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The Common Ion Effect

Section 18.2
QUESTION: What is the effect on the pH QUESTION: What is the effect on the pH of adding NH4Cl to 0.25 M NH 3(aq)? aq)? of adding NH4Cl to 0.25 M NH 3(aq)? NH3(aq) + H2O NH4+(aq) + OH--(aq) aq) aq) aq) NH3(aq) O NH4+(aq) (aq) 2 Here we are adding an ion COMMON to Here we are adding an ion the equilibrium. the equilibrium. Le Chatelier predicts that the equilibrium Le will shift to the ____________. will shift to the ____________. The pH will go _____________. The pH will go _____________. After all, NH 4+ is an acid! After all, NH 4+ is an acid!

The Common Ion Effect

Section 18.2
QUESTION: What is the effect on the pH of adding NH 4Cl QUESTION: What is the effect on the pH of adding NH 4Cl to 0.25 M NH3((aq)? aq)? to 0.25 M NH3 aq)? + aq) NH3(aq) + H2O NH4 +(aq) + OH--(aq) aq) aq) NH3(aq) (aq) 2O NH4 (aq)

The Common Ion Effect

Section 18.2
QUESTION: What is the effect on the pH of adding NH 4Cl QUESTION: What is the effect on the pH of adding NH 4Cl to 0.25 M NH3((aq)? aq)? to 0.25 M NH3 aq)? + aq) NH3(aq) + H2O NH4 +(aq) + OH--(aq) aq) aq) NH3(aq) (aq) 2O NH4 (aq)

Let us first calculate the pH of a 0.25 M Let us first calculate the pH of a 0.25 M NH3 solution. NH3 solution. [NH3] [NH4 +] [OH--] [NH3] [NH4 +] [OH ] initial 0.25 0 0 initial 0.25 0 0 change -x +x +x change -x +x +x equilib 0.25 - x x x equilib 0.25 - x x x

Kb

1.8 x 10 -5 =

[NH4+ ][OH- ] x2 = 0.25 - x [NH3 ]

Assuming x is << 0.25, we have [OH-] = x = [Kb(0.25)]1/2 = 0.0021 M This gives pOH = 2.67 and so pH = 14.00 - 2.67 = 11.33 for 0.25 M NH3

The Common Ion Effect

Section 18.2
Problem: What is the pH of a solution Problem: with 0.10 M NH 4Cl and 0.25 M NH3(aq)? aq)? with 0.10 M NH 4Cl and 0.25 M NH3(aq)? + aq) NH3(aq) + H2O NH4+(aq) + OH--(aq) aq) aq) NH3(aq) (aq) 2O NH4 (aq) We expect that the pH will decline on We expect that the pH will decline on adding NH 4Cl. Lets test that! adding NH 4Cl. Lets test that! [NH3] [NH4 +] [OH--] [NH3] [NH4 +] [OH ] initial initial change change equilib equilib

The Common Ion Effect

Section 18.2
Problem: What is the pH of a solution Problem: with 0.10 M NH 4Cl and 0.25 M NH3(aq)? aq)? with 0.10 M NH 4Cl and 0.25 M NH3(aq)? + aq) NH3(aq) + H2O NH4+(aq) + OH--(aq) aq) aq) NH3(aq) (aq) 2O NH4 (aq) We expect that the pH will decline on We expect that the pH will decline on adding NH 4Cl. Lets test that! adding NH 4Cl. Lets test that! [NH3] [NH4 +] [OH--] [NH3] [NH4 +] [OH ] initial 0.25 0.10 0 initial 0.25 0.10 0 change -x +x +x change -x +x +x equilib 0.25 - x 0.10 + x x equilib 0.25 - x 0.10 + x x

The Common Ion Effect

Section 18.2
Problem: What is the pH of a solution with 0.10 M NH 4Cl Problem: What is the pH of a solution with 0.10 M NH 4Cl and 0.25 M NH3((aq)? aq)? and 0.25 M NH3 aq)? + aq) NH3(aq) + H2O NH4+(aq) + OH--(aq) aq) aq) NH3(aq) (aq) 2O NH4 (aq)

Kb

1.8 x 10 -5 =

[NH4+ ][OH- ] x(0.10 + x) = 0.25 - x [NH3 ]

[OH-] = x = (0.25 / 0.10)K b = 4.5 x 10 -5 M This gives pOH = 4.35 and pH = 9.65

pH drops from 11.33 to 9.65 on adding a common ion.

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Buffer Solutions Buffer Solutions

HCl is added to pure water.

Buffer Solutions
The function of a buffer is to resist changes in the pH of a solution. Buffers are just a special case of the common ion effect. Buffer Composition Weak Acid + Conj. Base Conj. HOAc + OAcH2PO4+ HPO42Weak Base + Conj. Acid Conj. NH3 + NH4+

Buffer Solutions
Consider HOAc/OAc- to see how buffers work HOAc/ ACID USES UP ADDED OH We know that OAc- + H2O HOAc + OHhas Kb = 5.6 x 10-10 Therefore, the reverse reaction of the WEAK ACID with added OH has Kreverse = 1/ Kb = 1.8 x 109 Kreverse is VERY LARGE, so HOAc completely snarfs up OH- !!!!

HCl is added to a solution of a weak acid H2PO4- and its conjugate base HPO42-.

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Buffer Solutions
Consider HOAc/OAc- to see how buffers HOAc/ work CONJ. BASE USES UP ADDED H + HOAc + H2O OAc- + H3O+ has Ka = 1.8 x Therefore, the reverse reaction of the WEAK BASE with added H + has Kreverse = 1/ Ka = 5.6 x 104 Kreverse is VERY LARGE, so OAc- completely snarfs up H+ ! 10-5

Buffer Solutions
Problem: What is the pH of a buffer that has [HOAc] = 0.700 M and [OAc-] = 0.600 M? HOAc] [OAc HOAc + H2O OAc- + H3O+ Ka = 1.8 x 10 -5 [HOAc] HOAc] initial change equilib 0.700 -x 0.700 - x [OAc-] [H3O+] 0.600 0 +x +x x 0.600 + x

Buffer Solutions
Problem: What is the pH of a buffer that has [ HOAc] HOAc] = 0.700 M and [OAc-] = 0.600 M? [OAc - + H O+ HOAc + H2O OAc 3 Ka = 1.8 x 10 -5

[HOAc] [OAc-] [H3O+] HOAc] equilib 0.700 - x 0.600 + x x Assuming that x << 0.700 and 0.600, we have
Ka 1.8 x 10 -5 = [H3O + ](0.600) 0.700

[H3O+] = 2.1 x 10-5 and pH = 4.68

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Buffer Solutions
Notice that the expression for calculating the H+ conc. of the buffer is conc.
[H3O ] Orig. conc. of HOAc Orig. conc. of OAc Ka

Henderson-Hasselbalch Equation Henderson-Hasselbalch

[H3O ] [Acid] K [Conj. base] a

Adding an Acid to a Buffer

Problem: What is the pH when 1.00 mL of 1.00 M HCl is added to a) 1.00 L of pure water (before HCl, pH = HCl, 7.00) b) 1.00 L of buffer that has [ HOAc] = 0.700 HOAc] M and [OAc-] = 0.600 M (pH = 4.68) [OAc Solution to Part (a) Calc. [HCl] after adding 1.00 mL of HCl to 1.00 Calc. [HCl] L of water M1V1 = M2 V2 M2 = 1.00 x 10 -3 M

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Take the negative log of both sides of this equation

pH pK a - log [Acid] [Conj. base]

[H3O ]

[Acid] K [Conj. base] a

[OH ]

[Base] K [Conj. acid] b

pH

pK a + log

[Conj. base] [Acid]

Notice that the H + or OH- concs. depend on concs. K and the ratio of acid and base concs. concs.

The pH is determined largely by the pKa of the acid and then adjusted by the ratio of acid and conjugate base.

pH = 3.00

Adding an Acid to a Buffer

What is the pH when 1.00 mL of 1.00 M HCl is added to a) 1.00 L of pure water (after HCl, pH = 3.00) HCl, b) 1.00 L of buffer that has [HOAc] = 0.700 M and [HOAc] [OAc-] = 0.600 M (pH before = 4.68)

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Adding an Acid to a Buffer

What is the pH when 1.00 mL of 1.00 M HCl is added to a) 1.00 L of pure water (pH = 3.00) b) 1.00 L of buffer that has [HOAc] = 0.700 M and [HOAc] [OAc-] = 0.600 M (pH = 4.68)

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Adding an Acid to a Buffer

What is the pH when 1.00 mL of 1.00 M HCl is added to a) 1.00 L of pure water (pH = 3.00) b) 1.00 L of buffer that has [HOAc] = 0.700 M and [HOAc] [OAc-] = 0.600 M (pH = 4.68)

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Solution to Part (b) Step 1 do the stoichiometry H3O+ (from HCl) + OAc- (from buffer) ---> HCl) HOAc (from buffer) The reaction occurs completely because K is very large.

Solution to Part (b): Step 1 Stoichiometry [H3O+] + [OAc-] ---> [HOAc] [HOAc] 0.00100 0.600 0.700 Before rxn -0.00100 -0.00100 Change +0.00100 After rxn 0 0.599 0.701

Solution to Part (b): Step 2Equilibrium HOAc + H 2O H3O+ + OAc[HOAc] [H3O+] + [OAc-] HOAc] 0.701 0 0.599 Before rxn -x +x Change +x 0.701-x x 0.599 + x After rxn

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Adding an Acid to a Buffer

What is the pH when 1.00 mL of 1.00 M HCl is added to a) 1.00 L of pure water (pH = 3.00) b) 1.00 L of buffer that has [HOAc] = 0.700 M and [HOAc] [OAc-] = 0.600 M (pH = 4.68) OAc-]

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Adding an Acid to a Buffer

What is the pH when 1.00 mL of 1.00 M HCl is added to a) 1.00 L of pure water (pH = 3.00) b) 1.00 L of buffer that has [HOAc] = 0.700 M and [HOAc] [OAc-] = 0.600 M (pH = 4.68) OAc-]

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Preparing a Buffer Preparing a Buffer

You want to buffer a solution at pH = 4.30. This means [H3O+] = 10-pH = 5.0 x 10 -5 M It is best to choose an acid such that [H 3O+] is about equal to Ka (or pH pKa). then you get the exact [H 3O+] by adjusting the ratio of acid to conjugate base.

Solution to Part (b): Step 2Equilibrium HOAc + H 2O H3O+ + OAc[HOAc] [H3O+] + [OAc-] HOAc] After rxn 0.701-x 0.599+x x Because [H 3O+] = 2.1 x 10 -5 M BEFORE adding HCl, we again neglect x relative to 0.701 and HCl, 0.599.

Solution to Part (b): Step 2Equilibrium HOAc + H 2O H3O+ + OAc[H3O ] [HOAc] [OAc - ] Ka 0.701 (1.8 x 10 -5 ) 0.599

= 2.1 x M ------> pH = 4.68 The pH has not changed on adding HCl to the buffer! [H3O+] 10-5

[H3O ]

[Acid] K [Conj. base] a

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Preparing a Buffer Preparing a Buffer

You want to buffer a solution at pH = 4.30 or [H3O+] = 5.0 x 10 -5 M POSSIBLE ACIDS Ka HSO4 - / SO421.2 x 10-2 HOAc / OAc1.8 x 10-5 HCN / CN 4.0 x 10-10 Best choice is acetic acid / acetate.

Preparing a Buffer Preparing a Buffer

You want to buffer a solution at pH = 4.30 or [H3O+] = 5.0 x 10 -5 M

Preparing a Buffer Preparing a Buffer

A final point CONCENTRATION of the acid and conjugate base are not important. It is the RATIO OF THE NUMBER OF MOLES of each. Result: diluting a buffer solution does

[H3O ]

5.0 x 10-5 =

[HOAc] [OAc- ]

(1.8 x 10 -5 )

Solve for [HOAc]/[OAc-] ratio [HOAc]/[OAc

2.78 1

not change its pH

Therefore, if you use 0.100 mol of NaOAc and 0.278 mol of HOAc, you will have pH = HOAc, 4.30.

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Preparing a Buffer Preparing a Buffer

Buffer prepared from HCO3weak acid CO32conjugate base HCO3- + H 2O H3O+ + CO32-

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