Mary K.

Campbell
Shawn O. Farrell
http://academic.cengage.com/chemistry/campbell

Chapter Two
Water: The Solvent for Biochemical Reactions

Paul D. Adams University of Arkansas

What makes water polar

What is a polar bond:
Electrons are unequally shared,more negative charge found closer to one atom.
Due to difference in electronegativity of atoms involved in bond.

Electronegativity
Electronegativity: a measure of the force of an
atoms attraction for electrons it shares in a chemical
bond with another atom
Oxygen and Nitrogen, more electronegative than
carbon and hydrogen
Fluorine is most electronegative (4)

Polar Bonds & Molecules

Molecules such as CO2 have polar bonds but, given
their geometry, are nonpolar molecules; that is, they
have a zero dipole moments

Solvent Properties of H2O

Ionic compounds (e.g.,KCl) and low-molecularweight polar covalent compounds (e.g., C2H5OH and
CH3COCH3) tend to dissolve in water
The underlying principle is electrostatic attraction of
unlike charges; the positive dipole of water for the
negative dipole of another molecule, etc.
ion-dipole interaction: e.g., KCl dissolved in H2O
dipole-dipole interactions: e.g., ethanol or acetone
dissolved in H2O
dipole induced-dipole interactions: weak and generally
do not lead to solubility in water

Hydration Shells Surrounding Ions in Water

Ion-dipole and Dipole-dipole Interactions

Ion-dipole and dipole-dipole interactions help

Solvent Properties of H2O

Hydrophilic: water-loving
tend to dissolve in water
Hydrophobic: water-fearing
tend not to dissolve in water

Amphipathic: has characteristics of both properties

molecules that contain one or more hydrophobic and
one or more hydrophilic regions, e.g., sodium palmitate

Amphipathic molecules
both polar and nonpolar character
Interaction between nonpolar molecules is very weak
called van der Waals interactions

Micelle formation by amphipathic molecules

Micelle: a spherical arrangement of organic
molecules in water solution clustered so that
their hydrophobic parts are buried inside the sphere
their hydrophilic parts are on the surface of the sphere
and in contact with the water environment
formation depends on the attraction between
temporary induced dipoles

Examples of Hydrophobic and Hydrophilic

Substances

Hydrogen Bonds
Hydrogen bond: the attractive interaction between
dipoles when:
positive end of one dipole is a hydrogen atom bonded
to an atom of high electronegativity, most commonly O
or N, and
the negative end of the other dipole is an atom with a
lone pair of electrons, most commonly O or N

Hydrogen bond is non-covalent

Interesting and Unique Properties of Water

Each water molecule can be involved in 4 hydrogen
bonds: 2 as donor, and 2 as acceptor
Due to the tetrahedral arrangement of the water
molecule (Refer to Figure 2.1).

Hydrogen Bonding
Even though hydrogen bonds are weaker than
covalent bonds, they have a significant effect on the
physical properties of hydrogen-bonded compounds

Other Biologically Important Hydrogen bonds

Hydrogen bonding is important in stabilization of 3-D
structures of biological molecules such as: DNA,
RNA, proteins.

Acids, Bases and pH

Acid: a molecule that behaves as a proton donor
Strong base: a molecule that behaves as a proton
acceptor

Acid Strength
One can derive a numerical value for the strength of an
acid (amount of hydrogen ion released when a given
amount of acid is dissolved in water).
Describe by Ka:

Written correctly,

Ionization of H2O and pH

Lets quantitatively examine the dissociation of water:

Molar concentration of water (55M)

Kw is called the ion product constant for water.

Must define a quantity to express hydrogen ion concentrationspH

Henderson-Hasselbalch
Equation to connect Ka to pH of solution containing
both acid and base.
We can calculate the ratio of
weak acid, HA, to its conjugate
base, A-, in the following way

Henderson-Hasselbalch (Contd)
Henderson-Hasselbalch equation
pH = pK a + log

[Conjugate base]
[Weak acid]

From this equation, we see that

when the concentrations of weak acid and its
conjugate base are equal, the pH of the solution
equals the pKa of the weak acid
when pH < pKa, the weak acid predominates
when pH > pKa, the conjugate base predominates

Titration Curves

Titration: an experiment in which measured amounts of acid (or base) are added to
measured amounts of base (or acid)
Equivalence point: the point in an acid-base titration at which enough acid has
been added to exactly neutralize the base (or vice versa)

a monoprotic acid releases one H+ per mole

a diprotic acid releases two H+ per mole
a triprotic acid releases three H+ per mole

Buffers
buffer: a solution whose pH resists change upon
addition of either more acid or more base
consists of a weak acid and its conjugate base

Examples of acid-base buffers are solutions

containing
CH3COOH and CH3COONa
H2CO3 and NaHCO3
NaH2PO4 and Na2HPO4

Buffer Range
A buffer is effective in a range of about +/- 1 pH unit
of the pKa of the weak acid

Buffer Capacity
Buffer capacity is related to the concentrations of
the weak acid and its conjugate base
the greater the concentration of the weak acid and its
conjugate base, the greater the buffer capacity

Naturally Occurring Buffers

H2PO4-/HPO42- is the principal buffer in cells
H2CO3/HCO3- is an important (but not the only) buffer
in blood

hyperventilation can result in increased blood pH

hypoventilation can result in decreased blood pH
(Biochemical Connections p. 60)

Selecting a Buffer
The following criteria are typical
suitable pKa
no interference with the reaction or detection of the
assay
suitable ionic strength
suitable solubility
its non-biological nature

Laboratory Buffers