The Color Change of the Indicator Bromthymol Blue

Fig. 19.5
Acid-Base Indicators
Usually dyes that are weak acids and display different
colours in protonated/deprotonated forms.
HIn(aq.) H
+
(aq.)

+In
-
(aq.)


In general we seek an indicator whose transition range (1pH
unit from the indicator pK
a
) overlaps the steepest part of the
titration curve as closely as possible
| || |
| | HIn
In H
K
-
a
+
=
Strong acids give weak bases.
Weak acids give strong bases.
CH
3
C
O
O H
+
H
CH
3
C
O
O
H Cl
+
H Cl
H C H
H
H
H C
H
H
+
H
-7

pK
a
4.74

~50

Strong acids give weak bases.
Weak acids give strong bases.
CH
3
C
O
O H
+
H
CH
3
C
O
O
H Cl
+
H Cl
H C H
H
H
H C
H
H
+
H
acidity
basicity
Colors and Approximate pH Range of
Some Common Acid-Base Indicators
Which molecule is the stronger acid, ethanol
or acetic acid?
CH
3
C
O
O
CH
3
C
O
O H
CH
3
C
O
O
H
+
acetic acid
CH
3
CH
2
OH
+
H CH
3
CH
2
O
ethanol
K
a
10
-16
10
-4.74
more stable anion
because of
resonance and
inductive effects
CH
3
CH
2
OH
+
H CH
3
CH
2
O
CH
3
C
O
O H
CH
3
C
O
O
H
+
the stronger
acid
C C
O
OH
H
H
H
H
+ C C
O
O
H
H
H
Predict whether trifluoroacetic acid will be a
stronger or weaker acid than acetic acid.
C C
O
OH
F
F
F
trifluoroacetic acid
acetic acid
H
+ C C
O
O
F
F
F
K
a
10
-0.23
10
-4.74
more acidic acid
Fluorine is more electro-
negative than hydrogen. Anion
is more stable.
pK
a
48

38

15.7

C H
H
H
H C
H
H
H + H
N H
H
H N
H
H + H
O
H
O
H
+ H H
increasing
electronegativity
It is a general principle that the more stable
the anion the more acidic is the acid.
The principle is also successful across a row of
the periodic table.
Biological fluids are often buffered (constant pH) an
it is useful to know the predominant species present
at a given pH.
In chemistry, particularly biology, a large
number of compounds are acids and bases.
HO
HO
NH
2
HO
HO
NH
3
H
+
CO
2
H HO
CO
2
H CO
2
H
+
H
CO
2
HO
CO
2
H CO
2
H
dopamine
citric acid
at pH = 4.74
Consider acetic acid with a K
a
= 10
-4.74
at lower pH, more acidic
than 4.74, acetic acid is the
major species present
[CH
3
CO
2
H] [CH
3
CO
2
]
=
H
at pH = 4.74
Consider acetic acid with a K
a
= 10
-4.74
at lower pH, more acidic
than 4.74, acetic acid is the
major species present
[CH
3
CO
2
H]
[CH
3
CO
2
]
>
H
[CH
3
CO
2
H]
at pH = 4.74
Consider acetic acid with a K
a
= 10
-4.74
at lower pH, more acidic
than 4.74, acetic acid is the
major species present
at higher pH, less acidic
than 4.74, acetate ion is
the major species present
[CH
3
CO
2
H] [CH
3
CO
2
] <
[CH
3
CO
2
H]
[CH
3
CO
2
]
OH
The pH of blood is maintained at ~ 7.4
If the pH of blood was 4.74 then the
acetate ion would be equal to the acetic
acid ion concentration.
If acetic acid is introduced into the blood
what will be the predominant species present?
Will it be acetate ion or acetic acid?
[HOCCH
3
] =
O
[ OCCH
3
]
O
at pH = 4.74
If the pH is raised to 7.4 will the
concentration of acetate ion increase or
decrease?
If acetic acid is introduced into the blood
what will be the predominant species present?
Will it be acetate ion or acetic acid?
[HOCCH
3
] =
O
[ OCCH
3
]
O
pH 4.74 7.4
If the pH is raised to 7.4 (more basic)
will the concentration of acetate ion
increase or decrease?
O H
If acetic acid is introduced into the blood
what will be the predominant species present?
Will it be acetate ion or acetic acid?
[HOCCH
3
] =
O
[ OCCH
3
]
O
at pH = 4.74
If the pH is raised to 7.0 will the
concentration of acetate ion increase or
decrease?
Acetate ion is the major species present
if acetic acid is introduced into blood.
The Henderson-Hasselbalch Equation
Take the equilibrium ionization of a weak acid:
HA
(aq)
+ H
2
O
(aq)
= H
3
O
+
(aq)
+ A
-
(aq)
K
a
=
[H
3
O
+
] [A
-
]
[HA]
Solving for the hydronium ion concentration gives:
[H
3
O
+
] = K
a
x
[HA]
[A
-
]
Taking the negative logarithm of both sides:
-log[H
3
O
+
] = -log K
a
- log
( )
[HA]
[A
-
]
pH = -log K
a
- log
( )
[HA]
[A
-
]
Generalizing for any conjugate acid-base pair :
pH = -log K
a
+ log
( )
[base]
[acid]
Henderson-Hasselbalch
equation
H-A
+
H A
pK
a
= pH + log (1) pK
a
= pH
when

[H-A] [ A ] =
a useful concept:
p H = -log [H

]
Biological fluids are often buffered (constant pH) an
it is useful to know the predominant species present
at a given pH.
pH = pKa + log
[A
-
]
[HA]
HENDERSON-HASSELBALCH EQUATION
[HA]
] ][A [H
K
a
+
=
|
|
.
|

\
|
=
+
[HA]
] ][A [H
log K log -
a
|
|
.
|

\
|
=

+
[HA]
] [A
log ] [H log
For acids:
For bases:
] [BH
[B]
log pK pH
a
+
+ =
B + H
2
O BH
+
+ OH
-

acid base acid base


K
a

K
b

pK
a
applies
to this acid
When [A
-
] = [HA],
pH = pK
a

Derivation:
HA H
+
+ A
-
|
|
.
|

\
|
=

[HA]
] [A
log pH pK
a
|
|
.
|

\
|
+ =

[HA]
] [A
log pK pH
a
|
|
.
|

\
|
+ =

[HA]
] [A
log pK pH
a
BUFFERS
Mixture of an acid and its conjugate base.
Buffer solution resists change in pH when acids
or bases are added or when dilution occurs.
Mix:
A moles of weak acid + B moles of conjugate base
Find:
moles of acid remains close to A, and
moles of base remains close to B
Very little reaction
HA H
+
+ A
-
Le Chateliers principle
Why does a buffer resist change in pH when small
amounts of strong acid or bases is added?
The acid or base is consumed
by A
-
or HA respectively
A buffer has a maximum capacity to resist change to pH.
Buffer capacity, |:
Measure of how well solution resists change in
pH when strong acid/base is added.
pH
C
pH
C
a b
d
d
d
d
= = |
?
Larger | more resistance to pH change
How a Buffer Works
Consider adding H
3
O
+
or OH
-
to water and also to a buffer
For 0.01 mol H
3
O
+
to 1 L water:
[H
3
O
+
] = 0.01 mol/1.0 L = 0.01 M pH = -log([H
3
O
+
]) = 2.0

So, change in pH from pure water: ApH = 7.00 2.00 = 5.0
For the H
2
CO
3
-
/ HCO
3
-
system:
pH of buffer = 7.38

Addition of 0.01 mol H
3
O
+
changes pH to 7.46

So change in pH from buffer: ApH = 7.46 7.38 = 0.08 !!!
How a Buffer Works
Consider a buffer made from acetic acid and sodium acetate:
CH
3
COOH
(aq)
+ H
2
O
(l)
CH
3
COO
-
(aq)
+ H
3
O
+
(aq)
K
a
= or
[CH
3
COO
-
] [H
3
O
+
]
[CH
3
COOH]
[CH
3
COOH]
[CH
3
COO
-
]
[H
3
O
+
] = K
a
x
How a Buffer Works
Lets consider a buffer made by placing 0.25 mol of acetic acid and
0.25 mol of sodium acetate per liter of solution.

What is the pH of the buffer?

And what will be the pH of 100.00 mL of the buffer before and
after 1.00 mL of concentrated HCl (12.0 M) is added to the buffer?

What will be the pH of 300.00 mL of pure water if the same acid
is added?
pH = -log[H
3
O
+
] = -log(1.8 x 10
-5
) = pH = 4.74 Before acid added!
[H
3
O
+
] = K
a
x = 1.8 x 10
-5
x
[CH
3
COOH]
[CH
3
COO
-
] (0.25)
(0.25)
= 1.8 x 10
-5

How a Buffer Works
1.00 mL conc. HCl 1.00 mL x 12.0 mol/L = 0.012 mol H
3
O
+
Added to 300.00 mL of water :
0.012 mol H
3
O
+
301.00 mL soln.
= 0.0399 M H
3
O
+
pH = -log(0.0399 M)
pH = 1.40 Without buffer!
What is pH if added to pure water?
How a Buffer Works
After acid is added to buffer:
Conc. (M) CH
3
COOH
(aq)
+ H
2
O
(aq)
CH
3
COO
-
+ H
3
O
+
Initial 0.250 ---- 0.250 0
Change +0.012 ---- -0.012 0.012
Equilibrium 0.262 ---- 0.238 0.012
Solving for the quantity ionized:
Initial 0.262 ---- 0.238 0
Change -x ---- +x +x
Equilibrium 0.262 - x ---- 0.238 + x x
Assuming: 0.262 - x = 0.262 & 0.238 + x = 0.238
pH = -log(1.982 x 10
-5
) = 5.000 - 0.297 = 4.70 After the acid is added!
Conc. (M) CH
3
COOH
(aq)
+ H
2
O
(aq)
CH
3
COO
-
+ H
3
O
+
[CH
3
COOH]
[CH
3
COO
-
]
[H
3
O
+
] = K
a
x =1.8 x 10
-5
x

(0.262)
(0.238)
= 1.982 x 10
-5

How a Buffer Works
Suppose we add 1.0 mL of a concentrated base instead of an acid. Add
1.0 mL of 12.0 M NaOH to pure water and our buffer, and lets see what
the impact is: 1.00 mL x 12.0 mol OH
-
/1000mL = 0.012 mol OH
-

This will reduce the quantity of acid present and force the equilibrium
to produce more hydronium ion to replace that neutralized by the
addition of the base!
Conc. (M) CH
3
COOH
(aq)
+ H
2
O
(aq)
CH
3
COO
-
+ H
3
O
+
Initial 0.250 ---- 0.250 0
Change - 0.012 ---- +0.012 +0.012
Equilibrium 0.238 ---- 0.262 +0.012
Assuming: Again, using x as the quantity of acid dissociated we get:
our normal assumptions: 0.262 + x = 0.262 & 0.238 - x = 0.238
[H
3
O
+
] = 1.8 x 10
-5
x = 1.635 x 10
-5
0.238
0.262
pH = -log(1.635 x 10
-5
) = 5.000 - 0.214 = 4.79 After base is added!
How a Buffer Works
By adding the 1.00mL base to 300.00 mL of pure water we would get a
hydroxide ion concentration of:
301.00 mL
0.012 mol OH
-
[OH
-
] = = 3.99 x 10
-5
M OH
-
This calculates out to give a pH of:
The hydrogen ion concentration is:
[H
3
O
+
] = = = 2.506 x 10
-10
K
w
[OH
-
]
1 x 10
-14
3.99 x 10
-5
M
pH = -log(2.5 6 x 10
-10
) = 10.000 - 0.408 = 9.59 With 1.0 mL of the
base in pure water!
In summary:
Buffer alone pH = 4.74
Buffer plus 1.0 mL base pH = 4.79 Base alone, pH = 9.59
Buffer plus 1.0 mL acid pH = 4.70 Acid alone, pH = 1.40
Problem:
Calculate the pH of a solution containing 0.200 M NH
3

and 0.300 M NH
4
Cl given that the acid dissociation
constant for NH
4
+
is 5.7x10
-10
.
NH
3
+ H
2
O NH
4
+
+ OH
-
acid base
K
a

] [BH
[B]
log pK pH
a
+
+ =
pK
a
applies
to this acid
pK
a
= 9.244
pH = 9.244 + log
(0.200)
(0.300)
pH = 9.07