0 10 20 30 40 50 Buffers and Acid/Base Titration Reaction of Weak Bases with Water The base reacts with water, producing its conjugate acid and hydroxide ion: CH3NH2 + H2O CH3NH3+ + OH- Kb = 4.38 x 10-4 [CH 3 NH 3 ][OH ] Kb 4.38 x 10 [CH 3 NH 2 ] 4 Kb for Some Common Weak Bases Many students struggle with identifying weak bases and their conjugate acids.What patterns do you see that may help you? Formula Conjugate Acid Kb NH3 NH4+ 1.8 x 10-5 Methylamine CH3NH2 CH3NH3+ 4.38 x 10-4 Ethylamine C2H5NH2 C2H5NH3+ 5.6 x 10-4 Diethylamine (C2H5)2NH (C2H5)2NH2+ 1.3 x 10-3 Triethylamine (C2H5)3N (C2H5)3NH+ 4.0 x 10-4 Hydroxylamine HONH2 HONH3+ 1.1 x 10-8 Base Ammonia Hydrazine H2NNH2 H2NNH3+ 3.0 x 10-6 Aniline C6H5NH2 C6H5NH3+ 3.8 x 10-10 Pyridine C5H5N C5H5NH+ 1.7 x 10-9 Reaction of Weak Bases with Water The generic reaction for a base reacting with water, producing its conjugate acid and hydroxide ion: B + H2O BH+ + OH [ BH ][OH ] Kb [ B] (Yes, all weak bases do this – DO NOT endeavor to make this complicated!) Buffered Solutions A solution that resists a change in pH when either hydroxide ions or protons are added. Buffered solutions contain either: A weak acid and its salt A weak base and its salt Acid/Salt Buffering Pairs The salt will contain the anion of the acid, and the cation of a strong base (NaOH, KOH) Weak Acid Formula of the acid Hydrofluoric HF Formic HCOOH Benzoic C6H5COOH Acetic Carbonic Propanoic Hydrocyanic CH3COOH H2CO3 HC3H5O2 HCN Example of a salt of the weak acid KF – Potassium fluoride KHCOO – Potassium formate NaC6H5COO – Sodium benzoate NaH3COO – Sodium acetate NaHCO3 - Sodium bicarbonate NaC3H5O2 - Sodium propanoate KCN - potassium cyanide Base/Salt Buffering Pairs The salt will contain the cation of the base, and the anion of a strong acid (HCl, HNO3) Formula of the base Example of a salt of the weak acid NH3 NH4Cl - ammonium chloride Methylamine CH3NH2 CH3NH2Cl – methylammonium chloride Ethylamine C2H5NH2 C2H5NH3NO3 - ethylammonium nitrate Aniline C6H5NH2 C6H5NH3Cl – aniline hydrochloride Base Ammonia Pyridine C5H5N C5H5NHCl – pyridine hydrochloride Titration of an Unbuffered Solution 13 12 11 10 A solution that is 0.10 M CH3COOH is titrated with 0.10 M NaOH 9 pH 8 7 6 5 4 3 2 1 0.00 5.00 10.00 15.00 20.00 25.00 milliliters NaOH (0.10 M) 30.00 35.00 40.00 45.00 Titration of a Buffered Solution 13 12 11 A solution that is 0.10 M CH3COOH and 0.10 M NaCH3COO is titrated with 0.10 M NaOH 10 9 pH 8 7 6 5 4 3 2 1 0.00 5.00 10.00 15.00 20.00 25.00 milliliters NaOH (0.10 M) 30.00 35.00 40.00 45.00 Comparing Results Gra ph pH Buffered Unbuffered mL 0.10 M NaOH Comparing Results Buffered 13 13 12 12 11 11 10 10 9 9 8 8 7 pH pH Unbuffered 6 6 5 5 4 4 3 3 2 1 0.00 7 2 5.00 10.00 15.00 20.00 25.00 milliliters NaOH (0.10 M) 30.00 35.00 40.00 45.00 1 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 milliliters NaOH (0.10 M) In what ways are the graphs different? In what ways are the graphs similar? 40.00 45.00 Henderson-Hasselbalch Equation [ A ] [base] pK a log pH pK a log [acid ] [ HA] [ BH ] [acid ] pKb log pOH pKb log [base] [ B] This is an exceptionally powerful tool, and it’s use will be emphasized in our problem solving. Weak Acid/Strong Base Titration 13 12 11 10 9 Endpoint is above pH 7 pH 8 7 A solution that is 0.10 M CH3COOH is titrated with 0.10 M NaOH 6 5 4 3 2 1 0.00 5.00 10.00 15.00 20.00 25.00 milliliters NaOH (0.10 M) 30.00 35.00 40.00 45.00 Strong Acid/Strong Base Titration 13 12 11 10 9 pH 8 7 Endpoint is at pH 7 A solution that is 0.10 M HCl is titrated with 0.10 M NaOH 6 5 4 3 2 1 0.00 5.00 10.00 15.00 20.00 25.00 milliliters NaOH (0.10 M) 30.00 35.00 40.00 45.00 Strong Acid/Strong Base Titration 13 12 A solution that is 0.10 M NaOH is titrated with 0.10 M HCl 11 10 9 pH 8 7 Endpoint is at pH 7 It is important to recognize that titration curves are not always increasing from left to right. 6 5 4 3 2 1 0.00 5.00 10.00 15.00 20.00 25.00 milliliters HCl (0.10 M) 30.00 35.00 40.00 45.00 Strong Acid/Weak Base Titration 13 12 11 10 9 pH 8 7 6 5 Endpoint is below pH 7 4 A solution that is 0.10 M HCl is titrated with 0.10 M NH3 3 2 1 0.00 5.00 10.00 15.00 20.00 25.00 milliliters NH3 (0.10 M) 30.00 35.00 40.00 45.00 Selection of Indicators Indicator Indicator Transitions Low pH color Transition pH range High pH color Gentian violet (Methyl violet 10B) yellow 0.0–2.0 blue-violet Leucomalachite green (first transition) Leucomalachite green (second transition) yellow green 0.0–2.0 11.6–14 green colorless Thymol blue (first transition) red 1.2–2.8 yellow Thymol blue (second transition) yellow 8.0–9.6 blue Methyl yellow Bromophenol blue red yellow 2.9–4.0 3.0–4.6 yellow purple Congo red blue-violet 3.0–5.0 red Methyl orange Bromocresol green Methyl red Methyl red red yellow red red 3.1–4.4 3.8–5.4 4.4–6.2 4.5–5.2 orange blue yellow green Azolitmin Bromocresol purple Bromothymol blue Phenol red Neutral red Naphtholphthalein Cresol Red red yellow yellow yellow red colorless to reddish yellow 4.5–8.3 5.2–6.8 6.0–7.6 6.8–8.4 6.8–8.0 7.3–8.7 7.2–8.8 blue purple blue red yellow greenish to blue reddish-purple Phenolphthalein Thymolphthalein Alizarine Yellow R Litmus colorless colorless yellow red 8.3–10.0 9.3–10.5 10.2–12.0 4.5-8.3 fuchsia blue red blue Source: Wikipedia