Unit 1 Mod 2 Buffers page 1 of 4 BUFFERS A buffer solution is one which resists changes in pH when small quantities of an acid or an alkali are added to it. Acidic buffer solutions An acidic buffer solution is simply one which has a pH less than 7. Acidic buffer solutions are commonly made from a weak acid and a salt of the weak acid usually the sodium salt. CH3COOH CH3COO- + H+ CH3COONa CH3COO- + Na+ What happens when an acid is added to an acidic buffer solution There would be an INCREASE in the concentration of hydrogen ions. Via Le Chatelier’s Principle the system would then try to DECREASE the concentration of H+ ions. Hydrogen ions would then combine with the ethanoate ions to make ethanoic acid. This means the equilibrium reaction shifts to the LEFT. NOTE Although the reaction is reversible, since the ethanoic acid is a weak acid, most of the hydrogen ions added from the acid are removed in this way. The pH of the buffer solution will still drop but by a very small amount. What happens when an alkali is added to an acidic buffer solution The excess hydroxide ions will combine with the hydrogen ions and be removed from the buffer. In essence by adding hydroxide ions, this causes a DECREASE in the hydrogen ion concentration. The system would then try to INCREASE the concentration of H+ ions. More ethanoic acid molecules would dissociate producing more hydrogen ions. This means the equilibrium reaction shifts to the RIGHT. NOTE Most of the hydrogen ions removed by the hydroxide ions are replaced The pH of the buffer solution will still rise but by a very small amount. Alkaline buffer solutions An alkaline buffer solution has a pH greater than 7. Alkaline buffer solutions are commonly made from a weak base and one of its salts. NH3 + H2O O NH4+ + OHNH4Cl NH4+ + ClWhat happens when an acid is added to an alkaline buffer solution The hydrogen ions will combine with the hydroxide ions and remove them from the buffer. In essence by adding hydrogen ions, this causes a DECREASE in the hydroxide ion concentration. Unit 1 Mod 2 Buffers page 2 of 4 The system would then try to INCREASE the concentration of OH- ions. More ammonia molecules would dissociate producing more hydroxide ions. This means the equilibrium reaction shifts to the RIGHT. NOTE Most of the hydroxide ions removed by the hydrogen ions are replaced The pH of the buffer solution will still drop but by a very small amount. Adding an alkali to an alkaline buffer solution There would be an INCREASE in the concentration of hydroxide ions. The system would then try to DECREASE the concentration of OH- ions. Ammonium ions would then combine with the hydroxide ions to make ammonia. This means the equilibrium reaction shifts to the LEFT. NOTE Although the reaction is reversible, since the ammonia is a weak base, most of the hydroxide ions added are removed in this way. The pH of the buffer solution will still rise but by a very small amount. Checkpoint A Tick the pairs of substances can act as buffers or cannot act as buffers. Of those pairs which CAN act as buffers, write the letters “Ac” to represent acidic buffers or “Al” to represent alkaline buffers, a) HNO3 + NaOH b) CH3COOH + CH3COONa c) H3PO4 + HCl d) NH3 + NH4Cl How to calculate the pH of buffer solutions Henderson-Hasselbalch equation Where [A-] represents the MOLAR CONCENTRATION of the salt and [HA] represents the MOLAR CONCENTRATION of the weak acid Example 1 a) A 1.0 mol dm-3 buffer is prepared from 0.25 mol of ethanoic acid and 0.25 mol of sodium ethanoate. pKa ethanoic acid = 4.7 pH = 4.7 + log (0.25/0.25) = 4.7 + log 1 = 4.7 + 0 = 4.7 b) Calculate the change in pH if 0.15 mol of OH- ions are added to the buffer. Note the reaction of ethanoic acid and hydroxide ions react in a 1:1 ratio CH3COOH + OH- CH3COO- + H2O Therefore the # of moles of ethanoic acid would DECREASE by 0.15 and the # of moles of ethanoate ions would INCREASE by 0.15. Therefore the NEW molar concentrations are [CH3COOH] = 0.25 – 0.15 = 0.1 and [CH3COO-] = 0.25 + 0.15 = 0.40 Hence the new pH = 4.7 + log (0.4/0.1) = 4.7 + log 4 = 5.3 Unit 1 Mod 2 Buffers page 3 of 4 Example 2 A buffer solution was made by dissolving 10.0 grams of sodium ethanoate in 200.0 mL of 1.00 M ethanoic acid. Calculate the pH of the ethanoic acid/sodium ethanoate buffer solution. Ka acid is 1.7 x 10-5. pKa = 4.7 [A-] = mass of salt / molar mass of salt = 10 / 82 = 0.122 x 5 = 0.611 [HA] = 1 Hence pH = 4.7 + log(0.61/1) = 4.77 – 0.22 = 4.55 Checkpoint B 1. Calculate the pH of a buffer solution containing 0.12 mol dm-3 ethanoic acid and 0.34 mol dm-3 sodium ethanoate. The pKa of ethanoic acid is 4.75 2. 1 dm3 of a buffer contains 0.325 g of aspirin and 0.01M of the salt of aspirin Ka aspirin = 3.3 x 10-4 a) Calculate the molar concentration of the aspirin (molar mass 180 g) b) Calculate the pKa of aspirin ……………………………… c) Assuming that aspirin is a monobasic acid, write the Ka equilibrium d) Using the answer from part (a) and the Ka value, calculate the [H+] e) Calculate the pH of the buffer solution The Carbonic-Acid-Bicarbonate Buffer in the Blood By far the most important buffer for maintaining acid-base balance in the blood is the carbonic-acid-bicarbonate buffer. The simultaneous equilibrium reactions of interest are H+ (aq) + HCO3- (aq) ↔ H2CO3 ↔ H2O + CO2 Other buffers perform a more minor role like the phosphate buffer consists of phosphoric acid (H3PO4) in equilibrium with dihydrogen phosphate ion (H2PO4-) and H+. Haemoglobin also acts as a pH buffer in the blood. Unit 1 Mod 2 Buffers page 4 of 4 How exercise affects the pH of blood When we exercise, our heart rate etc increases and the body's metabolism becomes more active, producing CO2 and H+ in the muscles. Eventually, with strenuous exercise, our body's metabolism exceeds the oxygen supply and begins to use alternate biochemical processes that do not require oxygen. The pH of the blood begins to decrease. Due to Le Chatelier’s Principle, the addition of CO2 and H+ causes an increase in the concentration of H2CO3 thereby decreasing the concentration of CO2 and H+. However this occurs with mild exercise, with strenuous exercise, the buffer system cannot adequately handle the drastic changes in pH that would occur. When there is strenuous exercise, the lungs remove CO2, the kidneys remove HCO3- ions, but the high heart rate can hinder CO2 removal. Why would buffer systems in enzyme catalysed reactions and in food chemistry industry be required? Checkpoint C