Solvation

Dihydrogen Monoxide
pH
Ionization Hydrophobic effects

H−bonds Osmotic pressure Structure pKw Buffers Interactions

 Water

² Accounts of 70% of the mass of human body.

² Nearly all biological molecules assume their shapes in
response to the properties of the surrounding water.
² It is a medium for the majority of biological molecules.
² Active participant in many reactions.
² Strong ligand
² Ionizable: OH−,H+ (H3O+)
² [10−7 M] at pH 7.0
 Structure and Polarity
electronegativity difference
1.4
H O
polar covalent bond
2.1 (0.5 to 1.7) 3.5
net molecular

—
δ+ H—O δ− dipole moment

—
δ−
O
: :

H O H δ+ δ+
—
—

H H
 Solvation of ions

δ− interacts with cations

hydrated
ions
δ+ interacts with anions
δ− δ−
δ+ O δ+
H2O forms charge density due to H H
its polar characteristics.
Bond distance 0.958 Å
 Hydrogen Bonding

A hydrogen bond can be represented as D−H---A

•  D−H is a weakly acidic donor group
•  A is weakly basic acceptor group

The energy of a hydrogen bond (~20 kJ/mol)

Form with others polar solutes

The O H bond distance is ~ 1.8 Å

Van der Waals distance ~2.6 Å

H2O(l) forms flickering clusters, lasting ~ 2×10−11 s,

with 3.4 bonds per molecule on average.
 Hydrogen Bonding

Liquid water is only ~ 15% less H−bonded than ice at 0oC

In ice, each water molecule

interacts tetrahedrally with four
other water molecules forming
hexagonal symmetry.
 Hydrogen Bonding

Most sable when the donor O,

the proton, and the acceptor
O are in a straight line
 Hydrogen Bonding in Biomolecules

Protein/peptide backbones

Thymine (T)

H-bonding

Adenine (A)

Bases nucleic acids

 Hydrogen Bonding in Biomolecules
Electrostatic Interactions

Polar Amphipathic
O

O-
OH OH

O
O- O O
HO
OH Lactate OH OH O

O Glucose NH3

O Phenylalanine
O
O NH3 Aspartate
Oleat
O
OH
H2N
OH Nonpolar goups
HO OH
Glycine
Glycerol
 Hydrophobic Effect
Nonpolar regions are held together by hydrophobic interactions

Amphipathic (amphiphilic)
Molecules that contain both
polar and nonpolar groups, and
are thus attracted to both polar
and nonpolar environments.
i.e. Fatty acids
In Enzyme Catalyzed Reactions
 Osmotic Pressure

Osmosis, solvent movement across a semipermeable

membrane driven by differences in osmotic pressure.

Hypertonic Isotonic Hypotonic

Living cells are typically surrounded by a solution of

similar osmotic pressure to control the net flow of water.
 Osmotic Pressure

Osmotic pressure is the pressure that prevents the influx of

water, 22.4 atm for a 1 M solution.
Van’t Hoff equation: Π = icRT
Estimates the pressure (Π) measured as a force to resist water
movement through a semipermeable membrane. (ic = osmolarity)
 Dialysis: Diffusion of Water

Dialysis is a lab techniques that allows solutes smaller

than the pore size of a dialysis membrane to exchange
between the solution and the sample until equilibrium is
reached.
at equilibrium
 Water Ionization

Water readily ionizes to H3O+ and OH−.

[H+] [OH−]
H2O H+ + OH− Kd =
[H2O]
At 25°C, Kw = 10−14 M Kw = [H+] [OH−]
[H+] = [OH−] = 10−7M
pH = −log [H+]
pOH = −log [OH−]
14 = pH + pOH
 Effect of Weak Acids and Weak Bases

[H3O+] [A−]
HA + H2O H3O+ + A− Ka =
Conjugate
[HA]
base
pKa = −log [Ka]

[HO−] [HA]
A− + H2O HA + OH− Kb =
Conjugate [A−]
acid
pKb = −log [Kb]

For a weak acid/base equilibrium: Kw = Ka × Kb

K<1 weak acids (partially ionizable in solution)
K>>1 strong acids (i.e. HCl, fully ionizable in solution)
The smaller the
pKa the stronger
the acid.

The larger the

pKa the weaker
the acid.
 Henderson-Hasselbalch Equation
The relationship between the pH of a solution and the
concentration of its acid and conjugate base can be given
by:
[H+] [A−] [A−]
K= pH = pK + log
[HA] [HA]
Rearranged to Only for weak acids, and does not
account for water ionization itself.
[HA]
[H+] =K
[A−]
Taking the −log of each term
[HA]
−log [H+] = −log K − log
[A−]
 Buffers
²  An aqueous solution consisting of a mixture of a weak
acid and its conjugated base or a weak base and its
conjugated acid.
²  Resist changes in pH if any acid or base is added.
²  It is essential for maintaining the structure and function
of biological molecules.
²  Optimum buffering capacity occurs when the pH = pKa

²  When [HA]≈[A−], the pH of the solution is relatively

insensitive to the addition of strong base or strong acid.
 What is the ratio of NaH2PO4 and Na2HPO4 at
pH 7.0? Given: pKa of (H2PO4−/HPO42−) = 6.82

H2PO4− H+ + HPO42-
[A-]
pH = pKa + log
[HA]
[HPO42−] [HPO42−]
7.40 = 6.82 + log = 10 (7.0−6.82) = 1.5
[H2PO4−] [H2PO4−]
 Titration Curves

Useful buffer range within

one pH unit of its pKa

i.e. 6.8±1 for H2PO4−/HPO42−

The slope of each titration curve is

much lower near its midpoint than
near its wings
 Titration of a Polyprotic Acid

H3PO4 H+ + H2PO4−
pK1 = 2.15
12.38
H2PO4 − H+ + HPO4 2−

pK2 = 6.82
HPO42− H+ + PO43− 6.82
pK3 = 12.83

2.15