Name: ______________________________

Homework #5. Due at 1 PM on Friday, May 6. (85 points total)

For this assignment, NO LATE SUBMISSIONS WILL BE ACCEPTED, so that an answer key can
be posted for a full weekend ahead of the course final exam. All students should do all problems.
There are no course-specific problems in this assignment.
There are two parts to this assignment. Part I includes material that we have already covered in
class as of April 26th. You should start working these problems immediately. Part II includes
material that we will cover in the next few lectures. You should work these problems once the
appropriate topics have been covered in lecture.
PART I (Questions 1 through 3)
1. (18 points) Many molecules or polymers have portions that are hydrophobic and portions that are
hydrophilic. For example, detergent molecules typically have long hydrocarbon chains that are very
hydrophobic, and these chains are attached to so-called head groups that are hydrophilic, either charged or
dipolar. When placed in water, such molecules tend to form multi-molecular assemblies such that their
hydrophobic portions are all in contact with one another, and their hydrophilic portions are exposed to
water. A typical example of such an assembly is a micelle, with a schematic shown in the figure below.

(Image is from M. Pasquali, Nature Materials, 9 (2010) 381-382.)

We want to develop a simple estimate of how likely such molecules are to be found in structures like
micelles versus being dissolved in water as individual molecules.

a) Consider a simple model that treats a detergent molecule as a cylinder, where one end of the cylinder is
hydrophilic, and the sides and the other end are hydrophobic. The cylinder is assumed to be 1 nm in
length, and 0.7 nm in diameter (0.35 nm radius). A picture is shown below.
Hydrophilic End

1nm
height

Hydrophobic sides
and base

0.7nmdiameter

Calculate the surface area of the hydrophobic region of this model molecule. (Hint: The answer will be
the area of the sides of cylinder, plus one base of a cylinder of diameter 0.7 nm and height 1 nm)

b) We can estimate the free energy difference between having the molecule in a micelle and it being fully
exposed to water in the following manner. For the molecule fully exposed to water, the hydrophobic
surface area calculated in part a will lead to a free energy cost due to the hydrophobic effect. In class, we
estimated that free energy cost to be 7 kBT/nm2. That free energy penalty is entirely removed when the
molecule is present in a micelle, since the entire hydrophobic surface is protected from being exposed to
water.
Using this reasoning, together with the result of part a, calculate G (per molecule) for the process of a
detergent molecule in water moving to be a detergent molecule in a micelle. You can leave your answer
written in terms of kBT.

c) Based on your answer to part b, does it seem likely that isolated detergent molecules in water would
enter into micelles if possible? Explain your reasoning.

2. (18 points) A lipid molecule contains a polar head group, which may be charged. It also has a
hydrophobic region, which usually consists of two long hydrocarbon chains. When lipids are assembled
into bilayer membranes, the head groups are in very close contact with one another. If the head groups are
schematically represented as circles, and the hydrocarbon chains are represented by wavy lines, then the
structure of a biological membrane (with embedded proteins, which are not relevant to this problem) can
be schematically drawn as the following (taken from Figure 11-4 A of Physical Biology of the Cell)

a) Suppose that the head group of each lipid contains a single negative electronic charge (that is, a charge
of 1.6x10-19 Coulombs). If two head groups are separated by a distance of 0.7 nm, calculate their
interaction energy. You should assume that the lipid head groups are effectively fully exposed to water, so
that a dielectric constant D = 80 can be used. Express your answer in terms of a multiple of kBT, for T =
310 K.

b)Inparta,youshouldhavefoundaninteractionthatisrepulsive(i.e.,G>0,anddecreasingasthe
separationdistanceincreases),sotheelectrostaticinteractionoftheheadgroupswilltendtopushthelipid
moleculesapartfromoneanotheranddestabilizethemembrane.Whatisthedominantattractive
interactionthatwillcounterbalancethiselectrostaticrepulsion,andthereforeleadtoanoverallstable
membranestructure.Explainyouranswer.

c)Supposethatlipidswereplacedinasolventthatwasotherwiseidenticaltowater,buthadadielectric
constantD=2.Doesitseemlikelythatthebilayermembranestructureshowninthefigurewouldbe
stable?Explainyourreasoning.

3.(24points)WediscussedtheselfenergyortheBornenergyassociatedwithcreationofanionina
dielectricmaterial.Foranionofradiusa,theformulaforthefreeenergyrequiredwas:

GBorn

1 1 q2
2 4 0 D a

whereqisthecharge,0isthepermittivityoffreespace(8.85x1012C2/Nm2),andDisthedielectric
constantofthesolvent.
a)ConsideraCa2+ion,whichhasachargeof3.2x1019C,andanestimatedionicradiusa=0.99x1010
meters.Calculatetheselfenergyinthecaseofadielectricconstantof80(water)andadielectricconstant
of2(oil).

b)Whatisthedifferenceofthetwovaluesyouobtainedinparta(oilminuswater)?Expresstheenergy
differenceintermsofmultiplesofthermalenergy,kBT,atT=300K.

c)Considerthecasewheretheioncouldeitherbeinawaterphaseorinanoilphase.SincetheBorn
energyforboththewatercaseandtheoilcasewascalculatedrelativetothesamereferenceenergy,then
thedifferenceinBornenergiesfoundinpartbcorrespondstothestandardfreeenergydifference(G0)
forthereactionofanionmovingfromwatertooil.Basedonthevalueyouobtained,whatwouldbethe
equilibriumconstant,Keq,atT=300Kelvinforthereactioninwhichcalciumionsinwater(Ca 2+water)are
equilibratedwithcalciumionsinoil(Ca2+oil):

2+

2+ Caoil
Cawater

d)Frompartc,whatcanyouconcludeabouthowlikelyitwouldbethataCa 2+ionmightbelocatedinthe
hydrophobicinteriorofabiologicalmembrane?Explainyouranswer.

PART II (Questions 4 and 5)

4. (10 points) Consider the following four aqueous solutions for T = 300 Kelvin:
100 mM NaCl
250 mM NaCl
100 mM CaCl2
10 mM KCl
a) For each of these four cases, calculate the ionic strength.

b) For 100 mM NaCl under these conditions, the Debye length is 1 nm. For each of the remaining three
cases, calculate the Debye length in nanometers.
(Hint: You should be able to quickly carry out this calculation without evaluating the full expression of Debye length
for each solution. From part a, you will know the ionic strength of 100 mM NaCl as well as the ionic strength of the
remaining three solutions, and you can use the general relationship of how the Debye length depends on ionic
strength to calculate the Debye length of the remaining three solutions.)

5. (15 points) Consider a charged surface (silica) placed in an ionic solution with a Debye length of 1.0
nm. For silica, the surface potential will be less than zero (the surface is negatively charged).
a) Sketch the shape of the electrical potential as a function of the distance away from the surface. On your
sketch, indicate where the level V0 occurs on the vertical axis (you do not need to calculate an actual
numerical value of V0), and indicate where the value of the Debye length occurs on the horizontal axis.

b) Indicate how the plot you made in part a would change on both the horizontal and vertical axes if the
ionic strength of the solution were increased, with all other factors such as the surface charge density
remaining fixed. You can use the linearized form of Gouy-Chapman theory.

c) Indicate how the plot you made in part a would change on both the horizontal and vertical axes if the
ionic strength of the solution were decreased, with all other factors such as the surface charge density
remaining fixed. You can use the linearized form of Gouy-Chapman theory.