WATER

Chapter 2
Part 1 of 2
in biochem book 6e, starts on page 47
 WATER
In this course we shall study the structure and func3on of the major
classes of cellular chemical cons3tuents:

§  water (Chapter 2)
§  amino acids and proteins (Chapters 3 through 6)
§  sugars and polysaccharides (Chapter 7)
§  fa@y acids and lipids (Chapter 10)
§  membranes (Chapters 11)

We begin with WATER because its proper3es affect the structure

and func3on of all other cellular cons3tuents
 WATER: THE SOLVENT OF LIFE
Because it was in water that the biochemical reac3ons evolved, all
aspects of cell structure and func3on adapted to the physical and
chemical proper3es of water.

Water is needed for:

•  Biochemical reac3ons
•  Transporta3on of chemical substances
•  Maintaining body temperature
•  Dissolving waste products for excre3on

•  Producing diges3ve fluids

•  Governing structure, stability, dynamics, and func3on of biological
macromolecules. Water is considered integral component of
biomolecular systems.
 WATER
Water accounts for about 70% of the weight of most
organisms.

water
other

In our body, a loss of 10% of water is serious. A loss of 20% is

fatal.
 WATER
Water is a compound that consists of two hydrogen atoms
and one oxygen atom a@ached together by two COVALENT
bonds and with two lone pairs of electrons around the
oxygen atom.

Only two of the six outer-shell electrons of oxygen are used

for bonding, leaving four electrons which are organized into
two non-bonding pairs.
 WATER
The geometry of the molecule is dictated by
the presence of two nonbonding electron
pairs on the oxygen atom.

nonbonding
The electron geometry is e-
pairs
TETRAHEDRAL, with a hydrogen
atom at each of two ver3ces, and
unshared pairs at the other two.

bonding e- pairs

The H – O – H bond angle is 104.9°, less than the bond angle of a

perfect tetrahedron (due to the compression from the oxygen
nonbonding electron pairs).
 WATER
Because of the presence of polar bonds and of the bent geometry (that
results in a net dipole moment greater than zero), WATER IS A POLAR
MOLECULE.

Due to the difference in
electronega3vity between hydrogen
and oxygen, bonded electrons are
shared unequally, and the electrons
are more oaen in the vicinity of the
oxygen atom than the hydrogen.

The oxygen atom bears a par3al

nega3ve change (δ-), and each
hydrogen a par3al posi3ve change
(δ+).
 WATER
The par3al charges on the oxygen and the hydrogen allow for water to
par3cipate in

hydrogen bonding

a rela3vely STRONG form of INTERMOLECULAR a@rac3on.

intermolecular
molecule molecule
a@rac3on
 HYDROGEN BONDING
Molecules with hydrogen atoms bonded to electronega3ve
atoms such as O, N, and F tend to exhibit unusually strong
intermolecular interac3ons.
O or N or F
molecule N H molecule O H F H

NH3 H2O HF
ammonia water hydrogen fluoride

The name hydrogen bond is something of a misnomer, as it

is not a true bond but a parNcularly strong dipole-dipole
aPracNon, and should not be confused with a covalent
bond.
 WATER
When hydrogen is bonded to highly electronega3ve ions
such as oxygen the resul3ng covalent bond is VERY polar.

Highly
Highly
posi3ve
nega3ve
Hydrogen bonding
δ+ δ- δ+ δ-
Ÿ Ÿ
Ÿ Ÿ Ÿ
Ÿ
H O Ÿ H O Ÿ
δ+ δ+
H H
this H is e- deficient
and will borrow
a lone pair from the O
of an adjacent molecule

 HYDROGEN BONDING

Water is unique because its H H

oxygen atom has TWO lone O
O
pairs and TWO hydrogen H H
atoms, meaning that the O
total number of hydrogen H H
bonds of a water molecule H
H
H H
O O
is FOUR.

11
 HYDROGEN BONDING
Hydrogen bonds are weaker than covalent bonds.

Hydrogen bond is a
INTERMOLECULAR FORCE.

The hydrogen bond in liquid water has a bond energy (energy to

break a bond) of about 20 kJ/mol, while it take about 460 kJ to break
1 mol of covalent bonds between H and O.

H-O-H H O H
20 kJ

H-O-H
460 kJ
 COMMON HYDROGEN BONDS
IN BIOLOGICAL SYSTEMS
Alcohols, aldehydes, ketones, and compounds containing N-H bonds all
form hydrogen bonds.

Hydrogen bonds play a crucial role in the structure and func3on of

macromolecules such as proteins and nucleic acids.
 HYDROGEN BONDING
Hydrogen bonds “are both weak and strong”:

WEAK: they easy to break them when it is needed to

break them.

STRONG: they “add up” becoming strong and

stabilizing structures.
 WATER
At any given 3me, most of the molecules in liquid water are engaged
in hydrogen bonding, but the life3me of each hydrogen bond is just 1
to 20 picoseconds (1 ps = 10-12 s); upon breakage of one hydrogen
bond, another hydrogen bond forms, with the same partner or a new
one.
PROPERTIES
OF
WATER
16
 PROPERTIES OF WATER
Water has long been known to exhibit many physical
proper3es that dis3nguish it from other small molecules of
comparable mass.

Chemists refer to these as the "anomalous" proper3es of

water, but they are by no means mysterious.

All are enNrely predictable consequences of formaNon of

hydrogen bonding.
 PROPERTIES OF WATER

•  High melNng point

•  High boiling point

•  Unusual liquid and solid phase densiNes

•  High molecular cohesion

- Capillary ac3on
- Meniscus
- High surface tension

•  High heat capacity

 PROPERTIES OF WATER
High MelNng Point
Water has an unusually high mel3ng point, due to the hydrogen
bonding between water molecules.

In its solid form (ice), each

water molecule is subject to
FOUR hydrogen bonds
 PROPERTIES OF WATER
High Boiling Point
Just like with its mel3ng point, water molecules also have a higher
boiling point than other substances.
Likewise, the reason for this is the hydrogen bonding between
neighboring water molecules. Because hydrogen bonding is a
rela3vely strong intermolecular force, high heat energy is required to
break up the force.
 PROPERTIES OF WATER
Liquid and Solid Phase DensiNes (expansion upon freezing)
Water is one of the few substances that has the excep3on
of having less dense solid than its liquid.

Ice is less dense than liquid water

 PROPERTIES OF WATER
Liquid and Solid Phase DensiNes (expansion upon freezing)
Each water molecule in ice forms four
hydrogen bonds to its neighbors,
crea3ng a regular crystal la_ce.

The hydrogen bonds keep each

molecule at a DISTANCE that makes
ICE LESS DENSE THAN LIQUID WATER.

The expansion upon freezing comes

from the fact that water crystallizes
into an open hexagonal form. This
hexagonal laqce contains more space
than the liquid state.
 PROPERTIES OF WATER
Liquid and Solid Phase DensiNes (expansion upon freezing)

No3ce the greater openness of the ice structure which is necessary to

ensure the strongest degree of hydrogen bonding in a uniform,
extended crystal laqce.
 PROPERTIES OF WATER
High molecular cohesion
Molecules in the liquid state experience strong intermolecular
a@rac3ve forces.

Ø  When those forces are between
like molecules, they are referred
to as cohesive forces.

Ø  When the a@rac3ve forces are
between unlike molecules, they
are said to be adhesive forces.
 PROPERTIES OF WATER
High molecular cohesion

High cohesion among water molecules results into:

•  FormaNon of meniscus

•  Capillary acNon

•  High surface tension

 PROPERTIES OF WATER

When a liquid comes into contact with a

surface (such as the walls of a graduated
cylinder or a tabletop), both cohesive and
adhesive forces will act on it.

These forces govern

the shape which the
liquid takes on.
 PROPERTIES OF WATER
💪 high cohesive forces, weak adhesive forces

Due to the effects of ADHESIVE

FORCES, liquid on a surface can
spread out to form a thin,
rela3vely uniform film over the
not as strong cohesive forces???
surface.

Alterna3vely, in the presence of

strong COHESIVE FORCES, the
liquid can divide into a number
of small, roughly spherical beads
💪 high adhesive forces, low cohesive
which stand on the surface,
maintaining minimal contact
with the surface.
 PROPERTIES OF WATER
– FormaNon of meniscus
The meniscus (from the Greek for
"crescent") is the curve in the surface of
a liquid in a container.

28
 PROPERTIES OF WATER
– FormaNon of meniscus

GLASS

29
 PROPERTIES OF WATER
– Capillary AcNon
Capillary ac3on is the rising of a liquid though a narrow
tube, due to the cohesive forces between the liquid
molecules and the adhesive forces between the liquid
molecules and the wall of the container.

 PROPERTIES OF WATER
– Capillary AcNon
The adhesive forces are some3mes
stronger than water’s cohesive forces,
especially when the water is exposed to
charged surfaces such as those found on
the inside of thin glass tubes known as
capillary tubes.
Adhesion is observed when water “climbs” up the tube
placed in a glass of water: no3ce that the water appears to
be higher on the sides of the tube than in the middle. This is
because the water molecules are a@racted to the charged
glass walls of the capillary more than they are to each other
and therefore adhere to it.
 PROPERTIES OF WATER
– Capillary AcNon

The smaller the diameter of the tube is, the higher the
liquid climbs.
 PROPERTIES OF WATER
– Capillary AcNon
Many medical tests require drawing a small amount of
blood, for example to determine the amount of glucose in
someone with diabetes. This procedure can be easily done
because of capillary ac3on, the ability of a liquid to flow up
a small tube against gravity.

When the weight of the

liquid in the tube generates a
downward force equal to the
upward force associated with
capillary ac3on, the liquid
stops rising.
 PROPERTIES OF WATER
If you place one end of a paper towel in spilled wine, the
liquid wicks up the paper
towel. A similar process
occurs in a cloth towel
when you use it to dry
off aaer a shower.

These are examples of capillary ac3on—when a liquid flows

within a porous material due to the a@rac3on of the liquid
molecules to the surface of the material and to other liquid
molecules. The adhesive forces between the liquid and the
porous material, combined with the cohesive forces within
the liquid, may be strong enough to move the liquid
upward against gravity.
 PROPERTIES OF WATER
Towels soak up liquids like water
because the fibers of a towel are made
of molecules that are a@racted to water
molecules.
Most cloth towels are made of co@on, and paper
towels are generally made from paper pulp.
Both consist of long molecules of cellulose that contain
many −OH groups.
Water molecules are a@racted to these −OH groups and
form hydrogen bonds with them, which draws the H2O
molecules up the cellulose molecules. The water molecules
are also a@racted to each other, so large amounts of water
are drawn up the cellulose fibers.
 PROPERTIES OF WATER
– Capillary AcNon
The cohesion of water molecules is a crucial property in
the transporta3on of water to plants.
Strong capillary ac3on is essen3al to plants in the effec3ve
transport of water.
 PROPERTIES OF WATER
– High Surface Tension

Surface tension is revealed in the

floa3ng of some objects on the
surface of water, even though they
are denser than water, the forma3on
of droplets, and in the ability of some
animals to run on the water surface.

37
 PROPERTIES OF WATER
– High Surface Tension

38
 PROPERTIES OF WATER
High Cohesion – High Surface Tension
The cohesive forces between molecules down into a liquid
are shared with all neighboring atoms.

Molecules on the surface have no

neighboring like-molecules
above, and exhibit stronger
a@rac3ve forces upon their
nearest neighbors on the surface.

This enhancement of the intermolecular aPracNve forces

at the surface is called surface tension.
39
 PROPERTIES OF WATER
– High Surface Tension
Water exhibits a dis3nctly high surface tension due to
strong hydrogen bonding between its molecules. As a
result, the surface of water represents a rela3vely “tough
skin” that can withstand considerable force without
breaking.

Some insects, even though they are denser than water,

move on its surface because they are supported by the
surface tension.
 PROPERTIES OF WATER
– High Surface Tension

Surface tension helps The high surface tension of

water to form water causes it to contract to
spherical droplets. the smallest possible area.
 PROPERTIES OF WATER

high medium low

surface surface surface
tension tension tension

surfactant

42
 PROPERTIES OF WATER
High Cohesion – High Heat Capacity (specific heat)
Water has the highest specific heat of any common
substance, 1 calorie/g°C = 4.186 J/g°C.
It therefore takes a long 3me to heat and long 3me to cool.
Because it takes a great deal of
heat to warm up water, water
stays cool longer, and acts as an
effec3ve coolant. This is why cool
"sea breezes" are welcome on a
hot summer's day.

On the contrary, once the water is warmed up, it takes a great deal of
heat release to cool the water. This keeps warm winds blowing in off
large lakes and oceans in the fall and into the winter, making the
temperatures not as frigid as they otherwise could be.
 PROPERTIES OF WATER
High Cohesion – High Heat Capacity (specific heat)

Water is used as coolant

car radiators. Due to its
high specific heat capacity,
it can absorb a large
amount of heat energy
from the engine of the car,
but its temperature does
not rise too high.

WATER AS A SOLVENT
 SOLUBILITY OF BIOMOLECULES IN WATER

•  Water is a good solvent for charged and polar

substances
–  amino acids and pep3des
–  small alcohols
–  carbohydrates

•  Water is a poor solvent for nonpolar substances

–  nonpolar gases
–  aroma3c moie3es
–  alipha3c chains
open chains
 NONCOVALENT INTERACTIONS
In General Chemistry classes, you learned that there are two types of
bonds: IONIC and COVALENT.

Biomolecules are ocen immense in size, and are held
together by STRONG COVALENT BONDS.
Example: a pep3de
 NONCOVALENT INTERACTIONS
However, the weaker interacNons between different parts
of the same molecule and between different molecules are
the ones responsible for most of the structure and
funcNons of these macromolecules.

Example:

These non covalent interacNons are called:

noncovalent forces or noncovalent bonds

 NONCOVALENT INTERACTIONS

A typical carbon-carbon (C-C) covalent bond has a bond

length of 1.54 Å and bond energy in the range of 300-400 kJ
mol-1.
300-400 kJ mol-1

C C

Because this energy is rela3vely high, considerable energy

must be expended to break covalent bonds.

Biological noncovalent bonds are 10 to 100 3mes weaker.

 NONCOVALENT INTERACTIONS

Noncovalent intermolecular interac3ons include:

1) ElectrostaNc interacNons
2) van der Waals forces
3) Hydrophobic interacNons
4) Hydrogen bonds

Noncovalent interac3ons play important roles because they

are collecNvely strong.
 NONCOVALENT INTERACTIONS
1) ElectrostaNc interacNons
Electrosta3c interac3ons are formed between charged
par3cles.

CATION ANION
+ -
 NONCOVALENT INTERACTIONS
1) ElectrostaNc interacNons - Example
For example, Mg2+ ions associate with the nega3vely charged
phosphates of nucleo3des.
 NONCOVALENT INTERACTIONS
1) ElectrostaNc interacNons - Example
Within proteins, SALT BRIDGES
can form between nearby
charged residues, for example,
between a posi3vely charged
amino group and a nega3vely
charged carboxylate ion.
 NONCOVALENT INTERACTIONS
2) van der Waals forces
van der Waals forces (London forces) are weak forces between
temporary dipoles.
When nonpolar molecule are very close together, their surrounding
electron clouds influence each other.
Random varia3ons in the posi3ons of the electrons may create a
transient electric dipole, which induces a transient, opposite electric
dipole in the nearby molecule.
δ- δ+ δ- δ+

The average bond energy for van der Waals forces is on the order of
10 kJ/mol.
 NONCOVALENT INTERACTIONS
3) Hydrophobic interacNons
Hydrophobic interac3ons result when non-polar molecules
are in H2O (polar solvent). The non-polar molecules group
together to exclude water.

By doing so they minimize the surface area in contact with

the polar solvent.
 NONCOVALENT INTERACTIONS
3) Hydrophobic interacNons
The strength of hydrophobic interac3ons is not due to any
intrinsic a@rac3on between nonpolar moie3es.
Rather, it results from the system’s achieving greatest
thermodynamic stability by minimizing the number of
ordered water molecules required to surround hydrophobic
por3ons of the solute molecules.

hydrophobic
interac3ons
 NONCOVALENT INTERACTIONS
3) Hydrophobic interacNons - Example
Many biomolecules are amphipathic; proteins and the
sterols and phospholipids of membranes all have polar and
nonpolar surface regions.
Structures composed of these molecules are stabilized by
hydrophobic interac3ons among the nonpolar regions.
 NONCOVALENT INTERACTIONS
4) Hydrogen bonds
Hydrogen bonds form between oxygen or nitrogen of a molecule (or
part of a molecule) and a hydrogen atom covalently bonded to
another electronega3ve atom in another molecule (or in different part
of the same molecule).
“hydrogen acceptor”

“hydrogen donor”
 NONCOVALENT INTERACTIONS
4) Hydrogen bonds - Example
Alcohols, aldehydes, ketones, and compounds containing N-H bonds all
form hydrogen bonds with water molecules.

Hydrogen bonds play a crucial role in the structure and func3on of

macromolecules such as proteins, carbohydrates, and nucleic acids.

NONCOVALENT INTERACTIONS
 SOLUBILITY OF BIOMOLECULES IN WATER
Classifica3on of biomolecules based on their interac3ons with water:

•  HYDROPHILIC
Polar biomolecules that dissolve easily in water are referred to as
hydrophilic (water-loving).

•  HYDROPHOBIC
Nonpolar biomolecules that do not dissolve appreciably in water are
called hydrophobic (water-fearing).

•  AMPHIPATHIC
Amphipathic biomolecules have significant amounts of both
hydrophilic and hydrophobic structure.
(of a molecule, especially a protein) having both hydrophilic and hydrophobic parts
 SOLUBILITY OF BIOMOLECULES IN WATER

Types of solute:

§  Polar solutes (polar covalent)

§  Charged (ionic) solutes
§  Hydrophobic molecules (non polar covalent)
§  AmphipaNc molecules
§  Non polar gases
 WATER AND POLAR SOLUTES
Uncharged but polar molecules can easily be dissolved.

sucrose

This is primarily due to the a@rac3on between the

par3ally posi3ve hydrogen on water and a par3ally posi3ve atom on
the solute and the par3ally nega3ve oxygen on water and a par3ally
posi3ve atom on the solute
 WATER AND POLAR SOLUTES
Ketones, alcohols, aldehydes, and compounds that have N-
H bonds, form hydrogen bonds with water molecule. These
biomolecules tend to be very soluble in water.
 WATER AND CHARGED (IONIC) SOLUTES
Water dissolves ionic compounds such as NaCl.
When NaCl is placed in water, the sodium and chloride ions
are SEPARATED in the solvent.

H2O(l)
NaCl(s) Na+(aq) Cl-(aq)

solid

separate ions
(dissolved, hydrated)
 WATER AND CHARGED (IONIC) SOLUTES
Water molecules shield individual sodium and chloride ions
from one another by hydra3on.
By hydra3ng both ions (Na+ and Cl-), the interac3on
between ions are diminished and the solid becomes
dissolved.
 WATER AND CHARGED (IONIC) SOLUTES
This also applies to many charged func3onal groups present
in biomolecules such as carboxylic acid, and protonated
amines.
 WATER WITH NONPOLAR SOLUTES
Nonpolar covalent solutes DO NOT interact with polar
water.

Hydrophobic (non polar) molecules are NOT water soluble.

 WATER WITH AMPHIPATIC SOLUTES
Several biomolecules are AMPHIPATHIC: they contain both
a hydrophobic group and a hydrophilic group.

SDS (detergent)
 WATER WITH AMPHIPATIC SOLUTES
Oaen3mes, molecules will align themselves in a way such
that the hydrophilic, polar por3ons of the molecule will
shield the hydrophobic, non-polar por3ons from
surrounding water molecules, forming a MICELLE.
is an aggregate (or supramolecular assembly) of surfactant molecules dispersed in a
liquid colloid. A typical micelle in aqueous solution forms an aggregate with the
hydrophilic "head" regions in contact with surrounding solvent, sequestering the
hydrophobic single-tail regions in the micelle centre.
 WATER WITH AMPHIPATIC SOLUTES
Another example is the "lipid bilayer" in the plasma
membrane of a cell, where the polar heads align to shield
the non-polar fa@y acid tails from water outside of the cell.
Extracellular

Hydrophobic tail

Intracellular Hydrophilic head

This way, the hydrophilic heads are exposed to outside
water molecules while the hydrophobic tails are almost
completely free of water.
 WATER AND NONPOLAR GASES
The molecules of the biologically important gases
CO2, O2, and N2
are nonpolar and consequently poorly soluble in water.

Some organisms have water-soluble carrier proteins (hemoglobin and

myoglobin, for example) that facilitate the transport of O2

Carbon dioxide forms carbonic acid (H2CO3) in aqueous

solu3on and is transported as the HCO3- (bicarbonate) ion
(very soluble in water), or bound to hemoglobin.
Two other gases, NH3 and H2S, also have biological roles in
some organisms; these gases are polar and dissolve readily
in water
 COLLIGATIVE PROPERTIES OF WATER
Solutes of all kinds alter certain physical proper3es of the solvent,
water:

•  vapor pressure
•  boiling point
•  freezing point
•  osmoNc pressure
These are called COLLIGATIVE PROPERTIES, because the effect of
solutes on all four proper3es has the same basis: the concentra3on of
water is lower in solu3ons than in pure water.
depend upon the concentration of solute molecules or ions, but not upon the identity of
the solute. Colligative properties include vapor pressure lowering, boiling point
elevation, freezing point depression, and osmotic pressure.
OSMOSIS

74
 OSMOSIS
OSMOTIC PRESSURE
Osmosis is the spontaneous net movement of solvent molecules (H2O)
through a par3ally permeable membrane from a region of lower solute
concentra3on into a region of higher solute concentra3on.

Semi-permeable
membrane that
allows the passage
of solvent molecules
(not solute
molecules)

OsmoNc pressure is the pressure required to be applied so that there

is no net movement of solvent across the membrane.
 OSMOSIS
Biological membranes are semipermeable membranes.
Biological membranes are selec3vely permeable.

Selec3ve passage of CYTOPLASM

molecules
and ions

Water molecules
cross easily biological membranes
and osmosis provides the primary means
by which water is transported into and out of cells
 OSMOSIS

Cell submerged in Cell submerged in Cell submerged in

water with low water with conc. water with high
conc. of salts: of salts equal to conc. of salts:
water molecules conc. of salts water molecules
move into the inside the cell: move out of the
cell. water molecules cell.
move in and out
in each direc3on
at exactly the
same rate
 OSMOSIS

HYPOTONIC ISOTONIC HYPERTONIC

higher osmolarity
with lower osmolarity than
cell neither gains nor than the cytosol, the
the cytosol, the cell swells
loses water cell shrinks as water
as water enters
flows out