upon measurement of the amount of reagent consumed by the analyte. Volumetric titrimetry - involves measuring the volume of a solution of a known concentration that is needed to react completely with the analyte. Gravimetric titrimetry - the mass of the reagent is measured instead of its volume.

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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Billones Lecture Notes

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

- stable - reacts rapidly

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- reacts completely - selective

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UNIVERSITY OF THE PHILIPPINES MANILA Sample Calculation from Titration Data

A 0.8040-g sample of an iron ore is dissolved in acid. The iron is then reduced to Fe2+ and titrated with 47.22 mL of 0.02242 M KMnO4 solution. Calculate the results of this analysis in terms of a.) % Fe (55.847 g/mol) and b.) % Fe3O4 (231.54 g/mol). The reaction of the analyte with the reagent is described by the equation

MnO4- + 5Fe2+ + 8H+

Mn2+ + 5Fe3+ + 4H2O

5mmolFe 2 a) stoichiometric ratio ! 1mmolKMnO4

0.02242mmolKMnO4 amount KMnO4 ! 47.22mLKMnO4 x mLKMnO4

! 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

1mol 55.847gFe ! 5.2935mmolFe x x 1000mmol mol

2

UNIVERSITY OF THE PHILIPPINES MANILA 2

! 0.2956 3 gFe 2
%Fe 2 0.2956 3 gFe 2 ! x100 ! 36.77% 0.8040g

b. In order to derive a stoichiometric ratio, note that


Therefore,

5 Fe2+ = 1MnO41 Fe3O4 = 3 Fe2+ = 3/5 MnO45 Fe3O4 = 15 Fe2+ = 3 MnO4and

stoichiometric ratio = 5 mmol Fe3O4 3 mmol KMnO4

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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA 0.02242mmolKMnO4 massFe3O4 ! 47.22mLKMnO4 x mLKMnO4 5mmolFe3O4 0.2315gFe3O4 x x ! 0.4085 4 gFe3O4 3mmolKMnO4 mmolFe3O4

0.40854g %Fe3O4 ! x100 ! 50.81% 0.8040g 

Gravimetric Titrimetry

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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UNIVERSITY OF THE PHILIPPINES MANILA

The most convenient unit of concentration for weight titrations is weight molarity, Mw.

molsolute mmolsolute Mw ! ! kgsolution gsolution

TITRATION CURVES


pX

sigmoidal curve

equivalence point

Voltitrant
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UNIVERSITY OF THE PHILIPPINES MANILA Titration Data

Vol. of 0.100 M NaOH, mL [H3O+] mol/L Vol. of NaOH to cause a tenfold decrease in [H3O+], mL

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

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UNIVERSITY OF THE PHILIPPINES MANILA

TITRATION CURVES FOR STRONG ACIDS AND STRONG BASES
14 12 10 8 6 4 2 0 0 10 20 30 40 50 60 70 Volume NaOH, mL

Plot for data in table above.

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UNIVERSITY OF THE PHILIPPINES MANILA

The Titration of a Strong Acid with a Strong Base To derive a titration curve for a solution of a strong acid with a strong base, three types of calculations are required. (1) pre-equivalence (2) equivalence (3) post-equivalence

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

UNIVERSITY OF THE PHILIPPINES MANILA

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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UNIVERSITY OF THE PHILIPPINES MANILA

cHCl = original no. mmol HCl no. mmol NaOH added total volume solution
= (50.00 mL x 0.0500 M) (10.00 mL x 0.1000 M) 50.00 mL + 10.00 mL

= (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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UNIVERSITY OF THE PHILIPPINES MANILA

The concentrations of hydronium and hydroxide ions must be equal. Substituting this equality into the ion product constant for water yields.

[H3O+] = sqrt(Kw) = sqrt(1.0 x 10-14) = 1.0 x 10-7

pH = - log(1.0 x 10-7) = 7.00 After Addition of 25.10 mL of Reagent (Post-equivalence)

The solution now contains an excess of NaOH, and we can write cNaOH = 25.10 x 0.1000 50.00 x 0.0500 = 1.33 x 10-4 75.10
and the equilibrium concentration of hydroxide ion is [OH] = cNaOH = 1.33 x 10-4 M pOH = -log (1.33 x 10-4) = 3.88

pH = 14.00 3.88 = 10.12

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Billones Lecture Notes

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

1.3 1.6 2.15 2.87 3.87 7 10.12 11.12 11.8

3.3 3.6 4.15 4.87 5.87 7 8.12 9.12 9.8

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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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Billones Lecture Notes

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.

Pre-equivalence (sample > titrant)

[OH-] = cNaOH = orginal no. mmol NaOH no. mmol HCl added total volume of solution = (50.00 x 0.0500 24.50 x 0.1000) = 6.71 x 104M 50.00 + 24.50 [H3O+] = Kw / (6.71 x 10-4) = (1.00 X 10-14)/(6.71 X 10-4)

[H3O+] =1.49 x 10-11

pH = -log(1.49 x 10-11) = 10.83

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Billones Lecture Notes

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

pH = -log(1.00 x 10-7) = 7.00

Post-equivalence (titrant > sample)

[H3O+] = cHCl = (25.50 x 0.1000 50.00 x 0.050) = 6.62 x 10-14 75.50

pH = -log (6.62 x 10-4) = 3.18

Titration Curves
14 12 10 8 6 4 2 0 0 5 10 15 20 volume HCl, mL 25 30 35 40

concentrated dilute

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TITRATION CURVES FOR WEAK ACIDS

UNIVERSITY OF THE PHILIPPINES MANILA

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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UNIVERSITY OF THE PHILIPPINES MANILA

The pH is calculated from the concentration of this salt product.

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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UNIVERSITY OF THE PHILIPPINES MANILA

pH after Addition of 10.00 mL of Reagent
A buffer solution consisting of NaOAc and HOAc has now been produced.

The analytical concentrations of the two constituents are

cHOAc = 50.00 mL x 0.1000 M 10.00 mL x 0.1000 M = 4.000 M 60.00 mL 60.00 mL cNaOAc = 10.00 mL x 0.1000 M = 1.000 M 60.00 mL 60.00 mL

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

[H3O+] = 7.00 x 10-3

pH = 4.16
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UNIVERSITY OF THE PHILIPPINES MANILA

Equivalence Point pH At the equivalence point, all the acetic acid has been converted to sodium acetate.
cNaOAc = (50.00 mL x 0.1000 M)/100 mL = 0.0500 M OAc- + H2O
but [OH-] = [HOAc]

HOAc + OH-

[OAc-] = 0.0500 [OH-] 0.0500 M

Substituting in the base dissociation constant expression for OAc- gives

[OH-]2 = Kw = 1.00 x 10-14 = 5.17 x 10-10 0.0500 Ka 1.75 x 10-5

[OH-] =sqrt(0.0500 x 5.17 x 10-10) = 5.34 x 10-6

pH = 14.00 ( - log 5.34 x 10-6) = 8.73
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UNIVERSITY OF THE PHILIPPINES MANILA

pH after Addition of 50.10 mL of Base

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

pH = 14.00 (-log 1.00 x 10-4) = 10.00

Note that the titration curve for a weak acid with a strong base is identical to that for a strong acid with a strong base in the region slightly beyond the equivalence point.
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Billones Lecture Notes

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
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14

UNIVERSITY OF THE PHILIPPINES MANILA

Basic indicator Neutral indicator

pH

7
dilute

Basic pH at EP

concentrated

0 14
Ka = 10-9

50.00 mL (EP) Vol of NaOH

The smaller the Ka (the weaker the acid) the smaller the rise in pH

pH

Basic pH at EP

Ka = 10-2

50.00 mL (EP) Vol of NaOH

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UNIVERSITY OF THE PHILIPPINES MANILA

TITRATION CURVES FOR WEAK BASES The derivation of a curve for the titration of a weak base is analogous to that of a weak acid.

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

(a). 0.00 mL of reagent (HYDROLYSIS)

CN- + H2O HCN + OH[OH-][HCN] = Kh = Kw = 1.00 x 10-14 = 1.61 x 10-5 [CN-] Ka 6.2 x 10-10

[CN-] = cNaCN - [OH-] cNaCN = 0.0500

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UNIVERSITY OF THE PHILIPPINES MANILA

Substitution into the dissociation constant expression gives, after rearrangement,

[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:

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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)

The principal solute species is the weak acid HCN.

cHCN = 25.00 x 0.1000 = 0.03333 M 75.00

Ka = [H3O+]2/cHCN [H3O+] = sqrt(Ka cHCN) = sqrt(6.2 x 10-10 x 0.03333) [H3O+] = 4.55 x 10-6

pH = -log (4.55 x 10-6) = 5.34

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UNIVERSITY OF THE PHILIPPINES MANILA

(d) 26.00 mL of reagent (STRONG ACID)

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

25.00 mL (EP) Vol of HCl

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