Buffer Solution

What is buffer solution?

Buffer solution is a solution that resist changes in pH when small quantities of an acid or a base added to it. Buffer solution is used to keep pH almost constant. Buffer solution consist of weak acid with its conjugate base or weak base with its acid conjugate . 1. Acidic buffer solution An acidic buffer solution is simply one which has a pH less than 7. Acidic buffer solution consist of weak acid and its conjugate base. Example : 100 mL of 0,1 M acetic acid (CH3COOH) + 50 mL of 0,1 M sodium hidroxyde (NaOH). Mol of CH3COOH = 100 mL x 0,1 mmol mL-1 = 10 mmol Mol of NaOH = 50 mL x 0,1 mmol mL-1 = 5 mmol CH3COOH(aq) + NaOH(aq) NaCH3COOH(aq) + H2O(l) The ionic equations: CH3COOH(aq) + OH-(aq) CH3COO-(aq) + H2O(l) Initial Reaction Final 10 mmol 5 mmol 5 mmol 5 mmol 5 mmol 5 mmol

The mixed solution is a buffer solution, because its contain CH3COOH (weak acid) and CH3COO- (conjugate base of CH3COOH)

2. Base buffer solution A base buffer solution has a pH greater than 7. Base buffer solution consist of weak base and its conjugate acid. Example : 50 mL of 0,2 M ammonia (NH3) + 50 mL of 0,1 M hydrochloric acid (HCl). Mol of NH3 = 50 mL x 0,2 mmol mL-1 = 10 mmol Mol of NaOH = 50 mL x 0,1 mmol mL-1 = 5 mmol NH3 (aq) + HCl(aq) NH4Cl(aq) The ionic equations: NH3(aq) Initial Reaction Final 10 mmol 5 mmol 5 mmol + H+(aq) 5 mmol 5 mmol NH4+(aq) 5 mmol

The mixed solution is a buffer solution, because its contain NH3 (weak base) and NH4+ (conjugate acid of NH3)

How does buffer solution work?

Buffer solution works to maintain the pH value based on chemical equilibrium principle. Remember, the value of pH is affected by the concentration of H+ or OH-. In this case, the buffer solution need to contain things that can remove any H + ions or OHions that you might add to a reaction due to keep the concentration of H + or OH- will stay the same. As the result, the pH value will not show a significant change. However, acidic and alkaline (soluble base) buffer solution will do this in different ways. A. Acidic buffer solution We'll take a mixture of Ethanoic acid and Sodium Ethanoate as an example. Ethanoic acid is a weak acid, and the position of this equilibrium will be well to the left:

Adding Sodium Ethanoate to this adds lots of extra Ethanoate ions (because the concentration is higher). It will make the position of the equilibrium even further to the left. CH3COONa(aq) CH3COO-(aq) + Na-(aq)

As the result, the solution will contains these important things: a. Unionized Ethanoic acid (as its weak acid); b. Lots of Ethanoate ions from Sodium Ethanoate. c. Enough Hydrogen ions to make the solution acidic.

Adding an acid to this buffer solution The buffer solution must remove most of the new hydrogen ions that will cause the pH would drop significantly. Hydrogen ions combine with the ethanoate ions to make ethanoic acid. Although the reaction is reversible, since the ethanoic acid is a weak acid, most of the new hydrogen ions are removed in this way.

Since most of the new hydrogen ions are removed, the pH won't change very much but because of the equilibria involved, it will fall a little bit.

Adding an alkali to this buffer solution Alkaline solutions contain hydroxide ions and the buffer solution removes most of these. This time the situation is a bit more complicated because there are two processes which can remove hydroxide ions.

Removal by reacting with ethanoic acid The most likely acidic substance which a hydroxide ion is going to collide with is an ethanoic acid molecule. They will react to form ethanoate ions and water.

Because most of the new hydroxide ions are removed, the pH doesn't increase very much.

Removal of the hydroxide ions by reacting with hydrogen ions Remember that there are some hydrogen ions present from the ionisation of the ethanoic acid.

Hydroxide ions can combine with these to make water. As soon as this happens, the equilibrium tips to replace them. This keeps on happening until most of the hydroxide ions are removed.

Again, because you have equilibria involved, not all of the hydroxide ions are removed - just most of them. The water formed re-ionises to a very small extent to give a few hydrogen ions and hydroxide ions.

B. Alkaline buffer solution We'll take a mixture of ammonia and ammonium chloride solutions as an example.Ammonia is a weak base, and the position of this equilibrium will be well to the left:

Adding ammonium chloride to this adds lots of extra ammonium ions. According to Le Chatelier's Principle, that will tip the position of the equilibrium even further to the left.

As the result, the solution will contains these important things: a. lots of unreacted ammonia(as its weak acid); b. lots of ammonium ions from the ammonium chloride; c. Enough hydroxide ions to make the solution alkaline.

Adding an acid to this buffer solution There are two processes which can remove the hydrogen ions that you are adding.

Removal by reacting with ammonia The most likely basic substance which a hydrogen ion is going to collide with is an ammonia molecule. They will react to form ammonium ions.

Most, but not all, of the hydrogen ions will be removed. The ammonium ion is weakly acidic, and so some of the hydrogen ions will be released again.

Removal of the hydrogen ions by reacting with hydroxide ions

Remember that there are some hydroxide ions present from the reaction between the ammonia and the water.

Hydrogen ions can combine with these hydroxide ions to make water. As soon as this happens, the equilibrium tips to replace the hydroxide ions. This keeps on happening until most of the hydrogen ions are removed.

Again, because you have equilibria involved, not all of the hydrogen ions are removed - just most of them.

Adding an alkali to this buffer solution The hydroxide ions from the alkali are removed by a simple reaction with ammonium ions.

Because the ammonia formed is a weak base, it can react with the water - and so the reaction is slightly reversible. That means that, again, most (but not all) of the the hydroxide ions are removed from the solution.

C. Example Question Question: 1. A buffer solution is made by reacting Ammonia 1 M and Ammonium Chloride 0,8 M. What is the pH? (Ammonias Kb: 1,77 x 105) Answer: Kw = Ka.Kb 14 10 = (Ka).(1,77 x 105)

Ka pKa pH pH pH

= 5,65 x 1010 = - log Ka = - log 5,65 x 1010 = 9,248 = 9,248 - log (1 / 0,8) = 9,248 - 0,097 = 9,151

Calculating pH of Buffer Solution

Calculations involving a buffer made from a weak acid and its salt with a strong base. Therefore the weak acid Ka expression is: Ka= [H+(aq)][A- (aq)] [HA (aq)] 1. [A-(aq)] = acid conjugate 2. [HA(aq)]equilib., = [HA(aq)]initial since little of the weak acid is ionised. 3. [H+]= Ka a g pH= pKa log a g Calculations involving a buffer made from a weak alkaline and its salt with a strong acid. Kb= [OH-(aq)][L- (aq)] [LOH (aq)] [H+]= Kb b g pH= pKb log b b= moles of weak base g= moles of weak acid conjugate
mol/ dm 3 mol/ dm 3

a= moles of weak acid g= moles of weak base conjugate

Example :
1. A buffer solution was prepared which had a concentration of 0.20 mol dm -3 in

ethanoic acid and 0.10 mol dm-3 in sodium ethanoate. If the Ka for ethanoic acid is 1.74 x 10-5 mol dm-3, calculate the theoretical hydrogen ion concentration and pH of the buffer solution.

Answer :

Ka = [H+(aq)] [salt(aq)] [acid(aq)] 1.74 x 10-5 [H+(aq)] pH = [H+(aq)] x 0.10 / 0.20 = 1.74 x 10-5 x 0.20/0.10 = 3.48 x 10-5 mol dm-3 = -log(3.48 x 10-5) = 4.46

How to make a buffer solution?

1. Acid buffer solution can produced by: a. The weak acid mixed by its salt b. The excess weak acid mixed by strong base. It has to be excess weak acid, so that after strong base become limiting reactant, there is any weak acid that still consist which can become the acid component in buffer solution Weak Acid Concentration > Strong base concentration 2. Base buffer solution can produce by a. The weak base mixed by its salt b. The excess weak base mixed by strong acid It has to be excess weak base, so that after strong acid become limiting reactant, there is any weak base that still consist which can become the base component in buffer solution Weak Base Concentration > Strong Acid concentration Example: 1. Making acid buffer solution Weak acid CH3COOH only can decompose partially. To make acid buffer solution CH3COOH/CH3COO- , the consentration of CH3COO- has to be increased. CH3COOH(aq) Weak Acid H+(aq) Ionized partially + CH3COO-(aq) Conjugate Base

The concentration of conjugate base CH3COO- can be increased by a. Added salt, like CH3COONa to the weak acid CH3COOH(aq) H+(aq) CH3COO-(aq)

CH3COONa(aq) CH3COO-(aq) Salt Additional Conjugate Base So ,the acid buffer solution is CH3COOH/CH3COO-

+ Na+(aq)

b. Added strong base like NaOH to excess weak acid solution. CH3COOH(aq) + NaOH(aq) excess weak acid strong base Limiting Reactant So ,the acid buffer solution is CH3COOH/CH3COO-

Na+(aq) +

CH3COO-(aq) + H2O (l) Additional Conjugate Base

2. Making Base Buffer Solution Weak Base NH3 only can decompose partially. To make acid buffer solution NH3/NH4+ , the consentration of NH4+ has to be increased. NH3(aq) + Weak Base H2O (l) Ionized partially NH4+ (aq) + OH-(aq) Conjugate Acid

The concentration of conjugate acid NH4+ can be increased by a. Added salt, NH4+ Cl to the weak base NH3 NH3(aq) + H2O (l) NH4+ (aq) NH4+ Cl (aq) Salt + OH-(aq)

NH4+ (aq) + Cl-(aq) Additional Conjugate Acid

So ,the base buffer solution is NH3/NH4+ b. Added strong acid like HCl to excess weak base solution. NH3(aq) + HClaq) excess weak base strong acid Limiting Reactant So ,the base buffer solution is NH3/NH4+ Question: Check this solution, including buffer solution or not, prove it briefly! 1. CH3COOH + Ca(CH3COO)2 2. 50 mL CH3COOH 0,1 M + 50 mL NaOH 0,2 M Explanation 1. Themixture of solution of CH3COOH and Ca(CH3COO)2 is a buffer solution because its consist of weak acid CH3COOH and conjugate base CH3COO- from Ca(CH3COO)2 2. The mixture of 50 mL CH3COOH 0,1 M and 50 mL NaOH 0,2 M is not buffer solution because CH3COOH is not in excess CH3COOH + M R S : : : 5 mmol 5 mmol 0 OH10 mmol 5 mmol 5 mmol

Cl-(aq) +

NH4+ (aq) Additional Conjugate acid

CH3COO5 mmol 5 mmol

H2O 5 mmol 5 mmol