Volumetric Analysis

Wan Elina Faradilla Wan Khalid UiTM Negeri Sembilan

ACID-BASE TITRATIONS
Strong Acid-Strong Base Titrations NaOH (aq) + HCl (aq) OH- (aq) + H+ (aq) H2O (l) + NaCl (aq) H2O (l)

pH PROFILE OF THE TITRATION (TITRATION CURVE)

pH PROFILE OF THE TITRATION (TITRATION CURVE)

Before addition of NaOH - pH = 1.00 When the NaOH added - pH increase slowly at first Near the equivalence point (the point which equimolar amounts of acid and base have reacted) - the curve rises almost vertically Beyond the equivalence point - pH increases slowly

CALCULATION OF pH AT EVERY STAGE OF TITRATION

1) After addition of 10.0 mL of 0.100 M NaOH to 25.0 mL of 0.100 M HCl Total volume = 35.0 mL Moles of NaOH in 10.0 mL
M = mol L = 0.1 x (10 mL/1000 mL) = 1.00 x 10-3 mol

Moles of HCl in 25.0 mL

M = mol L = 0.1 x (25 mL/1000 mL) = 2.50 x 10-3 mol

Amount of HCl left after partial neutralization = (2.50 x 10-3)-(1.00 x 10-3) = 1.50 x 10-3 mol Concentration of H+ ions in 35.0 mL
M = mol L = 1.50 x 10-3 mol (35/1000) = 0.0429 M

[H+] = 0.0429 M, pH = -log 0.0429 = 1.37 2) After addition of 25.0 mL of 0.100 M NaOH to 25.0 mL of 0.100 M HCl [H+] = [OH-] = 1.00 x 10-7 pH = 7.00

3) After addition of 35.0 mL of 0.100 M NaOH to 25.0 mL of 0.100 mL of HCl Total volume = 60.0 mL Moles of NaOH added M = mol L = 0.1 x (35 mL/1000 mL) = 3.50 x 10-3 mol Moles of HCl in 25.0 mL solution = 2.50 x 10-3 mol After complete neutralization of HCl, no of moles of NaOH left = (3.50 x 10-3)-(2.50x10-3) = 1.00 x 10-3 mol Concentration of NaOH in 60.0 mL solution
M = mol L = 1.00 x 10-3 mol (60/1000) = 0.0167 M

[OH-] = 0.0167 M pOH = -log 0.0167 = 1.78 pH = 14.00 1.78 = 12.22

Weak Acid Versus Strong Base

The titration between acetic acid and NaOH CH3COOH + NaOH H2O + Na+ + CH3COO-

The acetic acid which is only a few percent ionized is neutralized to water and equivalent amount of NaOAc salt

(a) the initial point - This is essentially a weak acid (CH3COOH) (aqueous solution) (b) buffer region - In this region, the amount of strong base added is still not enough to neutralize completely the weak acid. Prior to reaching the equivalence point, part of CH3COOH is neutralized to CH3COOThus, the solution will now contain both CH3COOH and a significant amount of CH3COO(c) equivalence point - At this point, only the conjugate base (CH3COO-) of the weak acid needs our attention. Thus, at the equivalence point, we are simply dealing with a weak base solution (d) Strong base region (after equivalence point) - in this region, one can predict the pH by simply taking into account the amount of excess base.

Weak Base Versus Strong Acid

The titration between hydrochloric acid and ammonia NH3 + HCl NH4+ + Cl-

At the beginning of the titration, we have NH3 When the acid is added, some NH3 is converted to NH4+ (buffer region) Midpoint of the titration, NH4+ equals with NH3 Equivalence point, we have a solution of NH4Cl Beyond the equivalence point, the pH is determined by the concentration of H+ added in excess

Back Titration
Is useful when the titration reaction slow to achieve a complete reaction Allows the user to find the concentration of a reactant of unknown concentration by reacting it with an excess volume of another reactant of known concentration. The resulting mixture is then titrated, taking into account the molarity of the excess that was added.

The total analyte is determined by the differences. A fixed volume of titrant is added to the analyte in excess. This excess titrant is determined by titration with another standard solution.

Calculation
molreacted analyte = molused analyte molback titrated molback titrated analyte = moltitrant x factor (mol analyte/mol titrant)

Mg analyte = molreacted analyte x factor (mol analyte/mol titrant) x RMM analyte

Example: A 50 mL amount of water sample is treated to convert iron to ferric ion. A 25 mL of 0.002107 M K2Cr2O7 solution is added which gives the following reaction: 6Fe2+ + Cr2O72- + 14H+ 6Fe3+ + 2Cr3+ + 7H2O The excess of K2Cr2O7 was back titrated with 7.5 mL of 0.0098 M Fe2+ solution. Calculate the iron content (ppm) in the sample. RMM for Fe is 55.847.

Solution: 1) Mol Cr2O72- = volume Cr2O72- x molarity Cr2O72= (25/1000) x 0.002107 = 5.27 x 10-5 mol

2) 1 mol Cr2O72- = 6 mol Fe2+ 5.27 x 10-5 mol Cr2O72- = 5.27 x 10-5 mol Cr2O72 x 6 mol Fe2+ 1 mol Cr2O72= 3.16 x10-4 mol Fe2+

Mol Fe2+ back titration = volume Fe2+ x molarity Fe2+ = (7.5/1000) x 0.0098 = 7.35 x 10-5 mol Actual mol Fe2+ = (3.16 x10-4 mol - 7.35 x 10-5 mol) = 2.43 x 10-4 mol Concentration of Fe2+ = no. of mole = 2.43 x 10-4 mol = 4.86 x 10-3 M volume (L) (50/1000) 4.86 x 10-3 mol x 55.847 g = 0.271 g L mol L mg = 0.271 g x 1000 mg = 271 mg = 271 ppm L L 1g L