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Buffers

Buffer solution Some solutions resist changes in pH when small amounts of acid or base are added. On addition of acid the hydrogen ions get removed by one of the components of the mixture and on addition of base the hydroxide ions get removed by one of the components of the mixture. The effect is called buffering action an solutions that behave this way are called buffers. It must be remembered at this point that pH is a measure of the concentration of H+ ions. Also that the product of H+ ion and OH- ion concentrations is always constant (at constant temperature) and equal to 1 x 10-14 [H+] x [OH-] = 1 x 10-14 mol2 dm-6 There are two types of buffer. 1. Weak acid and the salt of the same weak acid, (for example a solution containing ethanoic acid and sodium ethanoate). This gives a buffer solution with a pH less than 7 2. Weak base and the salt of a the same weak base (for example ammonia and ammonium chloride solution). This gives a buffer with a pH greater than 7 The first (acidic) buffer works in the following way. If an acid is added it combines its free hydrogen ions with the ions from the salt of the weak acid making molecular weak acid that cannot affect the pH. If a base is added the OH- ions from the base react with the H+ ions that are present from the weak acid dissociation. Having been removed from the solution this stimulates the weak acid to produce more H+ ions (Le Chatelier's Principle) and the original pH is re-established. Example - an acidic buffer: A mixture of ethanoic acid and sodium ethanoate gives a buffer with a pH in the acidic range (there are free hydrogen ions in the solution). Two equilibria are established Equilibrium 1: CH3COOH molecules) Equilibrium 2: CH3COONa ethanoate ions) Hence, the mixture has large quantities of both ethanoic acid molecules [CH 3COOH] from the first equilibrium, and ethanoate ions [CH3COO-] from the second equilibrium. CH3COO- + Na+ CH3COO- + H+

The first equilibrium lies 99% to the left hand side (i.e. there is a large store of ethanoic acid

The second equilibrium lies almost 100% to the right hand side (i.e. there is a large store of

Bharti Dhakad..Department of biotechnology, Dr. H. S. Gour Central University Sagar (MP)

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there is a large reserve of free ammonia This equilibrium lies 100% to the right hand side (i.ions from equilibrium 1 and remove them. there is a large reserve of ammonia molecules available to dissociate from the left hand side making more OH.Buffers Addition of small quantities of acid (H+) The H+ ions added react with the excess ethanoate ions in equation 2 and are removed from the solution as ethanoic acid molecules (these have no effect on the pH). Example: A basic buffer A mixture of ammonium chloride (salt of a weak base) and ammonia solution (weak base) has buffering action.Department of biotechnology. a large reservoir of ethanoic acid on the left hand side of this equilibrium able to dissociate and make more hydrogen ions.e. however.1/0. Addition of small quantities of base (OH-) In this case. However. restoring the pH. S.it has the formula CH3COONa (relative molecular mass = 82) If 8.ions restoring the pH (remember that the value of [H+][OH-] must be constant under all conditions except a change of temperature) Addition of small quantities of base (OH-) Adding more OH. Hence the pH stays the same.ions react with the hydrogen ions from the first equilibrium removing them from the right hand side. The simplest way of preparing a buffer solution is to dissolve a known quantity of the salt of the weak acid (or base) in a solution of weak acid (or base ) of known concentration.2 g of sodium ethanoate are dissolved in 100 cm3 of ethanoic acid then: The concentration of the sodium ethanoate is equal to 0.ions that can react with the free ammonium ions (from equilibrium 2) producing more ammonia (as in equilibrium 1) and effectively being removed from the system. There is.1 = 1M The concentration of the ethanoic acid = 1M Bharti Dhakad.e. Dr. Example: Sodium ethanoate is the salt of a weak acid . H.. there is a large reserve of ammonium ions) Addition of small quantities of acid (H+) The H+ ions from the acid react with the OH. the OH. Once again two equilibria are established: Equilibrium 1: NH3 + H2O molecules) Equilibrium 2: NH4Cl NH4+ + ClNH4+ + OH- This equilibrium lies very much to the left hand side (i. Gour Central University Sagar (MP) Page 2 . The ammonia molecules have no effect on pH an therefore the pH remains the same.

05 moles molarity of acid = 0.05 x 1 = 0.log 1 pH = pKa In this case it can be easily appreciated that when the concentration of the acid and the salt are equal then pH =pKa This represents a rapid shortcut in questions of this type.05 moles This will neutralise and equal number of moles of the ethanoic acid = 0.05 moles / 0.1 dm3 = 0.05 moles Therefore moles of acid remaining = 0..5M The total initial acid moles : = 1 x 0.05 moles of sodium ethanoate CH3COOH + NaOH CH3COONa + H2O The concentration of the sodium ethanoate produced: = 0. Example: Add 50cm3 sodium hydroxide 1M solution to 50 cm3 1M ethanoic acid Moles of sodium hydroxide added = 0.Buffers Therefore the buffer solution will have pKa = pH Therefore the buffer has a pH value of 4. S.05 /0.1 moles Moles of acid reacted with sodium hydroxide = 0. If it can be shown that the weak acid concentration (or the weak base concentration) equals the salt concentration then pH = pKa and NO calculation needs to be carried out Bharti Dhakad. The neutralisation produces the salt of the weak acid (or base) 'in situ' and.78 Another way to prepare a buffer solution (much favoured by the IB examiners) is to neutralise an excess of weak acid (or weak base) with some strong base (or strong acid).05 = 0. as the weak acid was in excess.log[ethanoate ion]/[ethanoic acid] pH = pKa . Dr.0.Department of biotechnology.1 .5 M The buffer solution pH can then be obtained form the buffer law pKa = pH + log[ethanoate ion]/[ethanoic acid] pH = pKa .1 molarity of acid = 0. there will still be some weak acid in the mixture.1 = 0. Gour Central University Sagar (MP) Page 3 . The resultant mixture contains both the salt of the weak acid and the weak acid itself. H.05 moles and produce exactly 0.