Surface tension

Chemistry 433 Liquids tend to adopt shapes that minimize their surface area.
This places the maximum number of molecules in the bulk.
Droplets of liquids tend to be spherical because a sphere is
Lecture 23 the shape with the smallest surface-to-volume ratio. The work
needed to change the area by dσ is:

Physical Chemistry dw = γdσ

of Surfaces
The coefficient γ is called the surface tension. It has
dimensions of energy per unit area (J/m2). At constant
volume and temperature the work of surface formation is
NC State University equal to the Helmholtz free energy:

dA = γdσ

Since dA < 0 is a spontaneous change surfaces tend to contract.

Curved surfaces Capillary Rise

The pressure exerted by a column
A liquid surface is not generally flat. This has two consequences. of liquid of density ρ is:
1. The curvature of the surface affects the vapor pressure. P = ρgh
2. The capillary rise or of liquids in narrow tubes results. At equilibrium this hydrostatic
pressure matches the pressure
We consider bubbles (vapor trapped in liquid) or droplets (liquid difference Pin - Pout = ΔP = 2γ/R.
in vapor) as spheres of area 4πR2. Here we consider a bubble The height of a column of
where the pressure inside the cavity is Pin. The outward force is li id iin a narrow capillary
liquid ill iis
4πR2Pin . The force inwards arises from the external pressure obtained from:
Pout and the surface tension. The differential change in area is:
dσ = 4π(R + dR)2 - 4πR2 = 8πRdR 2γ/R = ρgh
Since, dw = 8πγRdR the force is F = 8πγR. Pressure is force per
unit area so: so that:
4πR2 Pin = 4πR2 Pout + 8πγR 2γ
h=
or: ρgR
Pin = Pout + 2γ/R

Capillary rise problem Capillary rise problem

Given that the surface tension of water is 0.0728 J/m2 Given that the surface tension of water is 0.0728 J/m2
calculate the capillary rise in a glass tube that is 1 mm in calculate the capillary rise in a glass tube that is 1 mm in
radius. radius.

A. 1 mm A. 1 mm

2γ 0 0728 J/m 2
2 0.0728
B. 1.5 mm B. 1.5 mm h= =
ρgR 1000 kg/m 3 9.8 m/s 2 10 – 3 m
C. 10 mm C. 10 mm
= 0.015 m = 1.5 cm
D. 15 mm D. 15 mm

1
 Capillary rise problem Capillary rise problem
Given that the surface tension of ethanol is 0.032 J/m2 Given that the surface tension of ethanol is 0.032 J/m2
calculate the capillary rise in a glass tube that is 0.1 mm in calculate the capillary rise in a glass tube that is 0.1 mm in
radius. Assume that density of ethanol is 0.71 g/cm3. radius. Assume that density of ethanol is 0.71 g/cm3.

A. 47 mm A. 47 mm

2γ 0 032 J/m 2
2 0.032
B. 65 mm B. 65 mm h= =
ρgR 710 kg/m 3 9.8 m/s 2 10 – 4 m
C. 91 mm C. 91 mm
= 0.91 m = 9.1 cm = 91 mm
D. 110 mm D. 110 mm

Vapor pressure and surface tension Gibbs adsorption isotherm

When water or other liquids are finely divided then we must add
a term to the free energy expression:
dG = VdP - SdT + γdσ + μdn
The term γdσ is the change in free energy when the surface area
is changed. The free energy of bulk water is μH2O. The
additional
dditi l tterm iimplies
li ththatt th
the ffree energy will
ill b
be minimized
i i i d as
the total surface area is minimized. This means that the liquid
will form a sphere if no other forces are acting on it. Furthermore,
the spheres will tend to combine to form the largest possible
sphere (thereby minimizing the surface-area-to-volume ratio).
This implies that smaller droplets of water that have a higher total
surface area have a higher vapor pressure than bulk water and
therefore transfer spontaneously into a larger drop.
Molecules at surfaces are attracted to the bulk. This creates
a force that tends to minimize surface area. If the surface is
stretched, the free energy of the system is increased. The
free energy per unit surface area is called the surface tension.
The SI units of surface tension are millinewtons per meter
(mN/m). The surface tension is also the surface free energy
per unit area given by:
γ = ∂G
∂σ T,P
where σ is the area. Substances that lower the surface tension
also lower the surface free energy and therefore they migrate
to the surface. The quantitative expression of this phenomenon
is called the Gibbs adsorption isotherm:
dγ dγ
Γ=– 1 ≈– 1
RT d ln a RT d ln c
Γ = adsorption (excess concentration) of solute at surface, mol/m2
γ = surface tension, N/m, a = activity, c = molarity

Measuring surface tension Measuring surface tension

Psurface(nM / m) = γ 0 – γ
γ γ0
Langmuir balance
The surface pressure is equal to the difference in the surface
tension of the pure water (γ0) and for the mixture (γ).
The surface pressure is usually plotted vs. the area per
molecule (in Å2/molecule). This is the reciprocal of the surface
Concentration (units can be either molecules/ Å2 or moles/m2).
As the surface pressure is increased the molecules pack
more closely and the area per molecule decreases.
There may be discontinuities
due to phase transitions.
The maximum surface
pressure is equal to the
surface tension of pure
water. At the surface
pressure the film collapses γ γ0
and γ = 0. Langmuir balance

2
 The hydrophobic effect Thermodynamic data for the
The free energy change for transfer of hydrocarbons from organic
solvent to water is positive. The dominant contribution to the
transfer of hydrocarbons to water
hydrophobic effect is the entropy. In the organic phase: HydrocarbonμH0(W)-μH0(H) HH0(W)-HH0(H) SH0(W)-SH0(H)
(kJ/mol) (kJ/mol) (J/mol-K)
μH(H) = μH0(H) + RT ln aH(H) -------------------------------------------------
C 2H 6 16.3 -10.5 -88
(H = hydrocarbon, W = water) C 3H 8 20.5 -7.1 -92
IIn water
t the
th chemical
h i l potential
t ti l iis: C4H10 24.7 -3.3 -96
C5H12 28.7 -2.1 -105
μH(W) = μH0(W) + RT ln aH(W) C6H14 32.4 0 -109
C 6H 6 19.2 +2.1 -59

Thermodynamic data for the transfer of hydrocarbons from

hydrocarbon solvents (H) to water (W) have been obtained
by Tanford.

Lipid polymorphism
Lipids and Surfactants
Both lipids and surfactants consist of a hydrophobic tail
region and a hydrophilic head group (amphipathic).
Both lipids and surfactants will orient with their head
groups pointed towards the water interface and their
tails sequestered from water.

Lipids have the ability to form a bilayer. This property

makes these molecules the constituents of biological
membranes. Bilayers can be gel-like or crystalline. They
can have a planar phase or form hexagonal phase.

Surfactants can tend to form micelles. Micelles are spherical.

The hydrophobic tails form the interior and the charged head
groups are on the surface. Biochemistry of Lipids, Lipoproteins
and Membranes, Vance & Vance, Elsevier 1996

Lipid structure The fluid mosaic model

Representative lipids are Plasma membrane
shown in Figure to the
right. There are two acyl
chains on a glycerol.
The third site is a
phosphodiester with a
number of possible
groups indicated.

Cytosol
Biochemistry of Lipids, Lipoproteins
and Membranes, Vance & Vance, Elsevier 1996

3
 Membrane asymmetry Detergents and
The inner and outer leaflets of membrane bilayers have Lysophospholipids
different compositions. Erythrocytes are the most studied. R
The cytosolic side is composed of PE and PS. The PE Detergents are amphipathic O-
O S O O
distribution is ca. 80% in the inner membrane and 20% in molecules that can have charged
the outer membrane. PS is negatively charged and PE is or uncharged head groups and OH
moderately negative in charge. The inner membrane is single hydrophobic tails. If one
thus largely
g y negative.
g of the acyl chains is cleaved from O
O
a lipid
li id th
then a llysophospholipid
h h li id iis
The outer membrane consists of PC, sphingomyelin, and created.
glycolipids. Cholesterol is also important and associates Other associating molecules
with the membrane to provide added fluidity. Plasma include aromatic or fused ring
membranes have equimolar quantities of cholesterol. By compounds (dyes, purines,
contrast, the endoplasmic reticulum and mitchondrial pyrimidines) and alicyclic fused
membranes have small amounts of cholesterol. ring compounds (bile salts,
cholesterol etc.).

SDS Lysophospholipid

Membrane fusion Membrane fusion

Membrane fusion occurs in fertilization, cell division, exo- and
endocytosis, viral infection and intracellular membrane transport.

Model Systems
Model membrane SUVs will undergo fusion when incubated
at or near Tc. For example, continued recycling of sonicated
PC vesicles
i l th
throughh Tc = 41 oC results
lt iin fformation
ti off larger
l
vesicles. For fusion events in vivo calcium is often required.

Biological Systems
It is difficult to determine the mechanism for membrane fusion.
Two proposals that pass through inverted micellar transition
states are shown on the next slide.

Drug Delivery Transmembrane Potential

The membrane potential is transmembrane electrical potential
The role of lipids in biology
must be understood in order difference expressed inside with respect to outside. Using the
to enhance drug delivery outside as the reference potential makes sense as all cells share
methods. Biological membranes
that outside. This choice of direction (or sign convention) affects
are permeable to small neutral
molecules (MW < 1000 Daltons). other measures of electrical properties, notably transmembrane
A number of strategies to current, which are all expressed inside with respect to outside.
enhance drug delivery involve
the use of liposomes. An example Thus our current convention is that current crossing the membrane
shown in the Figure consists of from inside to outside is positive.
a liposome that is targeted using In physics we express the potential as V (unit is the volt).
surface-attached monoclonal
antibodies that recognize a particular In chemistry the Nernst equation is used to describe the dependence
cell-surface antigen. of the oxidation potential on concentration. The symbol is E (or Eo)
and the unit is also the volt.

4
 The Nernst equation Application of the Nernst equation
The Nernst equation describes the potential for each half-reaction to membrane potential
a(Ox) + ne- b(Red) The free energy per mole of solute moved across the membrane
The standard potential (i.e. potential at 1 molar concentration) is Eo. ΔGconc = -RTln(Co/Ci) where Co is the concentration outside the
The electrode potential is given by: membrane and Ci is the concentration inside the membrane. The

[Red]
b difference in charge concentration results in a free energy contribution
E = E o – RT ln
nF [Ox] a from the voltage difference ΔGvolt = -FΔE (assuming n=1). The
where R is the gas constant and F is the Faraday (96,450 J/volt). balance of forces at equilibrium requires that ΔGvolt = ΔGconc so that
In an electrochemical cell where two half-reactions are combined the trans-membrane potential is obtained as follows.
to make a redox reaction, the electromotive force is: ΔGvolt = ΔGconc
Co
emf = E(+) - E(-) – FΔE = – RT ln
Ci
The free energy is G = -nFE. Therefore, the standard free energy Co
ΔE = RT ln
change for a redox process is ΔGo = -nF(Eoox - Eored) = -nFΔEo. F Ci

Problem Problem
At 25o C the Nernst equation can be simplified to: At 25o C the Nernst equation can be simplified to:

Co Co
ΔE = 0.059 log E = 0.059 log
Ci Ci

Calculate the transmembrane potential if the concentrations of K+ Calculate the transmembrane potential if the concentrations of K+
inside and outside the cell are [K+]i = 140 mM and [K+]o = 30 mM, inside and outside the cell are [K+]i = 140 mM and [K+]o = 30 mM,
respectively.
i l respectively.
i l
A. ΔE = -39 mV A. ΔE = -39 mV K+
E = 0.059 log o
= 0.059 log 30
B. ΔE = -59 mV B. ΔE = -59 mV K+ i
140

C. ΔE = -67 mV C. ΔE = -67 mV = – 0.039 V = – 39 mV

D. ΔE = -78 mV D. ΔE = -78 mV

Problem Problem
At 25o C the Nernst equation can be simplified to: At 25o C the Nernst equation can be simplified to:

Co Co
E = 0.059 log E = 0.059 log
Ci Ci

Calculate the transmembrane potential if the concentrations of H+ Calculate the transmembrane potential if the concentrations of H+
inside and outside the cell are [H+]i = 0.1 μM and [H+]o = 11 μM, inside and outside the cell are [H+]i = 0.1 μM and [H+]o = 11 μM,
respectively.
i l respectively.
i l
A. ΔE = 120 mV A. ΔE = 120 mV H+
E = 0.059 log o
= 0.059 log 11
B. ΔE = 197 mV B. ΔE = 197 mV H+ i
0.1

C. ΔE = 217 mV C. ΔE = 217 mV = 0.120 V = 120 mV

D. ΔE = 277 mV D. ΔE = 277 mV

5
 Review of Electrostatics Electrostatic potential is long range
Coulomb’s law: The force between two charges q1 and q2 is The Coulomb constant is:
qq 1 = 8.987 x 10 9 Nm 2/C 2
F = k 12 2 , k = 1 k=
4πε 0
r 4πε 0
ε 0 permittivity of vacuum 8.854 x 10 C /N/m Including the electron charge (so that the charges are now
– 12 2

just partial charges z1 = eq1 and z2 = eq2) and converting

The force is a vector quantity and can either be attractive
the distance to Å, the potential is:
(negative) or repulsive (positive). zz
U=K 1 2
+ + - + r(Å)

K= e 2 = 2.35 x 10 – 18 J = 1420 kJ/mol

The electric field is the force per unit charge. 4πε 0Å
qsource
Field = Force
Two charges at a distance of 10 Å
q = k r2 have a potential of 142 kJ/mol.

Electrostatic potential is derived Electric field across parallel plates

from the field The case of a constant electric field, as between charged
The electrostatic potential has units of volts and is derived parallel plate conductors, is a good example of the
from the field by: relationship between work and voltage.
q +++++++++++++
V= Edr = k r2
Volts V d
Field =
distance
To obtain an energy in MKS units volts are multiplied by
the electron charge e = 1.62 x 10-19 coulombs (C). ------------------
Therefore, 1 eV = 1.62 x 10-19 Joules. The electric field between parallel plates (and across a
The Faraday is just the charge of a mole of electrons membrane) is the voltage drop divided by the distance.
NAe = (1.62 x 10-19 C)(6.022 x 1023) = 96,450 C (J/V)
Remember Joules = Coulombs x Volts.

Physiological Aspects Voltage and Electric Field

Although the membrane potentials observed in cells are
Typical values
<0.1 volt, the electrical field is very large. Changes in this
Expressed with the above convention, all cells have membrane
field, brought about through changes in membrane potential can
potentials which are inside negative. The values observed vary
have marked affects on membrane proteins that themselves carry
a little from cell to cell and across different species, but for nerve
charges. Such influence on membrane proteins can markedly
and muscle cells that are veryy well studied, a typical
yp value is
change cell activity.
-80mV (ranging from -90mV to -60mV). (mV = millivolt = 10-3 volt)
The field is the voltage divided by the distance of the
Basis
voltage drop Field = V/d. The units of field relevant to the
The membrane potential is a manifestation of a small separation
dimensions of membranes are volts/nm. In the laboratory we
of charge across the lipid bilayer of the membrane. The lipid is the
often measure the field in volts/cm or volts/m.
dielectric of a parallel plate capacitor in which the salty (conductive)
solutions separated by the membrane are the plates of the capacitor.

6
 Changes in
Transmembrane Potential
Although the membrane potentials observed in cells are
<0.1 volt, the electrical field is very large. Changes in this
field, brought about through changes in membrane potential can
have marked affects on membrane proteins that themselves carry
charges. Such influence on membrane proteins can markedly
change cell activity.
Any process that changes the separation of charge across
the membrane will change membrane potential. These processes
can be natural or experimental, and an experimental one serves to
illustrate the phenomenon well. It is known as current injection.
Current Injection Experiment
The microelectrode is a very fine glass tube which can penetrate
the membrane, The solution inside the electrode (usually
concentrated KCl) will then be connected to the inside of the
cell and can be used to carry current into the cell, hence the
name current injection. For this to happen the circuit must be
completed: the switch must be closed, and the current must
go to the reference electrode outside the cell by passing outwards
through the membrane. This is shown in the following diagram.
The positive charges reaching the inside of the membrane will
tend to reduce the inside negativity, and the positive charge
carried away from the outer surface will also do so.

Transmembrane Potential Transmembrane Potential

Switch + - Switch + -

Microelectrode Microelectrode

Cell Cell
Reference Reference
- + Electrode - + Electrode

Transmembrane
Potential is reduced

There are several important points to note:

Although termed current injection the current is outward from
the membrane perspective.
There must be a circuit: in through the electrode, out through the cell.
The outward current will tend to make the membrane potential
become less negative. In other words the positive (outward)
transmembrane
b current will
ill tend
d to make
k the
h membrane
b potential
i l
move in a positive direction. If the current could be adjusted in
magnitude it could be made large enough to eliminate the original
charge separation altogether. This particular case is very important
in many attempts to understand membrane phenomena because
the membrane potential is temporarily eliminated from influencing
ion movements when V = 0.