Buffers

Common Ion Effect

Adding a common ion to an equilibrium system
will shift the equilibrium forward or reverse.
For a weak acid equilibrium this can affect the
pH of the solution.
For example: Adding NaF to a solution of HF.
HF
H + + FAdding F- ions will shift the equilibrium to
reactants and produce more HF and reduce [H+]
ions in the process.
This makes the pH increase.

Buffers
Buffers are solutions in which the
pH remains relatively constant,
even when small amounts of acid
or base are added
Contain a weak acid (HA) and its
salt(NaA); H2CO3 & NaHCO3
Or a weak base (B) and its
(BHCl); (NH3 and NH4Cl)

Buffers
A buffer system is better able to resist
changes in pH than pure water
Since it is a pair of chemicals:
one chemical neutralizes any acid
added, while the other chemical
would neutralize any additional
base
AND, they produce each other
in the process!!!

How a Buffer Works

Consider the following buffer system
HCO3- + H+
H2CO3
If you add more H+ this buffer system it will
react with the conjugate base HCO3- to
produce more H2CO3.
If you add base, OH-, it will grab an H+
from H2CO3 to produce more HCO3- ion as
follows
H2CO3 + OHH2O + HCO3-

Ionization of acetic acid:

Resisting changes both ways

OH

H 2O

Acetic acid
Ac

Acetate

(CH 3COO )

HAc

(CH3COOH)

Buffer Capacity
The buffer capacity is the amount of
acid or base that can be added
before a significant change in pH
This depends on the amounts of HA
and A- present in the buffer
Most efficient buffer is when
[A-]
=1
[HA]

Henderson-Hasselbach Equation
Derived from the equilibrium expression of
a weak acid and the pH equation.

[A-]
pH = pKa + log[HA]
This equation allows you to determine the
pH of a buffer solution
pKa = -log Ka

The Common Buffer Problems

1. Compute pH of a buffer given the
actual concentrations of the conjugate
acid and conjugate base.
The pH is easily calculated with:

pH = pKa + log

[A-]
[HA]

Example: Determine the pH in which 1.00

mole of H2CO3 (Ka = 4.2 x 10-7) and 1.00
mole NaHCO3 dissolved in enough water
to form 1.00 Liters of solution.

pH = pKa + log

[A-]

[HA]
pH = -log (4.2 x 10-7) + log (1.00M)/(1.00M)

pH = pKa = 6.4
** pKa of a weak acid can help determine pH of buffer
you will make if it is mixed in a 1:1 mole ratio!

Buffer Solutions
Buffer solutions are equilibrium systems, which maintain a relatively constant pH
when small amounts of acids or bases are added.

Acid Buffer Recipe

Weak Acid
HF

Salt (conjugate)
NaF

Buffer Equation Same as weak acid

HF
[High]

H+ +

F-

Buffer Solutions
Buffer solutions are equilibrium systems, which maintain a relatively constant pH when
small amounts of acids or bases are added.
Acid Buffer Recipe
Weak Acid

HF

Salt (conjugate)
NaF

Buffer Equation Same as weak acid

HF
[High]

H+ +
[low]

F-

Buffer Solutions
Buffer solutions are equilibrium systems, which maintain a relatively constant pH when
small amounts of acids or bases are added.
Acid Buffer Recipe
Weak Acid

HF

Salt (conjugate)
NaF

Buffer Equation Same as weak acid

HF

[High]

H+ +

[low]

F-

[High]

Buffer Equation Same as weak acid

HF
[High]

H+ +

F-

[low]

[High]

The [HF] is relatively high because HF is a weak acid and does not dissociate
very much.
The [H+] is low for the same reason.
The [F-] is high due to adding the salt NaF to the solution.
This buffer solution has high concentrations of HF and F -, which means it has
the ability to shift left or right and maintain the H+ concentration and hence the
pH remains at a relatively constant level.

1.0 M HCN is mixed with 2.0 M NaCN to make a buffer solution.

Write the equation for the buffer solution.
Determine the [HCN] and [CN-].
HCN
1.0 M

H+ +

CN-

1.0 M HCN is mixed with 2.0 M NaCN to make a buffer solution.

Write the equation for the buffer solution.
Determine the [HCN] and [CN-].
HCN
1.0 M

H+ +
Low

CN-

1.0 M HCN is mixed with 2.0 M NaCN to make a buffer solution.

Write the equation for the buffer solution.
Determine the [HCN] and [CN-].
HCN
1.0 M

H+ +
Low

CN2.0 M

Base Buffer Recipe

Weak Base

NH3

Salt (conjugate)
NH4Cl

Buffer Equation Same as weak base

NH3 +

H2O

NH4+

+ OH-

Base Buffer Recipe

Weak Base

NH3

Salt (conjugate)
NH4Cl

Buffer Equation Same as weak base

NH3 +
[High]

H2O

NH4+

+ OH-

Base Buffer Recipe

Weak Base

NH3

Salt (conjugate)
NH4Cl

Buffer Equation Same as weak base

NH3 +
[High]

H2O

NH4+
[High]

+ OH-

Base Buffer Recipe

Weak Base

NH3

Salt (conjugate)
NH4Cl

Buffer Equation Same as weak base

NH3 +
[High]

H2O

NH4+
[High]

+ OH[Low]

Fill in the blanks to get buffer solutions.

Acid
HCN

Base

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN
NaHCO3

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

NaH2PO4

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

NaH2PO4
KCH3COO

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

NaH2PO4

CH3COOH

KCH3COO

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

NaH2PO4

CH3COOH

KCH3COO

NH4Cl

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

NaH2PO4

CH3COOH

KCH3COO

NH4Cl

NH3

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

NaH2PO4

CH3COOH

KCH3COO

NH4Cl

NH3
Na2CO3

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

NaH2PO4

CH3COOH

KCH3COO

NH4Cl

NH3

NaHCO3

Na2CO3

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

NaH2PO4

CH3COOH

KCH3COO

NH4Cl

NH3

NaHCO3

Na2CO3

NaH2PO4

Fill in the blanks to get buffer solutions.

Acid

Base

HCN

NaCN

H2CO3

NaHCO3

H3PO4

NaH2PO4

CH3COOH

KCH3COO

NH4Cl

NH3

NaHCO3

Na2CO3

NaH2PO4

Na2HPO4

1. Pick the two buffer solutions

A. NH4Cl and
B. NaCl

HCl

and NaOH

C. HF and NaF
D. NH4Cl and NH3

1. Pick the two buffer solutions

A. NH4Cl and
B. NaCl

HCl

and NaOH

C. HF andNaF
D. NH4Cl andNH3

1. Pick the two buffer solutions

A. NH4Cl and
B. NaCl

HCl

and NaOH

C. HF andNaF
D. NH4Cl andNH3
2. Write the equations for the above two buffer solutions.
Label each species in the equation as high or low concentration.

1. Pick the two buffer solutions

A. NH4Cl and
B. NaCl

HCl

and NaOH

C. HF and NaF
D. NH4Cl and NH3
2. Write the equations for the above two buffer solutions.
Label the each species in the equation as high or low
concentration.
HF
H + + F[High]
NH3

[Low]
+

H2O =

[High]
NH4+

OH-

1. Pick the two buffer solutions

A. NH4Cl and
B. NaCl

HCl

and NaOH

C. HF and NaF
D. NH4Cl and NH3
2. Write the equations for the above two buffer solutions.
Label the each species in the equation as high or low
concentration.
HF
H + + FNH3

H2O =

NH4+

OH-

1. Pick the two buffer solutions

A. NH4Cl and
B. NaCl

HCl

and NaOH

C. HF and NaF
D. NH4Cl and NH3
2. Write the equations for the above two buffer solutions.
Label the each species in the equation as high or low
concentration.
HF
H+ + F[High]
NH3

[High]

[Low]
+

H2O =

[High]
NH4+

[High]

OH-

[Low]

Acid base indicators

An indicator is a substance which is used
to determine the end point in a titration. In
acid base titrations, organic substances
(weak acids or weak bases) are generally
used as indicators. They change their
colour within a certain pH range. The
colour change and the pH range of some
common indicators are tabulated below:

Indicator

pH range

Colour change

Methyl orange

3.2-4.5

Pink to yellow

Methyl red

4.4-6.5

Red to yellow

Litmus

5.5-7.5

Red to blue

Phenol red

6.8-8.4

Yellow to red

Phenolphthalein

8.3-10.5

Colourless to pink

Indicators
Methyl violet

HInd

Acid

H+

Ind-

Base

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift
At pH < 0.8

Colour

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift
At pH < 0.8

Colour
Left

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift
At pH < 0.8

Colour
Left

Yellow

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift
At pH < 0.8

Colour
Left

Yellow

[HInd] > [Ind-]

Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift
At pH < 0.8

Colour
Left

At pH > 0.8

Yellow

[HInd] > [Ind-]

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift

Colour

At pH < 0.8

Left

At pH > 0.8

Right

Yellow

[HInd] > [Ind-]

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift

Colour

At pH < 0.8

Left

At pH > 0.8

Right

Yellow
Blue

[HInd] > [Ind-]

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift

Colour

At pH < 0.8

Left

At pH > 0.8

Right

Yellow
Blue

[HInd] > [Ind-]

[HInd] < [Ind-]

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift

Colour

At pH < 0.8

Left

At pH > 0.8

Right

At pH = 0.8

Yellow
Blue

[HInd] > [Ind-]

[HInd] < [Ind-]

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift

Colour

At pH < 0.8

Left

At pH > 0.8

Right

At pH = 0.8

Middle

Yellow
Blue

[HInd] > [Ind-]

[HInd] < [Ind-]

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift

Colour

At pH < 0.8

Left

Yellow

At pH > 0.8

Right

Blue

At pH = 0.8

Middle

Green

[HInd] > [Ind-]

[HInd] < [Ind-]

Indicators
Methyl violet

HInd

H+

Ind-

Acid

Base

Yellow

Blue

Shift

Colour

At pH < 0.8

Left

Yellow

[HInd] > [Ind-]

At pH > 0.8

Right

Blue

[HInd] < [Ind-]

At pH = 0.8

Middle

Green

[HInd] = [Ind-]

Theory of acid-base indicators:

Two theories have been proposed to explain the change of
colour of acid-base indicators with change in pH.

1. Ostwald's theory:
According to this theory:
(a)The colour change is due to ionisation of the acid-base
indicator. The unionised form has different colour than
the ionised form.
(b) The ionisation of the indicator is largely affected in
acids and bases as it is either a weak acid or a weak
base. In case, the indicator is a weak acid, its ionisation
is very much low in acids due to common H+ ions while
it is fairly ionised in alkalies. Similarly if the indicator is a
weak base, its ionisation is large in acids and low in
alkalies due to common OH- ions.

Considering two important indicators phenolphthalein (a weak

acid) and methyl orange (a weak base), Ostwald theory can be
illustrated as follows:

Phenolphthalein: It can be represented as HPh. It

ionises in solution to a small extent as:

HPh H+ + Ph
Colourless

Pink

Applying law of mass action,

K = [H+][Ph- ]/[HpH]
The undissociated molecules of phenolphthalein are colourless
while Ph- ions are pink in colour. In presence of an acid the
ionisation of HPh is practically negligible as the equilibrium shifts to
left hand side due to high concentration of H+ ions. Thus, the
solution would remain colourless. On addition of alkali, hydrogen
ions are removed by OH- ions in the form of water molecules and
the equilibrium shifts to right hand side. Thus, the concentration of
Ph- ions increases in solution and they impart pink colour to the
solution

Let us derive Handerson equation for

an indicator
HIn + H2O H3O + + In'Acid form'
'Base form
Conjugate acid-base pair
Kln = [ln][H3O + ]/[HIn]

KIn = Ionization constant for indicator

[H3O + ] = Kln [ HIn] / [ln]
pH = -log10[ H3O + ] = -log10[KIn ] -log10] [ HIn] /[In- ]
pH = p KIn + log10[In-]/[Hln]

(Handerson
equation for indicator)
At equivalence point
[In- ] = [HIn]
And
pH = pKIn

Methyl orange:
It is a very weak base and can be represented as MeOH. It
is ionized in solution to give Me+ and OH- ions.
MeOH Me+ + OHYellow
Red
Applying law of mass action,

K = [Me+ ][OH- ]/[MeOH]

In presence of an acid, OH- ions are removed in the form
of water molecules and the above equilibrium shifts to right
hand side. Thus, sufficient Me+ ions are produced which
impart red colour to the solution. On addition of alkali, the
concentration of OH" ions increases in the solution and the
equilibrium shifts to left hand side, i.e., the ionisation of
MeOH is practically negligible. Thus, the solution acquires
the colour of unionised methyl orange molecules, i.e.,
yellow.

This theory also explains the reason why

phenolphthalein is not a suitable indicator for
titrating a weak base against strong acid. The
OH" ions furnished by a weak base are not
sufficient to shift the equilibrium towards right
hand side considerably, i.e., pH is not
reached to 8.3. Thus, the solution does not
attain pink colour. Similarly, it can be
explained why methyl orange is not a suitable
indicator for the titration of weak acid with
strong base.