Lecture 3 - PH

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Dr. DialaAbu-Hassan, DDS, PhD
Dr.abuhassand@gmail.com
Lecture 3
MD summer 2014
1 Dr. Diala Abu-Hassan
pH
Outline
pH
Henderson-Hasselbalch Equation
Monoprotic and polyprotic acids
Titration
Dr. Diala Abu-Hassan 2
pH = -log
10
[H
+
]
Measuring the acidity of solutions, pH
Garrett et al
3
Dr. Diala Abu-Hassan
Garrett et al
The pH scale is a logarithmic
scale.
One pH unit difference implies a
10-fold difference in [H+].
Example: lemon juice at pH 2.0
contains more than 100 times as
much H+as orange juice at pH
4.0
pH
Measuring acidity in aqueous solutions- pH scale
pH = - log [H
3
O
+
]
[H
3
O
+
] = 10
-pH
Example 1: [H
3
O
+
] in household bleach is 10
-12
M
pH = - log [10
-12
] = 12
Example 2: Orange juice has a pH of 4
[H
3
O
+
] = 10
-4
M
Example 1:
What is the pH of a solution whose hydrogen ion
concentration is 3.2 x 10
4
mol/L?
pH= -log [H
+
]
= -log (3.2 x 10
-4
)
= -log (3.2) log (10
-4
)
= -0.5 + 4.0
= 3.5
pH problem solving
Acidic = more H+
Basic = more OH
-
Acids
Neutral
Bases
pH in solutions
Strong Acids and pH
HCl H
+
+ Cl
-
Ka = [H
+
] [Cl
-
]
[HCl]
[H
+
] = [acid]
Ex.1 M solution of HCl has a pH of
1 mM HCl solution has a pH of
0
0.1 M NaOH solution has a pH of
3
13
8
Dr. DialaAbu-Hassan
K
w
= [H
+
] [OH
-
] = 10
-14
Valid for acidic, basic, neutral and pure H
2
O
pH = - log [H
+
]
pOH = - log [OH
-
]
pH + pOH = 14
Dissociation of water
Example: A solution has an [OH
-
] = 10
-9
M
[H
3
O
+
] = 10
-5
M pH = 5
pH scale for some common substances
Campbell 6
th
edition
Enzyme activity and pH
11
12
Example:
Find the K
a
of a 0.04 M weak acid HA whose pH is 4.0?
K
a
= [A
-
] [H
+
] / [HA] = [H
+
]
2
/ [HA] = 10
-4
x10
-4
/ 0.04 = 2.5 x 10
-7
HA H
+
+ A
-
Example 2:
What is the pH of a 0.05 M Ba(OH)
2
?
[OH
-
] = 2x 0.05 = 0.10 M = 1 x 10
-1
pOH = - log 1 x 10
-1
= 1
pH= 14-1 = 13
[H
+
] = 1x 10
-13
Ba(OH)
2
Ba + 2OH
-
Remember pOH = -log [OH
-
]
13
Example:
The K
b
for ammonia is 1.8 x 10
-5
M. What is the pH of 1 x 10
-2
M of ammonia?
K
b
= [NH
4
+
] [OH
-
] / [NH
3
]
1.8 x 10
-5
= [OH
-
]
2
/ 0.01
[OH
-
] = 4.24 x 10
-4
M
pOH = -log 4.24 x 10
-4
= 3.37
pH = 14 - 3.37 = 10.63
NH
3
+ H
2
O NH
4
+
+ OH
-
The dissociation of a weak acid is as follows:
The acid dissociation constant is as follows:
Rearranging this expression in terms of the parameter
of interest [H+] gives the following:
HA H
+
+A
-
K
a
=
[H
+
][A
-
]
[HA]
K
a
[H
+
] =
[HA]
[A
-
]
Take the log of both sides:
log K
a
+ log log[H
+
] =
[HA]
[A
-
]
Change the signs , remember pK
a
= -log K
a
:
pK
a
- log
pH =
[HA]
[A
-
]
pK
a
+ log
pH =
[A
-
]
[HA]
or
pH = pKa
pH < pKa
pH > pKa
pH= pKa -1
pH=pKa + 1
What happens when ..
Substance protonation and deprotanation are in equillibruim.
H
+
on, substance protonated
H
+
off, substance deprotonated
Base/acid = 0.1
Base/acid = 10
16
Dr. DialaAbu-Hassan
17
Monoprotic- and PolyproticAcids
1. Monoprotic acids have only one ionizable proton.
2. Polyprotic acids have more than one ionizable proton.
3. The protons are removed in steps, not all at once.
CH
3
COOH + NaOH CH
3
COO
-
Na
+
+ H
2
O
H
3
PO
4
H
2
PO
4
-
HPO
4
-2
PO
4
-3
+ + +
H
+
H
+
H
+
pK
a1
=2.14
pK
a2
=7.20 pK
a3
=12.4
Polyprotic Acids
Sulfuric acid is a strong acid in its first dissociation step
and a weak acid in its second step.
H
2
SO
4
(aq) H
+
(aq) + HSO
4
(aq) K
a1
1.0x10
2
HSO
4
(aq) H
+
(aq) + SO
4
2
(aq) K
a2
1.2x10
-2
Polyprotic Acids
It is always easier to remove the first proton in a
polyprotic acid than the second. That is, K
a1
> K
a2
> K
a3
A plot of the fractions of H
2
CO
3
, HCO
-
3
and CO
3
2-
At pH = 9.00 H
2
CO
3
0%, HCO
-
3
= 95%and CO
3
2-
= 5%
At pH = 10.00 H
2
CO
3
0%, HCO
-
3
= 68%and CO
3
2-
= 32%
K
a1
=4.3 x10
-7
K
a2
=4.8 x10
-11
21
Titration
Titration is an experiment in which measured amounts of
base are added to a measured amount of acid while
following up changes in pH using a pH meter.
22
Titration curves
[CH
3
COOH] =[CH
3
COO
-
]
CH
3
COOH + OH
-
CH
3
COO
-
+ H
2
O
In the region small pH changes
upon addition of acid or base, the
acid/base ratio varies within a
narrow range (10:1 at one end
and 1:10 at the other end ).
pH =pK
a
Inflection point
The point in the titration at which
the acid is exactly neutralized is
called the equivalence point.
Titration curves
Once OH
-
is added to the
reaction, it reacts completely with
HA to form A
-
x = the equivalents of OH
-
added
V represents the volume of the
solution.
[A
-
] =
x
V
[HA] =
V
[Base]
[HA
i
]-[Base]
( )
pK
a
pK
a
pK
a
pK
a
+ log
pH =
[HA
i
]-[Base]
Example:
Calculate the relative amounts of acetic acid and acetate ion
present and pH values when 1 mol of acetic acid is titrated with
sodium hydroxide.
0.1 mol of NaOH is added
When 0.1 mol of NaOH is added, 0.1 mol of acetic acid reacts
with it to form 0.1 mol of acetate ion, leaving 0.9 mol of acetic
acid. The composition is 90% acetic acid and 10% acetate ion.
pH = pKa + log 0.1/0.9
pH = 4.76 + log 0.1/0.9
pH = 4.76 - 0.95
pH = 3.81
CH
3
COOH + OH
-
CH
3
COO
-
+ H
2
O
http://www.nd.edu/
Titration curve of Glycine
Equivalents of OH
-
added

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