[2] Ionization of Water, Weak Acids, and Weak Bases

(1) Ionization of Water:

Slight tendency of H2O to undergo reversible ionization to

hydrogen ion (proton) and hydroxide ion:

H2O H+ + OH

BUT, free protons do not exist in solution:

protons are hydrated to hydronium ions:

H2O + H+ H3O+ (very fast due to proton hopping)

The ionization is expressed by an equilibrium constant (Keq)
H2O H+ + OH

[H+][OH]
Keq =
[H2O]

At 25 C, [H2O] = 55.5 M.
(55.5 M)(Keq) = [H+][OH] = Kw (ion product of water)
Keq is 1.8 x 10-16 M as determined by electro-conductivity exp.
Kw = (55.5 M)(1.8 x 1016 M) = [H+][OH] = 1.0 x 1014 M2
At neutral pH, [H+] =[OH] and [H+][OH-] = [H+]2
[H+] = 1.0 x 107 M in pure water at 25C.
Since Kw is constant,
when [H+] > 10-7 M [OH] < 10-7 M, and
when [H+] < 10-7 M [OH] > 10-7 M.
(2) The pH Scale
1
pH = log
[H+]

= log [H+]

pH 7 is neutral,
[ H+] = [OH]
pH < 7 is acidic,
[ H+] > [OH]
pH > 7 is basic,
[OH] > [ H+]

pH + pOH = 14
 The pH must be controlled in
an organism; where the breakdown
in pH regulation can lead to serious
metabolic disturbances:

The pH of blood is normally kept

within 7.35~7.45.
Outside the narrow range, the
organism can not function.
The pH of the cytosol of most cells
is ~ 7.4, however, in the lysosomal
organelles the pH is ~ 5.0. This is the
pH at which the degradative enzymes
(proteases) of the lysosome function
best, and they are actually inactive at
cytosolic pH!
 Negative pH ?
YES

http://en.wikipedia.org/wiki/PH

Most substances have a pH in the range 0 to 14,

although extremely acidic or extremely basic
substances may have pH less than 0 or greater than 14.

An example is acid mine runoff, with a pH = 3.6.

What is the pH of 0.1 M NaOH solution ? (p.62)
NaOH is a strong base and completely ionized in dilute aq.
solution.
[OH] = 0.1 M.
From Kw = [H+][OH] = 1.0 1014 M2,
[H+] = 10-14 M2/0.1 M = 1013 M. pH = log1013 = 13.
Or, from [OH] = 0.1 M, pOH = log 101 = 1.
Since pH + pOH = 14, pH of the solution is 13.

What is [OH] in a solution with [H+] of 1.3 x 104 M?

[OH] = Kw/[H+] = 1014 M2/1.3 10-4 M
= 0.769.... 1010 M
= 7.7 1011 M
(Notice the number of significant figures.)

pH meter: History and How it works

http://center.acs.org/landmarks/landmarks/phmeter/phmeter.html
(3) Weak Acids and Weak Bases

Acids proton (H+) donors; Bases proton acceptors

HA H+ + A (A : conjugate base)

[H+] [A]
Keq = Ka (dissociation constant) =
[HA]

Stronger acids larger Ka lower pKa ( logKa)

phosphoric acid (H3PO4): pKa = 2.34;

monohydrogen phosphate (HPO42): pKa = 12.4

Conjugate base of a strong acid is a weak base.

 (4) pKa and Titration Curve

- How do pH values of an
acetic acid solution
vary with added [OH]?
a titration curve

- Constructed by:
a) experiment
b) H-H equation

midpoint pH of titration =
pKa of corresponding acid:
b/c pH = pKa
when [HA] = [A]
* Slope lower near midpoint

When [HA] = [A],

pH is relatively insensitive to
addition of strong acid or base
i.e. buffered solution

Buffering capacity is maximal

when pH = pKa.

The useful range of a buffer is

within one pH unit of its pKa.
Above this, the pH will change
rapidly.
* Slope lower near midpoint

When [HA] = [A],

pH is relatively insensitive to
addition of strong acid or base
i.e. buffered solution.

Buffering capacity is maximal

when pH = pKa.

The useful range of a buffer is

within one pH unit of its pKa.
Above this, the pH will change
rapidly.
 Living Graph

Titration Curve for a Weak Acid

(5) Buffers

Buffer: A system whose pH changes only slightly

when small amounts of acid or base is added.

A buffer ordinarily consists of a weak acid and

its conjugate base, present in roughly equal amounts
(at pH = pKa of the acid)

Used to control the pH within a system

How buffer works? (Fig 2-19)
Buffer works because the added H+ or OH ions
are consumed and do not directly affect the pH.

HAc + OH H2O + Ac
Ac + H+ HAc

[buffer] >> added [H+]

or [OH]
(6) The Henderson-Hasselbalch (H-H) Equation

The pH of a solution, and the concentration of an acid and its

conjugate base are related by the H-H equation:
[A]
pH = pKa + log
[HA]

When the molar concentration of an acid (HA) and its conjugate

base (A) are equal ([A] = [HA]),
[A]/[HA] = 1; and log[A]/[HA] = log1 = 0
So the pH of the solution simply equals the pKa of the acid.

When [A] > [HA], pH > pKa.

When [A] < [HA], pH < pKa.
Derivation of the Henderson-Hasselbalch (H-H) Equation

From: Ka = [H+][A]/[HA], Solve for [H+], [H+] = Ka [HA]/[A]

Negative log of each side:
log [H+] = log Ka log([HA]/[A])
Convert to p scale: pH = pKa log([HA]/[A])
Invert log: pH = pKa + log([A]/[HA])

[proton acceptor]
pH = pKa + log
[proton donor]

Calculate the pH of a 2 L solution containing 10 mL of 5 M

acetic acid (CH3COOH) and 10 mL of 1 M sodium acetate
(CH3COONa). pKa of CH3COOH = 4.76.
 Living Graph

Henderson-Hasselbalch Equation (Box 2.3)

(7) Polyprotic Acids:
Substances that have more than one acid/base group.

H3PO4 H2PO4 + H+ HPO42 + H+ PO43 + H+

pKa1 = 2.14 pKa2 = 6.86 pKa3 = 12.4
Example: 1.00 mole of phosphoric acid (H3PO4) and 1.75 moles of NaOH are
added to 1 L of water. Calculate the pH.
Step 1: 1 mol of H3PO4 + 1.75 mol OH-
1 mol H2PO4- + 1 mol H2O + 0.75 mol OH-
Step 2: 1 mol of H2PO4- + 0.75 mol OH-
0.25 mol H2PO4- + 0.75 mol HPO42- + 0.75 mol H2O
Step 3: In the end, we have 0.25 moles of H2PO4- and 0.75 moles of HPO42-,
we can calculate the pH using the H-H equation:
Step 4: Look up the pKa of the reaction:
pKa for H2PO4- HPO42- + H+, is 6.86
Step 5: Calculate [HA] = [H2PO4-]: 0.25 mol/1 L = 0.25 M
Step 6: calculate [A-] = [HPO42-] : 0.75 mol/1 L = 0.75 M
Therefore: pH = pKa+ log[A-]/[HA]
= 6.86 + log((0.75 M)/(0.25 M)) = 7.34
Practice Questions
1. At 37oC, ion product for water (Kw) has a value
of 2.4 x 10-14.
What is the pH of pure water at 37oC? (6.81)

2. Hydroxide ions were released during an enzyme reaction

performed at pH 6.8.
Circle the buffer you would select for the enzyme assay.
CH3COOH/CH3COO- pKa = 4.76
H2PO4-/HPO42- pKa = 7.21
HCO3-/CO32- pKa = 10.0
Example: The addition of a 0.01 mL drop of 1 M HCl to 1 L of
water will change the pH from 7 to 5. A small
concentration of buffer can alter this so that there is
virtually no change in the pH, even with much larger
amounts of acid added!

Q13, p.74.
A buffer contains 0.010 mol of lactic acid (pKa=3.86) and
0.050 mol of sodium lactate per liter.
(a) Calculate the pH of the buffer.
(b) Calculate the change in pH when 5 mL of 0.5 M HCl is
added to 1 L of the buffer.
(c) What pH change would you expect if you added the same
quantity of HCl to 1 L of pure water (pH=7).

Work on Q1, 2, 3, 5(c), 8, 9, 10, 11, 12, 14, 15, 16 (p.73-4).

(8) Biological buffers:

HCO3 : H2CO3 pKa = 6.35

HPO42 : H2PO4 pKa = 6.86

pKa of amino acid, histidine = 6.0

Common buffers used in lab:
Buffer pKa (25oC) Effective pH Range
succinate (pK1) 4.21 3.2-5.2
acetate 4.76 3.6-5.6
citrate (pK2) 4.76 3.0-6.2
malate (pK2) 5.13 4.0-6.0
succinate (pK2) 5.64 5.5-6.5
MES 6.10 5.5-6.7
carbonate (pK1) 6.35 6.0-8.0
citrate (pK3) 6.40 5.5-7.2
imidazole 6.95 6.2-7.8
MOPS 7.14 6.5-7.9
phosphate (pK2) 7.20 5.8-8.0
HEPES 7.48 6.8-8.2
Trizma (Tris) 8.06 7.5-9.0
glycine (pK2) 9.78 8.8-10.6
carbonate (pK2) 10.33 9.5-11.1
Bicarbonate Buffer System in Blood and Lung
* Slope lower near midpoint

When [HA] = [A],

pH is relatively insensitive to
addition of strong acid or base
i.e. buffered solution

Buffering capacity is maximal

when pH = pKa.

The useful range of a buffer is

within one pH unit of its pKa.
Above this, the pH will change
rapidly.
Why does the titration curve of a week acid look the way it looks?
Using the H-H equation, lets follow the change of pH as we increase the ratio of [acid]/[base].
[CH3COO]
pH = pKa + log
[CH3COOH]
[CH3COO]/[CH3COOH] log([CH3COO]/[CH3COOH]) pH
1/10 log(1/10) = log10 = 1 4.76 1 = 3.76
1/4 log(1/4) = log4 = 0.602 4.76 0.602 = 4.16
1/2 log(1/2) = log2 = 0.301 4.76 0.301 = 4.46
3/4 log(3/4) = 0.125 4.76 0.125 = 4.64
1.0 log1 = 0 4.76
4/3 log(4/3) = 0.125 4.76 + 0.125 = 4.89
2/1 log2 = 0.301 4.76 + 0.301 = 5.06
4/1 log4 = 0.602 4.76 + 0.602 = 5.36
10/1 log10 = 1.0 4.76 + 1 = 5.76
and, so on....
From the H-H eq. we know that the pH is related to the ratio of [acid] and [conjugate base].
Since the relationship is logarithmic,
(1) pH decreases as the ratio approaches to 1.0 (titration midpoint), and
(2) the titration curve is symmetrical on both sides of the midpoint.
Conclusion: A solution made of a weak acid and its conjugate base has its highest buffer
capacity at pH equal to its pKa.
(9) Water as a Reactant
Hydrolysis (exergonic)
are catalyzed by hydrolases.
( Condensation)