Unit 8: Acids & Bases
PART 2:
pH, pOH & pKw
The pH Scale
• pH is a value chemists use
to give a measure of the
acidity or alkalinity of a
solution.
• Used because [H+] is usually
very small
The pH Scale
• pH stands for pouvoir of hydrogen.
– Pouvoir is French for “power.”
– The normal range of the pH scale is 0-14.
– However, it is possible (if the hydronium or
hydroxide concentrations get above 1 Molar) for
the pH to go beyond those values.
pH = -log[H ] +
Thus, [H+] = 10-pH
As pH decreases, [H+] increases exponentially (a
change of one pH unit represents a 10-fold
change in [H+]
[H+]
Example: If the pH of a solution is changed from 3 to 5,
deduce how the hydrogen ion concentration changes.
pH = 3 pH = 5
pH = -log[H+] 5 = -log[H+]
3 = -log[H+] [H+] = 10-5
-3 = log[H+]
[H+] = 10-3
Therefore [H+] has decreased by a factor of 100.
Calculations involving acids and bases
• Sig figs for Logarithms: The rule is that the number of
decimal places in the log is equal to the number of
significant figures in the original number.
• Another way of saying this is only numbers after
decimal in pH are significant.
Example: [H+] = 1.0 x 10-9 M (2 significant figures)
pH = -log(1.0 x 10-9) = 9.00 (2 decimal places)
Ion product constant of water, Kw
• Recall that water autoionizes:
H2O(l) H+(aq) + OH-(aq) (endothermic)
[H ][OH ]
• Therefore Kc =
[H2O]
Ion product constant of water, Kw
• The concentration of water can be considered to be
constant because so little of it ionizes, and it can
therefore be combined with Kc to produce a modified
equilibrium constant known as kw. In fact, liquids and
solids never appear in equilibrium expressions for
this reason.
Kc[H2O] = [H+][OH-]
Kw
Ion product constant of water, Kw
Therefore, Kw = [H ][OH ]
Ion product constant of water, Kw
• At 25C, K = 1.00 x 10-14
w
• In pure water, because [H+]=[OH-], it follows that
[H+] = K w
• So at 25C, [H+] = 1.0 x 10-7, which gives pH = 7.00
Kw is temperature dependent
• Since the dissociation of water reaction in
endothermic (bonds breaking), an increase in
temperature will shift the equilibrium to the RIGHT,
thus INCREASING the value of Kw.
H2O(l) H+(aq) + OH-(aq) (endothermic)
Kw is temperature dependent
• As Kw increases, so do the concentrations of H+
(aq) and OH-(aq) pH decreases
• However, since hydronium and hydroxide
concentrations remain equal, water does not
become acidic or basic as temperature
changes, but the measure of its pH does
change.
Kw is temperature dependent
Temp (C) Kw [H+] in pure water pH of pure water
K
w
- log [H ]
10
0 1.5 x 10-15 0.39 x 10-7 7.47
10 3.0 x 10-15 0.55 x 10-7
7.27
20 6.8 x 10-15 0.82 x 10-7 7.08
25 1.0 x 10-14 1.00 x 10-7
7.00
30 1.5 x 10-14 1.22 x 10-7 6.92
40 3.0 x 10-14 1.73 x 10-7 6.77
50 5.5 x 10-14 2.35 x 10-7
6.63
H+ and OH- are inversely related
Because the product [H+] x [OH-] is constant at a given
temperature, it follows that as one goes up, the other
must go down (since Kw = [H+][OH-])
Type of sol’n Relative pH at 25C
concentrations
Acid
[H+] > [OH-] pH < 7
Neutral
[H+] = [OH-] pH = 7
Alkaline
[H+] < [OH-] pH > 7
Example: A sample of blood at 25C has [H+]=4.60 x 10-8 mol dm-3.
Calculate the concentration of OH- and state whether the
blood is acidic, neutral or basic.
Kw = [OH-][H+]
1.00 x 10-14 = [OH-][4.60 x 10-8]
[OH-] = 2.17 x 10-7 M
Since [OH-] > [H+],
the sample is basic.
Example: A sample of blood at 25C has [H+]=4.60 x 10-8 mol dm-3.
Calculate the concentration of OH- and state whether the blood is
acidic, neutral or basic.
• How would you expect its pH to be altered at body
temperature (37C)?
As temp. ↑, Kw and [H+] ↑ pH ↓
pH and pOH scales are inter-related
pOH= -log[OH ] -
pH and pOH scales are inter-related
From the relationship:
KW = [H+][OH-]
-log KW = -log([H+][OH-])
-log KW = (-log[H+]) + (-log[OH-])
pKW = pH + pOH
at 25C, KW = 1.0 x10-14, thus
14.00 = pH + pOH at 25C
Given any one of the following we can find the other three: [H+],
[OH-],pH and pOH
[H ]
+
100 10-1 10-3 10-5 10-7 10-9 10-11 10-13 10-14
pH
0 1 3 5 7 9 11 13 14
Acidic Neutral Basic
14 13 11 9 7 5 3 1 0
pOH
10-14 10-13 10-11 10-9Basic
10-7 10-5 10-3 10-1 100
[OH-]
Summary of Key Equations
pOH= -log[OH-]
pH= -log[H+] NOTE:
These equations apply
to all aqueous solutions
KW = [H+][OH-] (not just to pure water)
pKW = pH + pOH, and thus
14.00 = pH + pOH (at 25C)
Example: Lemon juice has a pH of 2.90 at 25C.
Calculate its [H+],[OH-], and pOH.
pOH:
pOH= 14.00 – 2.90 = 11.10
[H+]:
pH = -log[H+]
2.90 = -log[H+]
[H+] = 10-2.90 = 1.3 x 10-3 mol dm-3
[OH-]:
[OH-] = 10-11.10 = 7.9 x 10-12mol dm-3
