BMS1011

Structure of Biological
Macromolecules
Chemical Equilibria

Prof. Tanja Junkers

School of Chemistry
Email: tanja.junkers@monash.edu
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Learning outcomes
At the end of this session, you should be able to:

• Predict strength of acids and bases

• Determine position of equilibrium in acid-base reactions
• Calculate pH, pKa and pKb using Ka and Kb
• Apply the Henderson-Hasselbalch equation to understand pH buffers
Chemical equilibrium
Many chemical reactions result in the virtually complete conversion of reactants
into products.

When the reactants and products are of similar stability, the reaction is
reversible.

A reversible reaction is one that can go in either direction, from products to

reactants or reactants to products.
Chemical equilibrium

• The reaction read from left to right as written is referred to as the

forward reaction, and the reaction from right to left is referred to as
the reverse reaction.
• Both reactions occur until the concentrations of reactants and
products undergo no further change.
• At this point, the reaction vessel contains a mixture of all reactants
and products, and the reaction is said to be in a state of chemical
equilibrium.
Chemical equilibrium
Chemical equilibrium

• All substances present are being made and unmade at the same
rate, so their concentrations are constant at equilibrium

• It is not necessary for the concentrations of reactants and products at

equilibrium to be equal.

ka [ B]eq
ka
K eq = =
kb [ A]eq kb
Chemical equilibrium

• K much smaller than 0.001: Only reactants are present at

equilibrium; essentially no reaction occurs.
• K between 0.001 and 1: More reactants than products are
present at equilibrium.
• K between 1 and 1000: More products than reactants are
present at equilibrium.
• K much larger than 1000: Only products are present at
equilibrium; reaction goes essentially to completion.
Chemical equilibrium
Le Châtelier’s principle
–
When a stress is applied to a system at equilibrium, the equilibrium
shifts to relieve the stress and to restore a equilibrium.
The word “stress” means anything that disturbs the original equilibrium.
Changes in concentration, temperature, and pressure affect equilibria, but
addition of a catalyst does not (except to reduce the time it takes to reach
equilibrium).
 Acids and Bases
Brønsted-Lowry Acid-Bases

An acid is a proton donor conjugate

acid base

It must contain H in its formula, e.g. HNO3, H2PO4-, H2SO4, HCl.

A base is a proton acceptor

conjugate
base acid

Must contain a lone pair of electrons to bind the H+ ion, e.g. NH3, CO32-, OH-.
Acids and Bases
Acid and Bases strength
HCl, HBr,
-
HNO3, H3PO3 ,
H2SO4,
CH3COOH,
C6H5COOH,
HNO2, H3PO4

NaOH, KOH,
CaO, Mg(OH)2

NH3, C5H5N

Strong acid/base dissociates completely and weak

acid/base DOES NOT.
The Concepts of pH, pOH and Kw
The scale used to measure how acidic or basic a solution is known as pH.
The “H” comes from H+, which is really H3O+ in solution

If the concentration of [H3O+] is known, we can determine the value of pH

pH = -log10 [H3O+]

Less commonly used is the pOH scale. The “OH” comes from OH-, more
commonly used for very basic solutions.

If the concentration of [OH-] is known, we can determine the value of pOH

pOH = -log10 [OH-]

The relationship between [H3O+] and [OH-] is shown in Kw

[H3O+] x [OH-] = 1 x 10-14 @ 25oC = Kw

The Concepts of pH, pOH and Kw

Example Problem:

If the concentration of hydroxide in an aqueous solution is

[OH-] = 1.25x10-11 M, determine:
a) [H3O+]
b) The pH of the solution

Discuss in teams and try to find a solution!

The Concepts of pH, pOH and Kw
Kw: The relationship between [H3O+] & [OH-]

Just as:
[H3O+ ] x [OH- ] = Kw
pH + pOH = 14
-log10[H3O+] + -log10[OH -] = -log10Kw

pH + pOH = -log10Kw
@ 25oC, pH + pOH = -log (1 x 10-14)
Chemical equilibrium and acid strength
The Concepts of Ka and Kb

For weak acid….Ka = the acid dissociation constant

H3CCOOH + H2O H3CCOO- + H3O+

pKa = -log10 Ka

When Ka is large, pKa is small = ‘strong acid’

For bases:
pKb = -log10 Kb
Acid strength
Titration

Strong
base

analyte
Acid strength
Determination of pKa
Buffers

Buffers are solutions that maintain the pH approx. constant

despite small addition of acid or base - resist changes in pH

Usually a mixture of a weak acid and its conjugate base

When small quantities of H3O+ or OH- are added to the buffer, they
cause a small amounts of one buffer component to convert into
the other.
Le Chatelier’s Principle
How buffers work
How buffers work
An example
Solution of 0.001 M acetic acid and 0.001 M sodium acetate is a
‘buffer solution’
Determine the pH of this solution given the Ka = 1.73 x 10-5
How buffers work
Hendersson-Hasselbalch equation
How buffers work
Calculating buffers
Example: You need a buffer solution with pH = 4.00
Choose an acid with pKa as close as possible to the desired
pH value
Formic acid has Ka = 1.77 x 10-4 ( pKa = 3.75)

Use HCOOH and Na+COO- in the ratio of 10(-0.25) = 0.56

How buffers work
Blood buffer

How does blood maintain its narrow pH (7.35 – 7.45)?

Summary and learning outcomes
After this lecture you should be able to:

• Predict strengths of acids and bases

• Determine position of equilibrium in acid-base reactions
• Calculate pH, pKa and pKb using Ka and Kb
• Apply the Henderson-Hasselbalch equation to understand pH buffers
PACKUP AND EXIT