Outline:

Importance of water for plants

Water structure and properties

Hydrophobicity

Surface tension and capillarity

Diffusion and Fick’s Law

We’re going to spend some time talking about water.

Why? Fundamental to plant life is the way plants

interact with water.

This figure shows that water availability limits

agricultural productivity.

For these crops, more water = higher yield.

Water also limits biomass accumulation in natural
environments.

In these two graphs we see that the more water is

available, the more biomass accumulation is possible.
Water has some interesting and unique properties.

Because of the difference in electronegativities of

oxygen and hydrogen, water is a polar molecule.

This allows it to form hydrogen bonds, with itself…

This property allows water to form ‘flickering clusters’
of transient higher order structures
Water also forms hydrogen bonds with other polar
molecules, like alcohols, carboxyls, amines.

These are very important for establishing protein

structure.
Because of its ability to form hydrogen bonds, it is an
excellent solvent for other polar molecules, i.e., NaCl.

The covalent bond between the oxygen and hydrogen

has a strength of about 460 kJ/mol, whereas the
hydrogen bond between water molecules has a
strength of about 20 kJ.

The importance of the hydrogen bond is that, even

though it is a low energy bond there are many of them
and they add.

10 to 20 hydrogen bonds has an energetic equivalence

of a covalent bond.
Water also has important thermal properties.

Specific heat of a substance is the amount of heat

required to raise the temperature by a set amount.

The specific heat of water is 4.186 K/g °C = 1 calorie /

g °C. This is higher than any other common substance.

Latent heat of vaporization is the energy needed to

separate molecules from the liquid phase to the vapor
phase.

For water at 25°C it’s 44 kJ/mol, higher than any

other known known liquid.

Why are the specific heat and latent heat of

vaporization so high for water? Hydrogen bonds.
Remember that at higher temperatures, molecules are
moving around more than at lower temperatures.
Hydrogen bonds keep water from moving as much. And
when a molecule goes from liquid to vapor phase, you
must break all the hydrogen bonds.

Hydrogen bonds are the key to understanding water.

Hydrophobic forces = entropic forces.
< 40 kJ/mol.

Hexane and water won't mix. In general, hydrocarbons

and water won't mix, because of hydrophobic forces.

The root cause is the entropy (disorder) of water.

Water becomes more ordered as it packs around a

hydrocarbon.

This causes a decrease in the system's entropy, and so is

not favored energetically.
Revisit the flickering cluster view. Note all the many
hydrogen bonds in the clusters.

These hydrogen bonds are all transitory, so that a

moment later a given water molecule interacts with
different neighbors.

Entropy is a measure of the number of degrees of

freedom for all the individual water molecules in the
solution.

The more random the water interactions, the higher

the entropy.
One formulation of the second law of thermodynamics
is that systems spontaneously seek their lowest energy
state.

Since G = H – TS, (G=Gibbs free energy, H = enthalpy,

T = temperature, and S = entropy) the higher the
entropy, the lower the energy.

So if system A is more randomized compared to

system B, then system A is in a lower energy state.
 What happens when you dissolve a non-polar
molecule in water?

Let the x’s represent water molecules that are trapped to solvate
the hydrocarbon. Ask yourself, how many water molecules are
not free to go anywhere randomly in the two configurations?

12 x’s per molecule x 2 = 24 x’s vs. 16 x’s. If the hydrocarbons

are in a solution with 100 water molecules, 76 water molecules
are free to move randomly on the left and 84 water molecules
are free to move randomly on the right.
Break hydrogen bonds when solvating non-polar
molecules, but can't compensate as in salts by new
interactions.

In fact, water is constrained to line up in an ordered

fashion around hydrocarbons, decreasing the system's
entropy.

Thus, increase in G as hydrocarbons dissolve.

Less entropy decrease by grouping the hydrocarbons

together and keeping the water together.

This is what causes water and oils not to mix. It isn't

actually that hydrocarbons "like" to be together, but
rather that water "likes" to exclude them.

This is the system seeking its lowest energy

configuration.
Molecules that act like these hydrocarbons in this example are
said to be "hydrophobic", i.e., 'afraid of water’.

Molecules that are easily solvated by water are termed

"hydrophilic", i.e., 'water loving'.
Surface tension is the energy needed to increase the
surface area of a gas-liquid interface.

Units are J/m2, but often written as force per length,

N/m.
If the surface is curved, the force generated by
surface tension is perpendicular to the interface.

When talking about a gas bubble in water, this leads to

a shrinkage of the bubble size as the force is directed
into the center of the bubble.

Water has a surface tension, equal to almost three

times that of ethanol.
Cohesion is the mutual attraction between molecules.

Adhesion is related to cohesion and describes the

attraction of water to a solid phase.

The strength of adhesion can be quantified by looking

at the contact angle measuring the shape of the air-
water interface.

Looking at the figure, see that a hydrophilic

surface, i.e., a wettable surface (clean glass,
primary cell walls) has a contact angle, θ < 90°.

The smaller the contact angle, the lower the

surface tension is in the droplet.

A hydrophobic surface (water repellant fabric,

mercury) has a contact angle, θ > 90°.
Capillarity is the action by which water rises or is
depressed when in contact with a solid, like a capillary
tube.

With a wettable surface, like glass, the contact angle

is < 90° (close to 0), and water rises up the surface.

Result of adhesion and surface tension.

The water rises until the upward force is balanced by

the force of gravity.
When a glass capillary tube is placed into Hg, the liquid
does not wet the walls of the tube.

Now the meniscus curves downward and the surface

tension lowers the liquid in the tube.
Capillarity applies not only to movement of water up a capillary tube, but to the
movement of water through soil, from xylem into cell walls, the absorption of water
by a towel, etc.

It does not have to be against the force of gravity.

Capillary rise can be calculated as

14.9 x 10-6 m2 / radius

Let’s do a few calculations:

How far will water rise in a capillary tube 1 mm in diameter?

14.9 x 10-6 m2 / 5 x 10-4 m = 0.00745 m = 7.45 mm

How far will water rise in a xylem vessel with a diameter of 50 μm?

14.9 x 10-6 m2 / 25 x 10-6 = 0.6 m

not enough to bring water up a tree, for instance.

But it is enough to extract water from the xylem into neighboring cell walls,
keeping the surfaces wet.
Diffusion is the movement of molecules by thermal
agitation.

Why this mixing? What principle at work here?

2nd law of thermodynamics. More randomized on the

right.
Diffusion is proportional to the position-dependent
concentration gradient:

Js = -Ds (Δcs / Δx)

With Js = rate of transport = flux density = the

amount of material crossing an area per unit time
(moles / m2s);

Ds is the diffusion constant, a measure of how easily

substance s crosses a particular medium; large
molecules have smaller Ds, etc., and it depends on the
medium and temperature.

Δcs / Δx is the change in concentration of substance s

over the distance Δx.
What does this mean?

Δcs / Δx is the change in concentration of substance s over the distance Δx.

Note: the steeper the concentration gradient, the

higher the flux.
Examples:
The average time it takes for a molecule to diffuse a
distance L is

t ≈ L2/2D

So diffusion works over short distances, but not so

well over long distances.