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pH and Buffers

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4/17/12

Acids and Bases


Definition Acid Arrhenius Proton (H+) donor Bronsted- Proton (H+) Lowry donor Lewis Electron pair acceptor Base Hydroxide (OH-) donor Proton acceptor Electron pair donor

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Acid Strength

Strong acid

Dissociates completely in water (100%) Ex. HClO4, HCl, HNO3, H2SO4

Weak acid

Do not dissociate completely in water Ex. CH3COOH, HCOOH, HF

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Weak Acids

Some substances, like acetic acid (vinegar!) dissociate poorly in water. Thus, they release protons, but only a small fraction of their molecules dissociate (ionize). Thus, while 1 M HCl is pH = 0 (why?), 1 M acetic acid is only pH = 2.4

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Weak acids thus are in equilibrium with their ionized species:

Governed by the Law of Mass Action, and characterized by an equilibrium constant:

HA

H+ + A-

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Keq = [H+] [A-] Acid Dissociation Constant (Ka) [HA] of Describes the extent of ionization

Water: A Very Weak Acid +


2 H2O base)

+
hydronium ion H3O+ (an acid) hydroxide ion + OH(a

But this hardly happens at all: In fact, at equilibrium, [H+] = [OH-] = 0.0000001 M = 10-7 M = pH 7

Indeed, only two of every 109 (1 billion) molecules in pure water are ionized at any instant - Can you confirm this? 4/17/12

Comparative Equilibrium Constants


Water: Acetic acid Keq = 1.0 x 10-14 Keq = 1.7 x 10-5

But still, of every 1000 acetic acid molecules in a 1 M solution of acetic acid, only 4 are ionized.

A 100 billion-fold difference

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pH

Power of Hydrogen Describes the concentration of H+ in solution pH = -log[H+]

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SOURCE: http://en.wikipedia.org/wiki/Image:PH_scale.png#file

[H+] M 100 10-1 102 103 104 105 10-6 107 108 109 10-10 1011 10-12 1013 10-14

pH

A strong acid

pH = -log[H+] Most living cells have a very narrow range of tolerance for pH, i.e. [H+]. The [H+] concentration will be important

A strong base

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To measure pH
Litmus Paper pH Paper

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To measure pH

pH meter

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pH

Explain why 1 M HCl is pH = 0 1 M acetic acid is only pH = 2.4

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Computations: pH
1.

Calculate the pH of the following H+ containing solutions a. [H+] = 1.75 x 10-5M b. [H+] = 6.50 x 10-10 M c. [H+] = 1.0 x 10-4 M

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Computations: [H+]
2. Calculate the [H+] from pH a. pH = 3.82 b. pH = 6.52 c. pH = 11.11

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Computations (pKa)

Calculate the pKa of acetic acid

Ka = 1.8 x 10-5

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Computations
4. Calculate the pH of the following solutions: a. [OH-] = 7.5 x 10-7 M b. [OH-] =2.52 x 10-5 M

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Computations: pH of a weak acid


5. The Ka for benzoic acid is 6.5 x 105. Calculate the pH of a 0.1M benzoic acid solution.

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Computations: pH of a weak acid


6. Calculate the pH of an acetic acid solution with a concentration of 0.008M and a pKa of 4.74.

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Buffer solution

A solution composed of a weak acid and its conjugate base or a weak base and its conjugate acid that resists a drastic change in pH

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For biological systems:

Ionization of a strong acid is

BIG!

TOO

Ionization of water itself is way

TOO LITTLE!

Ionization of a weak acid is JUST RIGHT!


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Henderson-Hasselbach eqn

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Maximum Buffering Capacity

pH = pKa 1 What is the maximum buffering capacity of a solution containing CH3COOH (Ka = 1.8 x 10-5) and CH3COONa?

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Computations
1. Calculate the pH of a buffer containing 0.020 mol of CH3COOH (pKa = 4.76) and 0.050 mol of CH3COONa per 1.5 L of solution. What is the maximum buffering capacity of this buffer? Is the pH of the buffer within its maximum buffering capacity?
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Computations
2. An important buffer stabilizing the blood plasma is the bicarbonatecarbonic acid system. The concentration of H2CO3 in the blood plasma is 0.00125M, calculate [NaHCO3] in the blood plasma if pH = 7.4 and pKa = 6.1.

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Computations
3. The internal pH of a liver cell is 6.4. Physiologically this pH is maintained by means of phosphate buffer system. What is the predominant acid-base pair in the cell and what is the ratio of the conjugate base and acid?

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Computations
4. Describe the preparation of a 1.0L, 0.10M phosphate buffer with a pH of 7.00 using solid NaH2PO4 (MW = 120 g/mol) and Na2HPO4 (MW = 142 g/mol). pKa = 7.21

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Acid Dissociation Constant (Ka)

Describes the extent of ionization of an acid Equilibrium constant CH3COOH = CH3COO- + H+ Ka = [CH3COO-] [H+] / [CH3COOH] Concentrations at equilibrium

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