Neutralization Titration Strong Acid Titrated with Strong Base Ex. HCl + NaOH NaCl + H2O Region 1.

. Before the equivalence point 2. At the equivalence point 3. After the equivalence point Major Constituents HCl + NaCl NaCl NaCl + NaOH Comments Treat as strong acid Treat as pure solvent Treat as strong base

Region 1: since the reaction is 1:1, addition of NaOH consumes an equal amount of HCl Amount HCl initial Amount of NaOH added Amount of HCl reacted Amount HCl remaining [H3O+] = CHCl

Region 2: [H3O+] results only from the ionization of water [H3O+] = Kw = 1.00 x 10 -7 M pH = 7.000

Region 3: Amount NaOH added Amount of HCl initial Amount of NaOH reacted Amount NaOH remaining

[OH-] = CNaOH = amount NaOH remaining/new volume Strong Base Titrated with Strong Acid - The curve for the titration of strong base is derived in an analogous manner to that of the strong acid. The solution is basic before equivalence point and acidic afterwards Weak Acid Titrated with Strong Base - Ex. CH3COOH + OH- CH3CO2- + H2O Region Before addition of titrant Before the equivalence point At the equivalence point After the equivalence point Major Constituents CH3COOH CH3COOH + CH3COONa CH3COONa CH3COONa + NaOH Comments Treat as weak acid Treat as buffer Treat as weak base Treat as strong base

1. 2. 3. 4. Region 1: Region 2:

[H3O+] = Ka[CH3COOH] = KaCCH3COOH Ka = [H3O+] CCH3COONa CCH3COOH Amount CH3COOH initial Amount of NaOH added Amount CH3COOH used Amount CH3COOH remaining

= amount of CH3COONa formed

And CCH3COONa = amount of CH3COONa formed Vol CCH3COOH = amount of CH3COOH remaining Vol

Region 3: [OH-] = Kb[CH3COO-] = KaCCH3COONa Amount of CH3COONa formed = amount of CH3COOH present initially And CCH3COONa = amount of CH3COONa formed Vol

Region 4: the procedure for is identical to that used in region 3 of a strong acid-base titration

Weak Base Titrated with Strong Acid - Analogous to that of a weak acid - Ex. NH3 + HCl NH4Cl + H+ Region Before addition of titrant Before the equivalence point At the equivalence point After the equivalence point Major Constituents NH3 NH3 + NH4Cl NH4Cl NH4Cl + HCl Comments Treat as weak base Treat as buffer Treat as weak acid Treat as strong acid

1. 2. 3. 4. Applications

Determination of Carbonate and Carbonate Mixtures Case 1: Na2CO3 alone o Two end points can be observed and the volume of titrant required to reach the phenolphthalein endpoint will equal the volume required to titrate from the phenolphthalein (Ph) to the methyl red (MR) end point o If titration is stopped at the phenolphthalein endpoint Amount HCl titrant = amount Na2CO3 o If titration is stopped at the methyl red end point Amount HCl titrant = 2 x amount Na2CO3 Case 2: Na2CO3 + NaOH o Sodium hydroxide will titrate along with the sodium carbonate prior to the phenolphthalein color change, that is, the volume of titrant needed to reach phenolphthalein end point will be greater than the volume needed to titrate from the phenolphthalein to the methyl red end point o At phenolphthalein end point Amount HCl to Ph = amount NaOH + amount Na2CO3 o At MR end point Amount HCl from Ph to MR = amount Na2CO3 o Amount of NaOH can be found by difference Case 3: Na2CO3 + NaHCO3 o Sodium bicarbonate does not begin to titrate until after the phenolphthalein color change and the volume of titrant needed to reach the phenolphthalein end point will be less than the volume needed to titrate from the phenolphthalein to the methyl red end point o At phenolphthalein end point Amount HCl to Ph = amount Na2CO3 o At methyl red end point Amount HCl from Ph to MR = amount Na2CO3 + NaHCO3 o The amount of sodium bicarbonate present in the original sample is found by difference Case 4: NaOH alone o Only one break will be observed o At either end point Amount HCl to Ph or MR = amount NaOH Case 5: NaHCO3 alone o One end point encompassing the methyl red transition range

At the end point Amount HCl to MR = amount NaHCO3

Determination of hydrogen The most popular method for determining nitrogen is Kjeldahl method It is based on the conversion of the bound nitrogen to ammonia, which is then separated by distillation and determined by titration

1. Digestion o The sample is oxidized in hot, concentrated sulfuric acid o The carbon and hydrogen in the sample are converted to carbon dioxide and water o If nitrogen exists as an amine or an amide as it does in proteins, it will be converted to the desired ammonium ion o If it exist in a higher oxidation state such as an azo or nitro group, it will be converted to elemental nitrogen or nitrogen oxides o Since this process is slow a catalyst can be used, ex. Potassium sulfate increases the boiling point of the sulfuric acid solution 2. Distillation o The oxidized solution is cooled and then treated with NaOH to liberate ammonia gas NH4+ + OH- NH3 (g) + H2O 3. Titration o Ammonia is collected, it reacts to form the borate ion H2BO3H3BO3 + NH3 NH4+ + H2BO3The titrated with HCl using methyl red indicator o An alternative method employs a back titration, Using an excess amount of HCl NH3 + HCl NH4Cl The excess HCl is determined using a standard NaOH solution HCl + NaOH NaCl + H2O Ammonia distilled is collected in a boric acid solution NH3 + H3BO3 NH4+ + H2BO3-2 Titrate the H3BO3 NH3 solution with standard acid H2BO3-2 + H3O+ H3BO3 + H2O