Lecture 5 - Acid Base Concepts
Lecture 5 - Acid Base Concepts
Lecture 5 - Acid Base Concepts
and Acid-Base
Chemistry
H+
H2O
OH
Keq
[H+][OH-]
[H2O]
Keq [H2O]
[H+][OH-]
[H+][OH-]
Kw
[H+]
= [OH ]
(Kw)
(1 x
10-14)
1/2
1 x 10-7 M
Any solution that contains equal concentrations of H+ and OH- (like pure water) is said
to be neutral.
Solutions with [H+] > [OH-] are acidic.
Solutions with [H+] < [OH-] are basic.
[H+][OH-]
1 x 10-14 M2
[H+][OH-]
1 x 10-14 M2
(1 x 10-3 M) [OH-]
1 x 10-14 M2
[OH-]
1 x 10-14 M2
(1 x 10-3 M)
[OH-]
1 x 10-11 M
note that the [H+] (1 x 10-3 M) is much higher than the [OH-] (1 x 10-11).
A hundred million times higher to be exact!
Because these number range so widely, we convert them to a logarithmic scale, called pH
H+
HCl
NaOH
Cl-
Na+ + OH-
[H+]
= [Cl-] = 0.1 M =
1 x 10-1 M H+
What is the pH of this solution? The pH is the negative log of the hydrogen ion concentration.
pH = -log10[H+]
pH = -log (1 x 10-1M)
pH = -(-1) = 1
pH = -log[H+]
[H+] = antilog (-pH)
[H+] = antilog (-1)
[H+] = 1 x 10-1 M
The pH scale
pH, which is defined as the negative logarithm of the
Hydrogen ion concentration, is a convenient scale
turning small and awkward numbers into
whole numbers
Moran p43
2. What is the [H+] in an aqueous solution of 0.2 M HCl. What is the pH?
3. You add 10 ml of 0.1 M HCl to 990 ml water. What are the [H+] and [OH-]
in this solution? What is the pH of the solution?
HA
H+
+ Aconjugate base of HA
weak acid
For example, acetic acid (CH3COOH) dissociates to the conjugate base CH3COO- and H+
H+
weak acid, acetic acid
(CH3COOH)
The strength of a weak acid (its ability to release H+ ions) can be determined using
following expression:
Ka
[H+][A-]
[HA]
for acetic acid, where Ka = 1.76 x 10-5 M we can calculate the [H+] in a 0.1 M solution
of acetic acid and also its pH:
1.76 x 10-5
1.76 x 10-5
Ka
[H+][CH3OO-]
[CH3COOH]
[H+][CH3OO-]
[CH3COOH]
x2
0.1 M
simplifying assumption:
concentration of acid remains
nearly constant.
Because Ka values vary over a wide range, they are expressed using a log scale:
pKa = -log10Ka
McKee p87
Buffers
Buffers are solutions that resist changes in pH
Ka
Ka
McKee p89
This is why, when we titrate (in the example below) a conjugate base by adding acid
this kind of curve is obtained:
acid
H2O
Kw
H+
OH-
H+
if we add extra H+ ions to water
they will combine with OH- ions
to form water, driving the equilibrium
towards H2O formation.
the problem is that the dissociation constant of water is so low, there are few OHions available to react with H+ ions. Thus when acid is added to
pure water, the pH plummets immediately (we therefore view water as
unbuffered).
Chemical reactions often produce or consume H+ ions. When we study these
reactions in the lab, we do not want the pH of the reaction liquid to change.
Thus we add a buffer: a mixture of weak acid and its conjugate base to resist the
change in pH that would otherwise occur and perhaps ruin (or confound)
the experiment.
Ka
[H+][A-]
[HA]
-log [H+]
[H+]
Ka
[HA]
-log Ka -log
[A-]
[HA]
pH = pKa -log
[A-]
[HA]
[A-]
-]
[A
= pKa + log
[HA]
-]
[A
pH = pKa + log
[HA]
A titration curve reveals that the best buffering situation (where a solution best
resists changes in pH when acid or base is added) occurs when the
concentrations of the acid [HA] and its conjugate base [A-] are equal.
This situation occurs when the pH of the solution equals the pKa of the acid:
pH = pKa + log [A ]
[HA]
pH = pKa + log (1)
pH = pKa
the most effective buffering occurs 1 pH unit above and below an acids pKa
Acetic acid has a pKa of 4.8. How many ml of 0.1 M acetic acid and 0.1 M Na acetate are
required to prepare 1 litre of 0.1 M buffer solution having a pH of 5.8?
pH = pKa + log
[A ]
[HA]
[A-]
antilog (1) =
[HA]
[A-]
[HA]
-]
[A
10 =
[HA]
= 10
1
10 volumes of acetate ion (Na acetate) must be added for every 1 volume of acetic acid
equaling a total of 11 volumes.
acetate needed
1
11
10
11
x 1000 ml = 91 ml
x 1000 ml = 909 ml
CH3COOH
H+
+ CH3COO-
pKa = 4.8
H3PO4
H+
H2PO4-
H+
2
HPO4
H+
H2PO4-
pKa1 = 2.2
HPO42-
pKa2 = 7.2
+ PO4
3-
pKa3 = 12.7
Moran p48
C
H
CH3
pKa1 = 2.3
H3N+
C
OH
C
H
O
C
O
CH3
pKa2 = 9.7
H2N
C
H
Some amino acids also have ionizable side chains as well, as we will see later.
O
C
O
All possess:
H2N C C
OH
H
The amino and carboxyl group can be ionized depending on the surrounding pH.
At the pH typical of cytoplasm (pH 6.8 7.4, physiological pH) the amino group will be
protonated and the carboxyl group will be deprotonated.
Thus we typically draw amino acids in this form:
H3N C C
O
H
The
zwitterionic form of
an amino acid
H2N C C
OH
H
R
+
H3N C C
O
H
note all amino acids
have ionized carboxyl
group above pH 2
and ionized amino
group below
pH 9-10
Key Concepts
Water itself ionizes to a very small degree into H+ (H3O+) ions and OH- ions
pH (a logarithmic scale) is used because the H+ concentrations can vary over such
a vast range.
pKa (a logarithmic scale) is a measure of the ability of a weak acid to dissociate
into H+ ions and the conjugate base of the weak acid
Buffers are mixtures of weak acids and their conjugate bases. They resist changes
in pH.
The Henderson-Hasselbalch equation relates pH and pKa and is useful for creating
buffers in the laboratory.
Naturally occurring buffers regulate pH in the blood, in cells, and other body fluids.
pH influences the ionization state of many biomolecules and thus influences their
chemical characteristics and the chemistry of the cell.
H+ ions participate ( are produced and consumed) in many chemical reactions in
the cell.