Chapter 7 Lecture

Biological Physics
Nelson
Updated 1st Edition

Entropic Forces at Work

Slide 1-1

Last time
We need Chapter 6 on ENTROPY, visit here:
Main points:

And the partition function Z

-kBT ln(Z) minimizes the free energy!

Entropic forces f = - dFa/dx
Slide 1-2

A great Sci-fi quote

The struggle between life elements is the
struggle for the free energy of a system.
DUNE, Frank Herbert, 1967

Slide 1-3

Outline
7.1 Microscopic view of entropic forces
Fixed volume and pressure approaches
7.2 Osmotic pressure
From ideal gas law and depletion forces
7.3 Beyond Equilibrium: Osmotic flow
Rectification of Brownian motion
7.4 A repulsive interlude
Electrostatics, Gauss Law and more
7.5 Properties of water (extra reading)
Water generates an entropic attraction
between nonpolar objects
Slide 1-4

Comment & Focus questions

F = E TS, macroscopic systems tend to lower
their free energy even if: The change actually increases the energy
(but increases TS more)
The change actually decreases entropy (but
decreases E/T more)
What keeps cells full of fluid?
How can a membrane push fluid against a
pressure gradient?
Osmotic pressure is a simple example of an
entropic force
Slide 1-5

7.1 Microscopic view of entropic forces

Constant volume case leads to (pressure case,
extra-reading). Derive p = kBNT/V from partition
function where in this case Z is

And Fa=-kBTln(Z(L)) where many of the terms

above are just constants
So Z is a constant L3N
F(L) A - kBTNlnL3
Using entropic force then recovers the ideal gas
law:
Slide 1-6

Osmosis and entropic forces?

Slide 1-7

7.2.1 Equilibrium osmotic pressure from

ideal gas law
Consider Fig. 1.3 (previous slide). For a dilute
concentration we apply same methods as for an
ideal gas to find the free energy
This time V is RHS of chamber in Fig. 1.3 and
derivative of ln Z is again N/V and (c = N/V)

How about when there is air (or atmospheric

pressure)? In this case we get p=zf m g
See figure 7.1 and the thistle-tube experiment
How does this work? Try Your Turn 7B
Slide 1-8

Osmotic pressure experiment

thistle-tube experiment
Slide 1-9

7.2.1 Cell safety: Laplaces formula

Estimates
Homework/whiteboard for now
Result is

Surface tension, , estimated ~1.510-3 N m-1

Enough to rupture a eukaryotic cell
membrane
Summary
Osmotic pressure is significant for cells
Slide 1-10

7.2.2 Depletion force for large molecules

1993. Used by permission of Springer-Verlag.

Slide 1-11

7.2.2 Osmotic pressure creates a depletion

force between large molecules
The hierarchy in Fig. 7.2 leads to surprising
entropic effects
Depletion interaction or molecular crowding
Consider two LARGE sheep in a bath
containing smaller sheepdogs with number
density c. The sheepdogs herd the larger sheep
together. How (see Fig. 7.3)
In order to decrease Fa depletion zone is short
range of order 2a (a size of sheepdog)
Pressure is change of free energy per change of
volume
Slide 1-12

The depletion zone (interactions)

Slide 1-13

Experimental data (depletion is real!)

1998, American Chemical Society. Used by permission.

Slide 1-14

7.3.1 Beyond Equilibrium: Osmotic Flow

Where does osmotic pressure come force from?
Ultimately, from membrane itself (see Fig.7.5)
Using
& hydrostatic eq:
Leads to Eq. 7.13:

where =

How do we solve this. We need a result for c(z)?

Using c=c0
and steps on p. 258 gives

This is just p=c0kBT or more generally:

Slide 1-15

Osmotic flow: Fluid forces

Slide 1-16

7.3.1 Osmotic flow

The equilibrium pressure difference across a
semipermeable membrane equals kBT times the
difference in concentration between the two force-free
regions on either side of the membrane.
Read 7.3.2 for homework (see section 5.3.4 as
well)
Generally we have

where is the filtration constant of the membrane

Reverse osmosis occurs when pckBT (see

Fig 7.6d)
Slide 1-17

Figure 7.6 (Schematic, sketch graphs.) Caption: See text.

Slide 1-18

Figure 7.6 Caption

Figure 7.6: (a) A literal model of a semipermeable membrane, consisting of a
perforated wall with channels too small for suspended particles to pass. (b)
The force along z exerted by the membrane on approaching particles is
dU/dz, where U is the potential energy of one particle. (c) In equilibrium, the
pressure p is constant inside the channel (between dashed lines), but p falls in
the zone where the particle concentration is decreasing. (d) Solid curve: If the
pressure on both sides is maintained at the same value, osmotic flow through
the channel proceeds at a rate such that the pressure drop across the channel
(from viscous drag) cancels the osmotic pressure jump. Dashed curve: In
reverse osmosis, an external force maintains a pressure gradient even greater
than the equilibrium value. The fluid flows oppositely to the case of ordinary
osmotic flow, as seen from the reversed slope of the pressure profile inside the
channel.

Slide 1-19

4.6.1 Recall Membrane Diffusion*

Imagine a long thin membrane/tube of Length L,
with one end in ink C(0)=c0 and in water C(L)=0
This leads to a quasi-steady state so we set
dc/dt =0 and hence d2c/dx2=0
This means that c is constant and js=-Dc/L
where c0=cL-c0 and subscript s means the flux
of solute not water
Now define js=-Psc where Ps is the permeability
of the membrane.
Slide 1-20

 In simple cases Ps roughly relates to the width of

the pore and thickness of the membrane (length
of pore)

Using dN/dt=-Ajs leads to

Slide 1-21

Last weeks homework: Your Turn 4C

Generalizing Fig. 7.6 to concentrations 1 & 2
a) = 1 2 < 1 2
b) = 1 2 > 1 2 (reverse osmosis)

Slide 1-23

Section 7.4

A REPULSIVE INTERLUDE

Slide 1-24

7.4.1 Bulk electroneutrality?

Example: For a raindrop with R=1 mm, how
much work is needed to remove 1 electron from
1% of the water molecules in the drip?
If we take away charge then we form a shell with
electrostatic potential energy
Eelectrostatic =

2
80

where

2
40

= 2.3 1028 Jm.

This implies
2
1% 2
103 61023
4
=

103 3 0.01
3

0.0018
3
2.31028
= 2 1011 = 4.1 1021 .
2

So electrically neutral!
Slide 1-25

7.4.1 Electrostatic interactions are critical

for cell functioning
From Your Turn 7D, if R=1 nm we see that
separation energy 0.7 .
Hence on nanoscales DNA is a macroion which
is nearly fully dissociated (cf. Chapter 8)
Even though the electrostatic interaction is of
long range in vacuum, in solution the screening
effect of counterions reduces its effective range,
typically to a nanometer or so.
Macroions will not feel each other until theyre
nearby. Once nearby, detailed surface pattern of
+ve and ve residues on a protein can be felt by
its neighbor, not just the overall charge.
Slide 1-26

Continued ...
While each individual electrostatic interaction
between matching charges is rather weak
(compared to kBTr), still the combined effect of
many such interactions can lead to strong
binding of two moleculesif their shapes and
orientations match precisely.
Molecular recognition implies we understand the
counterion cloud around a charged surface
This implies Gausss Law
This is not enough as we also need to worry
about orientation (stereospecificity)
Slide 1-27

7.4.2 The Gauss Law (for later use)

You should have already studied the Gauss law:

which for a flat charged surface gives

Considering Fig. 7 (next slide) we find that a

solid element satisfies
implying

Slide 1-28

7.4.2 The Gauss Law

Slide 1-29

7.4.3 Counterions on charged surfaces

Example: You might want to coax DNA into a
cell for gene therapy, but both are negatively
charged
We want to know by how much?
Consider the slightly simpler problem depicted
in Figure 7.8a
Assume monovalent counterions e.g. Na+
Problem is that we are not given the charge
distribution?
We need to find it, but an electrostatic force is
long range so we need to know positions of all
the other charges
Slide 1-30

7.4.3 Counterions near surfaces

Slide 1-31

7.4.3 Charged surfaces are surrounded by

neutralizing ion clouds
We need to evaluate the effect of many ions all
moving around and repelling each other?
This is too complicated so we make a very
common assumption in physics:
The Mean Field Approximation (MFA)
For a large no. of ions we assume that all the
other ions contribute to an average charge
density and can ignore individual
charges i between ions
Well use this to solve the Poisson-Boltzmann
equation but first we need to derive it ...
Slide 1-32

7.4.3 Poisson-Boltzmann Equation

The Boltzmann part comes from the MFA
assuming c+(x)0 with
c+(x)=c0exp[-eV(x)/kBT]
and V(0)=0 fixes c0=c+(x=0) is the no. of counterions at the surface
The Poisson relation comes from bulk Gauss
law: dE/dx = / with =-dV/dx gives
d2V/dx2=- /
Slide 1-33

7.4.3 Poisson-Boltzmann Equation*

Equating the charge now leads to
d2V/dx2=-ec+(x)/=-ec0/ exp[-eV(x)/kBT]

Defining
and dimensionless variables
gives

Problem: How to solve this equation?

Slide 1-34

Mean Field Approximation

Slide 1-35

7.4.3 Boundary conditions

Like any differential equation we need to find
boundary or initial conditions: d2z/dt2=-g does
NOT tell you how high a rock will rise into the air
Need to know how hard you threw it or its
initial speed and height.
Solution for Poisson-Boltzmann case?
Use boundary Gauss Law -dV/dx|surface = - /
or in terms of new variables

NB. Remember is a positive number

Slide 1-36

Solutions of the PB equation: Case 7.8a

We have the BC at surface (previous slide) plus
another solution at infinity: d/dx= 0 and (0)=0
PB eqn is non-linear and generally very difficult
to solve; however the exponent implies (x)=ln x
might be a solution, but this blows up at x=0:
Therefore try
We need to find B and x0? (class exercise)

This is the Gouy-Chapman layer with length x0

Slide 1-37

PB solution continued: Case 7.8a

A diffuse layer forms with thickness x0: The
counterions are willing to pay some electrostatic
energy to gain entropy
Note, turning off thermal motion (T0) implies
an infinite Bjerrum lenth and hence x00.
How much energy? Think of two sheets of
charge with capacitive energy E=qtot2/(2C) where
C = A/x0 . Combining the preceding formulae
we find (Case 7.8c?):

for no added salt

Slide 1-38

7.4.4 Repulsion of like charged surfaces

Solution of the PB equation for two negatively
charged surfaces, Case 7.8b
We now have a symmetric solution with 0 =
0: = 2 ln , where = 2 0 and
+ = 0 cos 2
Finally, applying surface charge b.c. leads to

4
= 2tan

This is a great example of solving a problem

graphically (used a lot in quantum mechanics)
The important point is that this has been
observed experimentally (see next next slide)
Slide 1-39

Graphical solution to Poisson-Boltzmann

Two oppositely charged surfaces (Fig. 7.8b)

Slide 1-40

Comparison with experiment: it works!

Slide 1-41

The Big Picture: Conclusion

What is the big picture from Chapter 7?
Entropic forces ubiquitous in the cellular world
Depletion Forces
Osmosis
Reverse osmosis
Neutral objects can be charged on nanoscales

Slide 1-42

Homework I
Read Section 7.5
Special properties of water
Figure out Figure 7.6 and try
Your Turn 7A, 7B and 7C and Poisson
Relation
Think about electric neutrality and whether or
not this is true for either macroscopic or
nanoscopic systems?
Try 7.4.3:- Track 2 on page 284 (book); pg.
250 of ebook. Including a salt solution
Slide 1-43

Chapter 8: Chemical Forces & Self Assembly

NEXT TIME

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