Chapter 21

The Liquid State

 21.1 Structure of Liquids

• A given amount of liquid has a fixed volume

but assumes the shape of its container.

• At the molecular level, however, liquids do

possess some degree of structure, or order, as
evidenced by several physical measurements.
 Structure of Liquids

• Choosing an arbitrary point as the origin, we

assign ρ(r) as the mean or average number of
atoms per unit volume at radius r from the
origin, which can be viewed as a density
function.
 Structure of Liquids
• The total number of atoms whose centers lie within
a spherical shell of radii r and r + dr is given by:

number of atoms in the shell =

(volume of shell) x (number of atoms per unit volume)

= 4πr2drρ(r) (21.1)
 Structure of Liquids

• The quantity 4πr2ρ(r) is called the radial

distribution function.

• Figure 21.1 shows radial distribution function

plots for liquid argon at different temperatures
and pressures.
• Radial distribution function of liquid Ar at Figure 21.1
a series of temperatures and pressures.
• The conditions are:
(1) 84 K and 0.8 atm;
(2) 91.6 K and 1.8 atm;
(3) 126.7 K and 18.3 atm;
(4) 144.1 K and 37.7 atm;
(5) 149.3 K and 46.8 atm.
(6) is the radial distribution curve for
gaseous Ar at 149 K and 43.8 atm.
• The vertical lines on top represent the
diffraction lines for solid Ar. [Modified
from A. Eisenstein and N. S. Gingrich,
Phys. Rev. 62, 261 (1940).]
 Structure of Liquids
• Liquid argon, like all other liquids, possesses
short-range order but lacks long-range order.

• Even its short-range order is disrupted by an

increase in the kinetic energy of the atoms when
the temperature is raised.

• In liquids, atoms are constantly in motion, so the

X-ray diffraction pattern corresponds to their
time-averaged positions.
 21.2 Viscosity

• The viscosity of a fluid—that is, a gas, a pure

liquid, or a solution—is an index of its
resistance to flow.

• Most viscometers monitor the ease with

which fluids flow through capillary tubing.
 Viscosity

• Let us derive an expression relating the

viscosity of a liquid, η, to the ex­perimental
parameters.

• Consider a certain liquid flowing through a

capillary tube of radius R and length L under
constant pressure, P (Figure 21.2).
 Viscosity

• Flow of a liquid through a

capillary tube of radius R.
 Viscosity

• The velocity of the liquid is zero at the walls

and increases toward the center of the tube,
reaching a maximum at the center.

• Imagine two concentric cylinders of radii r and

(r + dr).
 Viscosity
• According to Equation 3.20, the frictional drag,
F, between these two cylindrical layers is:

21.2

where 2πrL is the surface area of the inner

cylinder, and dv/dr is the velocity gradient.
 Viscosity
• Because the velocity decreases as r increases,
dv/dr is a negative quantity, and a negative sign
has been included in Equation 21.2 to make F a
positive number.

• For steady-state flow, the frictional drag must

be exactly balanced by the downward force,
which is given by the product of pressure, P, and
area, πr2.
 Viscosity
• Thus:
 Viscosity
• Integration between v = 0 (at r = R) and v = v
(at r = r) yields:

• Hence:
21.3
 Viscosity
• We see that the velocity of flow anywhere in the
tube is a parabolic function of r.

• Keep in mind that Equation 21.3 holds only for

laminar flow, which requires small diameters and
low flow rates.

• Without these conditions, Equation 21.3 is not

valid, and turbulent flow may result.
 Viscosity
• A useful distinction between turbulent and
laminar flow is provided by the Reynolds
number (after the British physicist Osborne
Reynolds, 1842-1912), defined as:

Reynolds number = (2Rvρ / η) 21.4

where ρ is the density of the liquid.

 Viscosity

• A Reynolds number less than about 2000

indicates laminar flow; a number greater than
3500 indicates turbulent flow.

• Intermediate values (between 2000 and 3500)

may accompany either type of flow, which
must be determined experimentally.
 Viscosity
• The volume of liquid that flows through a cross-
sectional element, 2πrdr, per second is simply
(2πrdr)v, and the total volume of the liquid
flowing per second, Q, is given by:

21.5

where V is the total volume, and t is the flow

time.
 Viscosity
• Equation 21.5, known as Poiseuille's law (after
the French physician Jean Poiseuille, 1799-
1869), applies to both liquids and gases.

• A relatively simple apparatus for measuring

viscosity is the Ostwald viscometer (devised by
the German chemist Wolfgang Ostwald, 1883-
1943), shown in Figure 21.3.
 Figure 21.3

• An Ostwald
viscometer. The time
a liquid takes to flow
between markings x
and y is measured and
compared with that of
a reference liquid. A,
bulb; B, capillary tube;
C, reservoir bulb.
 Figure 21.3
• It consists of a bulb (A) with markings x and v,
attached to a capillary tube (B) and a reservoir
bulb (C).

• A definite volume of the liquid under study is

introduced into C and sucked into A, and the
time (t) the liquid takes to flow between x and
y is recorded.
 Viscosity
• Rearranging Equation 21.5 gives:

21.6

• The pressure, P, at any instant driving the liquid

through B is equal to hρg, where h is the
difference in height between the levels of the
liquid in the two limbs, ρ is the density of the
liquid, and g is the acceleration due to gravity.
 Viscosity

• To be sure, this pressure varies during the

experiment because h decreases.

• But because the initial and final values of h are

the same in every case and g is a constant, the
applied pressure is clearly proportional to the
density of the liquid.
 Viscosity
• In practice, we do not use Equation 21.6 to
measure the value of n because of the
uncertainties in determining the radius of the
capillary tubing, R.

• (Note that the radius appears as R4, so a small

deviation in R can lead to a considerable error
in η.)
 Viscosity
• Instead, the viscosity of a liquid is most
conveniently determined by comparison with
a reference liquid of accurately known
viscosity, as follows.

• The ratio of the viscosities of a sample and a

reference liquid is given by:
 Viscosity
• Because V, L, and R values are the same if we use
the same viscometer and P = constant x p, the
preceding equation reduces to:

21.7

• Thus, the viscosity of the sample can be obtained

readily from the densities of the liquids and the
times of flow if ηreference is known.
Table 21.1
 Viscosity
• Equation 21.6 can be applied to the study of
blood flow in our bodies.

• Figure 21.4 shows a schematic diagram of the

various routes for blood circulation.

• The heart is, in effect, a single pump powering

a double circuit.
• Schematic diagram of the human
Figure 21.4
circulation system.
• Arterial blood, rich in
oxyhemoglobin, is pumped
through the left ventricle of the
heart to the tissues, where
oxygen is released and carbon
dioxide is taken up.
• The venous blood, rich in
dissolved carbon dioxide, is
pumped by the right ventricle of
the heart to the lungs, where the
carbon dioxide is released and
oxygen is taken up.
 Viscosity
• It contains four chambers—two atria and two
ventricles—and four sets of values.

• Freshly oxygenated blood is conducted away

from the aorta, the large artery, leading from
the left chamber and into smaller arteries that
carry it to the various parts of the body.
 Viscosity

• These, in turn, branch into still smaller arteries,

the smallest of which—the arterioles—break
up into a complex network of capillaries.

• These minute structures thread their way to

every part of the body to help the blood carry
out its vital function: trading oxygen and other
materials for carbon dioxide and waste with
the cells.
 Viscosity
• The capillaries join into tiny veins called
venules, which in turn merge into increasingly
larger veins that transport the deoxygenated
blood back to the right atrium of the heart.

• In the space of a single beat, the atria contract,

forcing blood into the ventricles, and then the
ventricles contract, forcing the blood out of the
heart.
 Viscosity

• Because of the pumping action of the heart,

blood enters the arteries in spurts, or pulses.

• The maximum pressure at the peak of the pulse

is called the systolic pressure; the lowest pressure
between pulses is called diastolic pressure.
 Viscosity

• In a healthy young adult, the systolic pressure

is about 120 mmHg (120 torr) and the diastolic
pressure is about 80 mmHg (80 torr).*

• These values represent the excess pressures

over atmospheric pressure.
 Viscosity

• Thus, the absolute systolic and diastolic

pressures are 880 and 840 mmHg, respectively
(assuming that atmospheric pressure is 760
mmHg), and the average value of the blood
pressure is about 100 mmHg.
 Viscosity

• The radius of the aorta is sufficiently large

(about 1 cm) that a small pressure difference
is required to sustain normal blood flow
through it.

• At rest, the rate of blood flow is roughly 0.08 L

s-1.
 Viscosity
• Equation 21.5 can be rewritten as:

21.8

where ΔP is the difference in pressure at two

points along the aorta, and L is the distance
between the points.
 Viscosity
• Setting L = 0.01 m and converting Q to 8 x 10-5
m3 s-1, we find that:
 Viscosity
• A drop in pressure equal to 6 x 10-3 mmHg per
cm is negligibly small compared with the total
blood pressure.

• The situation is different as the blood enters

the other major arteries.
 Viscosity
• Because these vessels have much smaller radii
than the aorta, a pressure drop of about 20
mmHg is required to maintain the flow
through them.

• Therefore, the pressure is only 80 mmHg

when the blood enters the arterioles.
 Viscosity
• Because these vessels have still smaller radii,
there is another drop in pressure of about 50
mmHg.

• A further drop of 20 mmHg results when the

blood flows through the capillaries.
 Viscosity
• Note that although the capillaries have much
smaller radii than arterioles, there are so
many of them that the amount of blood
passing through each one is very small.

• By the time the blood reaches the veins, its

pressure has been reduced to about 10
mmHg.
 Viscosity
• Fortunately, veins are fitted with cup-shaped
valves to prevent backflow at this low pressure.

• The movement of blood in veins is promoted by

the massaging effect of surrounding skeletal
muscle or by the adjacent arteries.

• Finally, the blood returns to the right atrium,

ready to be circulated again.
 Equation 21.8
• An interesting comparison can be made
between Equation 21.8:

and Ohm's law:

 Equation 21.8

• By analogy, the resistance to flow is given by

8Lη/πR4.

• Equation 21.8 can be applied to study the flow

of blood in arteries, arterioles, and capillaries.
 Equation 21.8
• Because resistance is inversely proportional to
the fourth power of the radius, a decrease
from 2 x 10-4 cm, a typical capillary radius, to
1.5 x 10-4 cm caused by cholesterol deposits,
say, would result in an increase in the
resistance by a factor of 3.

• Normal blood flow would then be sustained

by higher blood pressure, causing a condition
known as hypertension.
 Equation 21.8
• On the other hand, if the resistance drops
while the blood pressure is unchanged, the
blood flow, Q, is increased.

• During vigorous exercise, both the blood

pressure and the radii of blood vessels
increase, a change known as vasodilation.
 Equation 21.8
• These two changes facilitate a greater blood
flow to meet the enhanced metabolic rate of
the body.

• Generally, the viscosity of a solution is greater

than that of the pure solvent
 Equation 21.8

• The presence of solute molecules disrupts the

smooth flow pattern, or velocity gradient, of
the fluid, resulting in an increase in viscosity.

• This viscosity change is particularly true for

solutions that contain macromolecules.
 Equation 21.8
• As we would expect, the viscosities of such
solutions also depend on the conformation of
the macro-molecules.

• The viscosity of a DNA solution, for example,

can vary greatly depending on whether the
solute molecules possess the native double-
helical conformation or are arranged in random
coils.
 Equation 21.8
• Often, the kinetics of denaturation from helix
to random coil can be conveniently measured
in terms of changes in the solution's viscosity
over a period of time.

• The viscosities of most liquids decrease with

increasing temperature.
 Equation 21.8
• A molecular interpretation is that liquids
possess a number of holes or vacancies and
molecules are continually moving into these
vacancies.

• This process permits a liquid to flow but

requires energy.
 Equation 21.8
• To be able to move into a vacancy, a molecule
must possess sufficient activation energy to
overcome the repulsion by the molecules that
surround the vacancy.

• At higher temperatures, more molecules

possess the necessary activation energy, so
the liquid flows more easily.
 Equation 21.9
• In fact, there is an analogous Arrhenius
equation for viscous flow, given by:

21.9

where η0 is a constant characteristic of the

liquid and Ev is the "activation energy" for
viscous flow.
 Equation 21.9
• In contrast to liquids, the viscosity of a gas
increases with temperature.

• In the kinetic molecular treatment of gases, the

origin of the viscous drag between two adjacent
layers is the momentum transfer of the
molecules from one layer to the other.

• The rate of transfer increases with temperature,

and therefore the viscosity of the gas also
increases.
 21.3 Surface Tension

• In vaporization, however, the molecules are

completely removed from the liquid, whereas
molecules in a surface layer are still under the
influence of strong intermolecular forces,
except that the forces are away from the
direction of the vapor phase (Figure 21.5).
 Figure 21.5
• Intermolecular forces
acting on a molecule in
the surface layer and
on a molecule in the
interior region of a
liquid.
 Figure 21.5
• This unbalanced interaction experienced by
surface-layer molecules results in a tendency
for the liquid to minimize its surface area. For
this reason, a small drop of liquid assumes a
spherical shape.
 Surface Tension
• Figure 21.6 shows a thin film, such as a soap
film, stretched on a wire frame that has a
movable side (called the piston) of length l.

• The force (F) required to stretch the film is

proportional to the length, l.
 Figure 21.6
• A wire frame supporting a liquid film. Work
has to be done to expand the surface area of
the film.
 Figure 21.6
• Because the film has two sides, the total
length of the film is 2l, so:

21.10

where the proportionality constant, γ, is the

surface tension of the liquid.
 Figure 21.6
• Thus, surface tension can be viewed as the
force exerted by a surface of unit length; it has
the units N m-1.

• Because N m-1 is equivalent to J m-2, we can

also interpret surface tension in terms of
surface energy.
 Figure 21.6
• The mechanical work done by moving the
piston a distance dx is Fdx, and the change in
surface area is 2ldx.

• The ratio of work done over the increase in

area is:
21.11
 Figure 21.6

• We see that surface tension can also be

defined as the surface energy per unit area.

• The surface energy is of mechanical rather

than thermal origin.
 Figure 21.6

• The work done in stretching the film results in

an increase in Gibbs energy, and the tendency
of a surface to reduce its area is just another
example of a system tending toward an
arrangement of lower Gibbs energy (at
constant temperature and pressure).
 The Capillary-Rise Method

• The capillary-rise method provides a simple

means for measuring the surface tension of
liquids.

• In this arrangement, a capillary tube of radius

r is dipped into the liquid under study (Figure
21.7a).
 Figure 21.7a
• Capillary-rise
phenomenon for liquids
in which adhesion is
greater than cohesion.
 The Capillary-Rise Method

• The force acting downward is the gravitational

pull on the liquid, given by πr2hρg, where πr2h
is the volume, ρ is the density of the liquid,
and g is the acceleration due to gravity.

• This weight must be balanced by an upward

force caused by the liquid's surface tension.
 The Capillary-Rise Method

• Acting along the periphery of the cylindrical

bore, between the liquid and the glass wall,
this force is given by 2πrγ cos θ, where 2πr is
the circumference of the bore, θ is the angle
of contact between the liquid and the capillary
tube in the meniscus, and cos θ gives the
vertical (upward) component of the force.
 The Capillary-Rise Method
• Equating the upward and downward forces,
we write:

or
21.12
Table 21.2
 The Capillary-Rise Method
• Although the rise of liquids up a capillary tube
is commonly observed, it is by no means a
universal phenomenon.

• For example, when a capillary tube is dipped

into liquid mercury, the upper level of the
liquid in the tube is actually lower than the
surface of free liquid (Figure 21.7b).
 Figure 21.7b
• When cohesion is greater
than adhesion, the liquid in
the capillary tube forms a
depression.
 The Capillary-Rise Method
• These two divergent behaviors can be
understood by considering the intermolecular
attraction between like molecules in the
liquid, called cohesion, and the attraction
between the liquid and the glass wall, called
adhesion.

• If adhesion is stronger than cohesion, the

walls become wettable, and the liquid will rise
along the walls.
 The Capillary-Rise Method

• Because the vapor-liquid inter­face resists

being stretched, the liquid in the center of the
column also rises.

• Conversely, if cohesion is greater than

adhesion, the liquid in the capillary forms a
depression.
 Example 21.1

• The typical radius of a xylem vessel of a plant

is about 0.020 cm.

• How high will water rise in such a vessel at 293

K?
 Example 21.1
• From Equation 21.12,

h = 2γcosθ
rgρ

• Because the contact angle is usually quite

small, we assume that θ = 0, so cos θ = 1.
 Example 21.1
• The data are:
γ = 0.07275 N m-1
r = 0.00020 m
g = 9.81 ms-1
ρ = 1 x 103 kg m-3
 Example 21.1
• Hence

h = 2(0.07275 N m-1)
[(0.00020 m)(9.81 m s-2)(l x 103 kg m-3)]
= 0.074 N s2 kg-1 = 0.074 m
(1 N = 1 kg m s-2)
 Example 21.1
• The result shows that the capillary-rise
phenomenon is partially responsible for the
rise of water in plants and soils but cannot
wholly account for it.

• The water is helped up by the major

mechanism, osmosis.
 Surface Tension
• The surface tension of aqueous solutions is
generally close to that of pure water if the
solutes are salts, such as NaCl, or sucrose and
other substances that do not preferentially
collect at the air-water interface.

• On the other hand, surface tension can

dramatically decrease if the dissolved
substance is a fatty acid or a lipid.
 Surface Tension
• These molecules consist of two regions: a
hydrophilic (water-loving) polar group such as
-COOH at one end, and a long hydrocarbon
chain that is non-polar and therefore
hydrophobic (water-fearing) at the other end.

• The nonpolar groups tend to line up together

along the surface of water with the polar
groups pointing toward the interior of the
solution (Figure 21.8).
 Figure 21.8
• Schematic diagram of fatty acid molecules in
water. The spheres represent polar groups and
the zigzag lines
represent the
non-polar
hydrocarbon
chains.
 Surface Tension

• Consequently, surface tension decreases.

• This effect depends on the nature of the

solute molecule.
 Surface Tension

• Thus, although a 0.01 M solution of caproic

acid [CH3-(CH2)4-COOH] lowers the surface
tension by about 0.015 N m-1, a decrease of
about 0.025 N m-1 in surface tension is
observed in a 0.0005 M solution of capric acid
[CH3-(CH2)8-COOH].
 Surface Tension

• Any substance that causes a reduction in

surface tension in this manner is called a
surfactant.

• Among the most effective surfactants are

soaps (salts of long-chain fatty acids) and
denatured proteins.
 Surface Tension in the Lungs

• The action of surfactants also plays an

important role in the breathing process.

• By far the most extensive surface of the

human body in contact with the surroundings
is the moist interior surface of the lungs.
 Surface Tension in the Lungs
• To carry on the active exchange of carbon
dioxide and oxygen between the circulating
blood and the atmosphere in an average adult
requires a lung surface area roughly that of a
tennis court.
• Such an area is encompassed in the relatively
small volume of the chest by
compartmentalization of the lungs into
hundreds of millions of tiny air spaces, or sacs,
called alveoli.
 Surface Tension in the Lungs

• The alveoli have an average radius of about

0.005 cm; they are connected by confluent
passages through the bronchial tree and the
trachea to the atmosphere (Figure 21.9).
 Figure 21.9
• The relationships between respiratory airways and
blood vessels.
 Figure 21.9
• Alveoli are the air spaces in the lungs through which
oxygen enters the blood and carbon dioxide leaves.
• An average alveolus expands and contracts about
15,000 times a day during breathing.
 Surface Tension in the Lungs
• During normal inhalation, the pressure in the
alveoli is about 3 mmHg below atmospheric
pressure, and we say that they have a gauge
pressure* of -3 mmHg, which enables air to
flow into them through the bronchial tubes.

• The alveoli are lined with mucous tissue fluid

that normally has a surface tension of 0.05 N m-
1.
 Surface Tension in the Lungs
• During inhalation, the radius of the alveoli
expands by about a factor of 2; the pressure
difference required to inflate an alveolus is
given by the equation (see Appendix 21.1 on
p889 for derivation:
21.13
where Pi and Po are the gauge pressures inside
and outside of the alveoli, γ is the surface
tension of mucous fluid, and r is the radius of
the alveoli.
 Surface Tension in the Lungs
• For such an expansion to occur, the pressure
difference must be at least:
 Surface Tension in the Lungs
• The pressure in the space between the lungs
and the pleural cavity that holds the lungs, P0,
is only -4 mmHg (or 756 mmHg in absolute
value).

• Therefore, we have:

which is only 1/15 of the pressure required to

expand an alveolus.
 Surface Tension in the Lungs
• To overcome this problem, the alveolar cells
secrete a special type of surfactant (called
dipalmityl lecithin), which effectively reduces
the surface tension, so that the alveolus can
expand without difficulty in the course of the
15,000 or so breaths that are drawn into the
lungs of an adult each day.
 Surface Tension in the Lungs

• A striking example of what occurs when

insufficient surfactant is present is the
disorder known as respiratory-distress
syndrome of the newborn, which frequently
afflicts premature infants in whom the
surfactant-synthesizing cells do not yet
function adequately.
 Surface Tension in the Lungs
• Even in the lungs of a normal healthy baby,
the alveoli are so collapsed at birth that a
pressure difference as large as 25 to 30 mmHg
is required to expand them the first time.

• Therefore, the first breath of life requires

extraordinary effort to overcome the surface
tension in the alveoli.
 Surface Tension in the Lungs

• The surface activity discussed above also has a

bearing on water conservation.

• Spreading a thin film of a cetyl alcohol

[CH3(CH2)14CH20H] over the surface of water
can cut down the evaporation rate of water in
reservoirs.
 Surface Tension in the Lungs

• A solid, cetyl alcohol is insoluble in water. It

has surface solubility, however, in the sense
that its molecules float on water and form a
thin film that spreads to cover the surface.
 Surface Tension in the Lungs

• If the film is disrupted by weather or other

disturbances, it readily reforms.

• Only 30 g of the material is sufficient to cover

about 10,000 m2 (3 acres) of water surface.
 21.4 Diffusion

• Diffusion is the process by which concentration

gradients in a solution spontaneously decrease
until a uniform, homogenous distribution is
obtained.
 Fick’s Laws of Diffusion
• Imagine a container with a solution on the
bottom and the pure solvent on top, as shown in
Figure 21.10a.

• Initially, there is a sharp boundary between the

solution and the solvent.

• As time progresses, solute molecules gradually

move upward by diffusion. This process continues
until the entire system is homogeneous.
 Figure 21.10a
• Diffusion of a solute from
a cell of uniform cross
section into the pure
solvent component.
 Figure 21.10b
• Plots of concentration,
c, versus x.
• At t = 0 (the t0 curve),
the boundary between
the solution and pure
solvent component is
infinitely sharp.
 Figure 21.10c
• Plots of concentration
gradient (∂c/∂x)t versus
x at various times t after
diffusion has begun.
• At t = 0, the gradient is
a vertical line of infinite
height and no width
centered at x = 0.
 Fick’s Laws of Diffusion

• In 1855, the German physiologist Adolf Eugen

Fick (1829-1901) studied the diffusion
phenomenon and found that the flux (J), that
is, the net amount of solute that diffuses
through a unit area per unit time, is
proportional to the concentration gradient.
 Fick’s First Law of Diffusion
• Expressing this relationship mathematically in
one dimension along the x axis, we write:

21.14
 Fick’s First Law of Diffusion
• Equation 21.14 is known as Fick's first law of
diffusion in one dimension.

• The quantity (∂c/∂x)t is the concentration

gradient of the diffusing substance at time t of
diffusion, and D is the diffusion coefficient of
the diffusing substance in the medium
concerned.
 Fick’s Laws of Diffusion
• Its units are m2 s-1 or cm2 s-1.

• The negative sign indicates that diffusion

proceeds from higher to lower concentration,
because concentration gradient is negative in
the direction of diffusion.

• Thus, the flux is a positive quantity.

 Fick’s Laws of Diffusion
• Let us investigate the diffusion process in a
little more detail by asking the following
question: What is the change of concentration
with time at a given point along the x axis?

• Consider a volume element, Adx (where A is

the area of cross section), shown in Figure
21.11.
 Figure 21.11

• Rate of accumulation of solute in a volume element, Adx,

during a diffusion process.
 Fick’s Laws of Diffusion
• At distance x measured from the original
boundary, the rate of solute molecules
entering the volume element is —DA(∂c/∂x)t.

• Because the rate at which the concentration

gradient changes with x is given by:
 Fick’s Laws of Diffusion
• The rate of solute molecules leaving the
volume element, after having traveled
distance dx, is:
 Fick’s Laws of Diffusion

• Thus, the rate of accumulation of solute in the

volume element is the difference of the foregoing
two quantities:

rate of accumulation rate of solute rate of solute

of solute in the = entering the — leaving the
volume element volume element volume element
 Fick’s Laws of Diffusion
rate of accumulation rate of solute rate of solute
of solute in the = entering the — leaving the
volume element volume element volume element
 Fick’s Laws of Diffusion

• Now, there is another way of arriving at an

expression for the rate of accumulation.

• As time goes on, the concentration of solute in

the volume element is steadily increasing as a
result of diffusion.
 Fick’s Second Law of Diffusion
• The rate of this increase is given by the
product of the volume element and the
change of concentration with time, that is,
(∂c/∂t)x(Adx).

• Equating these two rates of solute

accumulation, we obtain:
21.16
 Fick’s Second Law of Diffusion
• Equation 21.16 is known as Fick's second law
of diffusion.

• It says that the change of concentration with

time at a certain distance, x, from the origin is
equal to the product of diffusion coefficient
and the change of concentration gradient in
the direction of x at time t.
 Fick’s Second Law of Diffusion

• Equation 21.16 is a fundamental diffusion

equation; however, it must be integrated
before we can apply it to practical systems.

• To obtain the value of D from suitable

experimental measurements, the appropriate
boundary conditions must be applied.
 Fick’s Second Law of Diffusion
• If the columns of liquids shown in Figure 21.10
are effectively of infinite length so that the
concentrations of solute at top and bottom
remain zero and co, respectively, throughout
the experimental run, the following boundary
conditions will hold:
 Fick’s Second Law of Diffusion
• The solution of Equation 21.16 with the
boundary conditions given above is:

21.17

where
 Fick’s Laws of Diffusion
• Using Equation 21.17, we can calculate the
concentration of solute at a distance x from
the origin after it has diffused for time t.

• Figure 21.10b shows a graphical

representation of Equation 21.17
corresponding to various values of time t.
 Fick’s Laws of Diffusion
• We can also express Equation 21.17 in the
differential form as:

21.18

• Equation 21.18 allows us to plot the

concentration gradient, (∂c/∂x)t, versus x at
different times, t, (Figure 21.10c).
 Fick’s Laws of Diffusion
• Determining the diffusion coefficient accurately is
rather difficult.

• Optical methods, such as refractive index

measurements, are normally employed to monitor
the concentration gradients at various distances
from the origin after diffusion has started.

• One useful technique measures diffusion

coefficients of biomacromolecules from laser light
scattering.
 Fick’s Laws of Diffusion
• We would expect that the larger the molecule,
the slower its motion.

• In diffusion studies, it is important to

determine the distance traveled by solute
molecules from their place of origin in a given
time, t.
 Table 21.3

• The data in Table 21.3 qualitatively confirm the expectation

that the larger the molecule, the slower its motion.
 Fick’s Laws of Diffusion
• Although diffusion occurs in one definite
direction, the movement of each individual
molecule is completely random and
unpredictable.

• Thus, the average, or net, distance, x, traveled

by the molecules is zero.
 Fick’s Laws of Diffusion
• For this reason, we need to consider the
mean-square distance, x2͞ , defined as (see
Equation 21.18):
 Fick’s Laws of Diffusion
• This standard integral is tabulated in the
Handbook of Chemistry and Physics.

• The result is:

• Hence, the root-mean-square distance, , is

given by:
21.22
 Fick’s Laws of Diffusion
• Equation 21.22 gives us a simple, yet useful,
relation for estimating mean diffusion
distances.

• For a liquid solution, we would expect the

frictional force exerted by a solvent medium
to affect the diffusion of a solute molecule.
 Fick’s Laws of Diffusion

• In 1905, Einstein proposed the following

quantitative relationship:
21.23

where kB is Boltzmann's constant, and f is the

frictional coefficient of the solute molecule.

• The units off are N s m-1.

 Fick’s Laws of Diffusion

• Thus, the product of f and the velocity of the

solute molecule gives the frictional force of
resistance (in newtons) exerted on the particle
by the solvent.
 Stokes Law
• The British physicist Sir George Gabriel Stokes
(1819-1903) showed that for a spherical
particle: 21.24

where η is the viscosity of the solvent, and r is

the radius of the molecule.

• Equation 21.24 is known as the Stokes law.*

 Stokes Law
• Now Equation 21.23 becomes:

21.25

• Either Equation 21.23 or 21.25 provides a

physical interpretation of the diffusion
coefficient.
 Stokes Law
• The term kB T is a measure of the thermal or
kinetic energy of the molecule, whereas f or η
is a measure of the viscous resistance to
diffusion.

• The ratio of these two opposing values

determines how easily a solute molecule
diffuses in solution.
 Stokes Law

• Equation 21.25 suggests a way to measure the

radius of the molecule if both D and η are
known.

• See Examples 21.2 and 21.3

 21.5 Liquid Crystals
• Molecules that exhibit liquid crystallinity are
usually long and rodlike.

• An example is para-azoxyanisol (PAA):

which has the following "melting" or transition

points:
 Liquid Crystals

• There are two known types of liquid crystals,

called thermotropic and lyotropic.