Transport in and out of Cells - I

• Transport of molecules into (and out of) the cell can take
three main forms:
• Diffusion:
• Passive ("simple") diffusion: occurs along a
concentration gradient directly through the lipid
bilayer. Example: Oxygen and carbon dioxide
molecules.
• Facilitated diffusion: occurs along a concentration
gradient, but requires a protein channel as a conduit.
Example: aquaporins
• Ion channels: selective conduit proteins, usually gated,
which only allow the passage of specific ions, usually in
response to a triggering stimulus. Example: voltage-
gated sodium channels.
Transport in and out of Cells - II
Species Molecule Permeability coefficient (cm/s)
+ −14
Ions Na 5.0 × 10
+ −14
K 4.7 × 10 One might summarize molecular
susceptibility to passive diffusion as
1
Small O2 2.3 × 10 follows:
molecules CO 2 3.5 × 10
−1
• Molecular gases cross very rapidly
• Small molecules cross without
difficulty, especially if they are lipid
−3
H2O 3.4 × 10 soluble
Ethanol 2.1 × 10
−3
• Larger molecules cross without
Steroids
−3
10 to 10
−4
difficulty only if they are lipid soluble
Urea 4.0 × 10
−6
• For charged molecules (eg. ions), the
Glycerol 5.4 × 10
−6 lipid bilayer is virtually impermeable
−5 −6
Small molecule 10 to 10
drugs

−7
Peptides Cyclosporin A 2.5 × 10
All the studies were done on either some sort of purified phosphatidylcholine membrane or an
artificial lipid bilayer thought to mimic the properties of the real membrane.
Cell in a ‘bath’ - I There is a difference between
intracellular and extracellular ion
concentrations leading to a
chemical concentration gradient
between the two compartments.

When ion selective channels are

not open, the electrical neutrality
on either side of the membrane is
well maintained.

Equal concentrations of positive

and negative ions on each side of
the cell membrane means that
there is no potential difference
between the compartments.
Cell in a ‘bath’ - II
The potassium channels are open at
all times, at all membrane potential
voltages (i.e. these are not voltage-
gated channels), and they have no
natural gating ligands, nor are they
affected by any of the conventional
potassium channel blockers.

Though sodium channels do exist, they

are few - and so typical animal cells
are mainly permeable to potassium
ions, because of the presence of "leak
channels".
Cell in a ‘bath’ - III
Cell in a ‘bath’ - IV

“resting”
membrane
potential
 Ions and potentials - I

If electrical changes occur, the charges q = q1, q2, . . . , qM

on the species 1, 2, . . . , M must also be taken into
account as extensive variables in the energy function
U = U(S,V,N, q).

The electrostatic energy is qψ, where ψ is the

electrostatic potential felt by an ion due to the presence
of electrodes, nearby charged surfaces, or any other
constellations of charges. The fundamental equation,
augmented to include charge effects, is
where i = 1, 2, . . . , M are the charged species and
the electrostatic potential ψ = ψ(x,y, z) can depend
on spatial position in general.

The differential equation for the Gibbs free energy

including charge interactions is
 Ions and potentials - II
The total charge on species i is qi = zieNi, where zi is the valence
(the number of charges per ion), e is the unit charge on a
proton, and Ni is the number of ions of type i.

When an exchange process involves only charged particles, the

indices j and i coincide and the free energy is
This is defined as the
electrochemical potential

For uncharged species at constant T and p, equilibrium

occurs when the chemical potentials are equal.

For charged species, equilibrium occurs when the

electrochemical potentials are equal.

Partitioning, solvation, and the transport of charged particles

are governed by both chemical and electrostatic forces.
 Ions and potentials - III
Consider two different locations in space, r1 and r2, Now consider a single species of mobile ions (we
within a single solution. Let’s look at a one can drop the subscript i) that is free to distribute
dimensional problem. Suppose that r1 = x1 and r2 = x2. between locations x1 and x2. The mobile ions will
At location x1, some collection of fixed charges or be at equilibrium when the electrochemical
electrodes creates the electrostatic potential ψ(x1). potentials are equal:
At x2, you have ψ(x2).

By regarding μ◦ as independent of x in this case, we are

restricting our attention to situations in which x1 and x2
are in the same phase of matter.

Nernst the Boltzmann distribution law

equation for systems involving charges.
 Ions and potentials - IV
According to the Nernst equation, positive ions tend
to move away from regions of positive potential
ψ(x) > 0 and toward regions of negative potential.

Negative charges move the opposite way. These

tendencies increase with the charge on the ion or
decrease with the temperature.

While μ = μ◦ + kT ln c(x) describes a balance

between translational entropy and chemical affinity
for nonelectrolytes, the Nernst equation describes a
balance between translational entropy and
electrostatic forces for electrolytes.
The chemical potential describes the free energy of inserting
one particle into a particular place or phase, subject to any
If the electrostatic potential ψ(x)
appropriate constraint. Constraints are introduced explicitly. (a) is a linear function of distance x, then
(b) the concentration c(x) of ions depends
In contrast, the electrochemical potential always carries an exponentially on x, according to Nernst
implicit constraint with it: overall electroneutrality must be Equation. Positive ions are depleted near
obeyed. This is a very strong constraint. the positively charged surface.

Ions and potentials - V
Some biological membranes have protein pores or
channels that allow certain ions to pass through, but
not others. Figure shows a hole in a membrane that
represents a potassium channel, through which the
permeant K+ ions pass freely but other ions cannot.
Model for an ion channel. (a) The initial concentration of
positive ions on the left is high, before the system equilibrates.
If positive ions can flow, but negative ions cannot, then positive
ions tend to flow down their concentration gradient from left
to right. This creates a net positive electrostatic potential on
the right that opposes further flow. (b) The final equilibrium
state is more positive on the right.
Suppose you put a high concentration of KCl on the
left and a low concentration on the right. At first,
each side would be electroneutral with no electrical
driving forces.
Then K+ flows from left to right, down its
concentration gradient. There is no counter-
balancing flow of Cl−, because Cl− cannot permeate
the membrane. Therefore, a net positive charge
builds up on the right side of the membrane.
Equilibrium is achieved when the electrochemical
potential for K+ is the same on both sides:
In mammalian skeletal muscle, the extracellular
potassium concentration is [K+]out = 4mM and the
intracellular concentration is [K+]in = 155mM.
The K+ potential at 37C is given by ψin −ψout = −98mV.
Ions and potentials - VI where VK is the equilibrium electrical PD, which exactly
opposes the chemical energy of the chemical gradient,
the intracellular-to-extracellular K concentration ratio
The Nernst Equation defines ([K]in/[K]out). R is the gas constant with units of 8.31 J/(Kmol),
the potassium potential. T is absolute temperature in Kelvin (37°C = 310 K), F is
Faraday’s constant at 96,500 coulombs/mol, and z is the
valance of the ion question; 1 for K.

Other key contributions come from ions Na+ and

Cl- which permeate through the membrane.

The resting potential is given by the

Goldman-Hodgkin-Katz equation:

Pi is the membrane permeability (in cm/s)

for the indicated ion.
If the membrane were to become permeable only to
K, i.e., if PNa and PCl were zero, then the equation
simplifies to the Nernstian condition for K.

Note that to account for the differences in valence,

the anionic Cl concentrations are presented as “out
over in,” rather than as the “in over out” convention
used here for cations.
Ions and potentials - VII

The calculated Nernstian equilibrium potential for K, Na,

and Cl establish the “boundary conditions” for the
electrical PD across the cell membrane;
i.e., the cell cannot be more negative than 92 mV or more
positive than 64 mV (see Figure) because there are no
relevant chemical gradients sufficiently large to produce
larger PDs.
Ions and potentials - VIII
Although the PD at equilibrium is the result of the
physical separation by the membrane of cations
from anions, the actual number of ions separated to
produce this PD is very small.

To generate a 60 mV potential difference across

one square centimetre of cell surface, 6 × 10−13 mol
of potassium ions need to cross the membrane - a
quantity so small that no earthly instrument can
measure it.

At time zero, there were equal concentrations of cations and

anions on both Side 1 and Side 2 (i.e., 0.11 M each). On a
macroscopic scale, this is always the case and is the basis for the
presumption that “electroneutrality” must be maintained in any
system;
However, as K diffuses from Side 2 to Side 1, there will be a net
increase in positive charge along the Side 2 (outside) surface of the
membrane, producing a microscopic imbalance in charge with
respect to the residual negative charge (i.e., Cl) left behind along
the inside surface of the membrane.
The modest imbalance of charged particles arising
from the net efflux of K is effectively localized to the
region very near the membrane, with the excess
positive charge (in this case, K) in the extracellular
compartment held electrostatically along the outer
surface of the membrane by the excess negative
charge (in this case, Cl) that is arrayed along the
inner surface of the membrane.
Resting membrane potential
Resting membrane potential: the voltage (charge) difference between the
intracellular and extracellular fluid, when the cell is at rest (i.e not depolarised by
an action potential).
Mechanisms responsible for the resting membrane potential:
• Chemical gradients generated by active transport pumps: the concentration of
ions are significantly different between the intracellular and extracellular fluid,
eg. the ratio of potassium ions is 35:1.
• Selective membrane permeability: the cell membrane is selectively ion-
permeable, specifically it is much more permeable to potassium ions
• Electrical gradients are generated because potassium leak (via K2P channels)
from the intracellular fluid creates a negative intracellular charge. This charge
attracts potassium ions back into the cell and thus opposes the chemical
gradient.
• Electrochemical equilibrium develops when electrical and chemical forces are
in balance for each specific ion species, and this is described by the Nernst
equation.
• The Nernst potential for each ion is the transmembrane potential difference
generated when that ion is at electrochemical equilibrium
• The total membrane resting potential for all important ion species is described
by the Goldman-Hodgkin-Katz equation, which takes into account the different
membrane permeabilities for each ion.
• At rest, with normal intracellular and extracellular electrolyte concentrations,
the potential is negative, and is approximately -70 to -90 mV for mammalian
neurons.
 Changes in the membrane potential caused by
In most cells, the membrane
potential (Vm) is relatively stable with
changes in the relative permeability of ions.
little or no significant deviation from
the resting value. Therefore, in most
cells, Vm = Vrest.

This is because in these cells, the

relative ionic permeability values do
not change appreciably over time.

In excitable cells (such as neurons,

muscle cells and some endocrine
cells), there are large transient
changes in the relative permeability
values for ions and, therefore, the
membrane potential transiently
deviates from the "normal" resting
membrane potential.
Changes in the relative
permeability of ions can come
about as a result of channel
opening or closing caused by
physiological stimuli (e.g., opening
of voltage-gated channels) or by
the application of agonistic or
antagonistic drugs.
 Electrochemical Driving Force Acting on Ions
When two or more ions contribute to the membrane potential across the The magnitude of the driving force indicates how far the
plasma membrane (Vm) of a cell, it is likely that the membrane potential membrane potential (Vm) is from the electrochemical
would not be at the equilibrium potential (Veq.) for any of the contributing equilibrium (Veq.) of an ion. The arithmetic sign (i.e., positive
ions. Thus, no ion would be at its equilibrium (i.e., Veq. ≠ Vm). or negative) of the driving force acting on an ion along with
the knowledge of the valence of the ion (i.e., cation or anion)
This means that at the resting potential, K+, Na+, and Cl− are not at
can be used to predict the direction of ion flow across the
electrochemical equilibrium and, thus, the chemical and electrical
plasma membrane (i.e., into or out of the cell). See Table 1
forces acting on K+, Na+, and Cl− are not equal. When an ion is not at its
equilibrium, an electrochemical driving force (VDF) acts on the ion,
causing the net movement of the ion across the membrane down its
own electrochemical gradient. The driving force is quantified by the
difference between the membrane potential and the ion equilibrium
potential (VDF = Vm − Veq.).
• Vm is the membrane potential.
The membrane potential may be
obtained by direct measurement,
or may be predicted by using
the Goldman-Hodgkin-Katz (GHK)
equation.
• Veq. is the equilibrium potential
for the ion of interest. Its value
may be determined by using
the Nernst equation.
 EDF and Ion fluxes

Graphical representation of the electrochemical

driving force acting on potassium, sodium, and
chloride ions for a neuron at rest.
 Maintenance of the Membrane Potential - I
Under resting physiological conditions, there is constant
efflux of K+ from the cell, influx of Na+ into the cell, and
efflux of Cl− from the cell (see Figure).

Therefore, if the ionic concentration gradients are not

maintained, in the long run, because of the constant
ionic fluxes across the plasma membrane, the
concentration gradients will be dissipated.

Cells avoid this situation by having a primary active

transporter (i.e., pump) which pumps Na+ out of the cell
and K+ into the cell to counteract the constant
movements of these two ions down their
electrochemical gradients (see Figure).

Steady-state fluxes of K+ , Na+, and Cl− across the plasma

This protein is the Na+/K+ ATPase (commonly also
referred to as the Na+ pump) which couples the
hydrolysis of one ATP molecule to moving 3 Na+ ions
out of the cell and 2 K+ ions into the cell.
membrane under resting physiological conditions.
In many cells, the contribution of Cl− to the membrane potential
is small and VCl usually (but not always) follows Vm. This means
that Cl− distributes across the plasma membrane to adjust the
intracellular concentration to establish a VCl that is close to Vm.

Maintenance of the
Membrane Potential - II
(a plant-derived toxic substance – “arrow” poison)
Inhibition of the
Na+/K+ ATPase by ouabain
leads to a rapid but very
small depolarization of
the membrane (2),
generally < 5 mV .
However, prolonged inhibition
of the Na+/K+ ATPase leads to a
gradual dissipation of
transmembrane Na+ and
K+ concentration gradients and,
thus, a gradual decline of the
membrane potential until its
value reaches zero (3 and 4).
The gray bar represents a long
break in time (tens of seconds
or minutes) for the membrane
potential to completely
dissipate to the zero level (4).
At this point, the cell is dead!
The constant Na+ influx into the cell and
K+ efflux out of the cell abolish the
transmembrane Na+ and K+ concentration
gradients.
In the absence of concentration gradients,
the Nernst potential for each of these ions
would be close to zero leading to a
membrane potential of approximately zero.
Thus, in order to maintain the membrane
potential, cells have to expend energy to
maintain the proper intracellular Na+ and
K+ concentrations.
Therefore, although the Na+/K+ ATPase is
not responsible for the generation of the
membrane potential, it is responsible for
maintaining the normal intracellular K+ and
Na+ concentrations.

Two organ-systems (urinary and the

endocrine) are responsible for maintaining
Inhibition of the Na+/K+ ATPase leads to the the low extracellular K+ concentration and
ultimate loss of the membrane potential. the high extracellular Na+ concentration.
Typical membrane
potentials and …
Many of the most important energy transformations in
cells effectively use the membrane as a capacitor,
resulting in the storage of energy as a transmembrane
potential.

Energy-harvesting reactions, such as those involved

in photosynthesis and respiration, pump protons across
the membrane. On their return back across the
membrane, these protons are then harnessed
to synthesize ATP and to transport compounds against
their concentration gradients.

A pH difference between two compartments that are

membrane-bound adds 60 mV per pH unit difference to
the overall driving force for proton transport.
This sum of electric and concentration difference terms
is the so-called proton-motive force, and it is critical for
the operation of most membrane-anchored energy
transformations (for example, in chloroplasts).
Electric potential difference over a range of biological membranes.
Negative values indicate that the outer compartment is more positive than the inner
compartment.
The pmf is the total proton motive force, which includes the effect of pH. When the pH of the
media changes, the electric potential of single-celled organisms tends to change such that the
pmf remains in the range of –100 to –200 mV.
 Ion channels
• Rapid Signaling in the Nervous System Depends on Ion Channels

• Ion Channels Are Proteins That Span the Cell Membrane

• Currents Through Single Ion Channels Can Be Recorded

• Ion Channels in All Cells Share Several Characteristics

- The Flux of Ions Through a Channel Is Passive
- The Opening and Closing of a Channel Involve
Conformational Changes

• The Structure of Ion Channels Is Inferred from Biophysical,

Biochemical, and Molecular Biological Studies

Ion channels have three important properties:

(1) They recognize and select specific ions,
(2) they open and close in response to specific electrical,
mechanical, or chemical signals, and
(3) they conduct ions across the membrane.
From ‘Principles of Neural Science’, ed. Kandal et al., McGraw Hill Medical 5th edition (2013)
Ion channels and
Membrane potential
A neuron’s cell membrane has thin
Two types of ion channels—resting and clouds of positive and negative ions
gated—have distinctive roles in neuronal spread over its inner and outer surfaces.
signaling.
At rest the extracellular surface of the
Resting channels are primarily important in membrane has an excess of positive
maintaining the resting membrane charge and the cytoplasmic surface an
potential, the electrical potential across the excess of negative charge (Figure).
membrane in the absence of signaling.
This separation of charge is maintained
Some types of resting channels are because the lipid bilayer of the
constitutively open and are not gated by membrane is a barrier to the diffusion
changes in membrane voltage; other types of ions.
are gated by voltage but can open at the
negative resting potential of neurons. The excess of positive ions outside the
membrane and negative ions inside the
Most voltage-gated channels, in contrast, membrane represents a small fraction of
are closed when the membrane is at rest the total number of ions inside and
and require membrane depolarization to outside the cell at rest.
open.

From ‘Principles of Neural Science’, ed. Kandal et al., McGraw Hill Medical 5th edition (2013)
Responses of membrane potential

From ‘Principles of Neural Science’, ed. Kandal et al., McGraw Hill Medical 5th edition (2013)
Voltage-gated channel
Ions sometimes cross a biological membrane in one
direction but not the other. Figure below shows
experimental evidence that applying an external voltage
opens a protein channel to allow ions to pass through.

Here is a simple model for

voltage-gated ion conductance,
based on the assumption that the
applied field orients a dipole
within the protein channel.

(a) Current–voltage measurements for a potassium channel in the egg A voltage-gated channel.
cell membrane of a starfish. Source: (a) B Hille, Ionic Channels of Excitable
Membranes, Sinauer, Sunderland, MA, 1984. Data are from S Hagiwara, S (a) Gate closed.
Miyazaki, and NP Rosenthal, J Gen Physiol 67, 621–638 (1976). (b) Applied potential opens gate.
Electrical circuit analogy
The cell is not in equilibrium but rather
in a steady state: There is a continuous
passive influx of Na+ and efflux of K+
through resting channels that is exactly
counter-balanced by the Na+-K+ pump.
Ion channels are passive conduits that
allow ions to move down their
electrochemical gradient.
Pumps transport ions against their
electrochemical gradient by expending
chemical energy.
The dependence of membrane potential on
ionic permeability and concentration is given by
the Goldman-Hodgkin-Katz equation:
This equation applies only when Vm is not changing.
It cannot be used to determine how rapidly the
membrane potential changes in response to a
change in permeability. It is also inconvenient for
determining the magnitude of the individual Na+, K+,
and Cl− currents.
This information can be obtained using a simple
mathematical model derived from electrical
circuits. The model, called an equivalent circuit,
represents all of the important electrical properties
of the neuron by a circuit consisting of conductors
or resistors, batteries, and capacitors.
Equivalent circuit - I

Since there is normally a K+

concentration gradient, there is also
a chemical force driving K+ across the
membrane, represented in the
equivalent circuit by a battery.
(A source of electrical potential is
called an electromotive force and an
electromotive force generated by a
difference in chemical potentials is
called a battery.)
A cell membrane has many resting K+ channels, all of which
can be combined into a single equivalent circuit consisting of
a conductor in series with a battery. The total conductance
of all the K+ channels (gK), ie, the K+ conductance of the cell
membrane in its resting state, is equal to the number of
resting K+ channels (NK) multiplied by the conductance of an
individual K+ channel (K).

The electromotive force of this

battery is given by EK, the Nernst
potential for K+.

K : conductance of an individual K+ channel.

 The membrane is a leaky capacitor because it is studded with ion channels
that can conduct charge. Ion channels endow the membrane with
Equivalent circuit - II conductance and with the ability to generate electromotive force (emf).

The nonconducting phospholipid

bilayer of the membrane separates the Accounting for various ion channels
cytoplasm and extracellular fluid, both
of which are highly conductive
environments. The lipid bilayer itself
has effectively zero conductance or
infinite resistance.

The presence of a thin layer of

opposing charges on the inside and
outside surfaces of the cell membrane,
acting as a capacitor, gives rise to the
electrical potential difference across
the membrane.

The populations of Na+, K+, and Cl− ion channels can

each be represented by a battery in series with a
conductor. The directions of the battery poles reflect
the electromotive force generated by each ionic flux,
inside nega ve for K+ and Cl− and posi ve for Na+.
 Patch-clamp technique
The patch-clamp technique was developed in 1976 by
Erwin Neher and Bert Sakmann to record current from
single ion channels.

A small fire-polished glass micropipette with a tip

diameter of approx. 1 μm is pressed against the
membrane of a skeletal muscle fiber. The pipette is
filled with a salt solution resembling that normally
found in the extracellular fluid. A metal electrode in
contact with the electrolyte in the micropipette
connects the pipette to a special electrical circuit that
measures the current through channels in the
membrane under the pipette tip (see Figure).

In 1980 Neher discovered that applying a small amount

of suction to the patch pipette greatly increased the
tightness of the seal between the pipette and the
membrane. The seal lowered the electronic noise and
extended the usefulness of the patch-clamp technique
to the whole range of channels involved in electrical
excitability, including those with small conductances.
A. A pipette containing a low concentration
of acetylcholine (ACh) in saline solution is
used to record current through ACh receptor
channels in skeletal muscle.
(Adapted, with permission, from Alberts et
al. 1994.)
B. Patch-clamp recording of the
current through a single ACh
receptor channel as the channel
switches between closed and open
states. (Reproduced, with
permission, from B. Sakmann.)
 Time dependent response
The rate of change in the membrane potential
is slowed by the membrane capacitance.

The upper plot shows the response of the membrane potential

(Vm) to a step current pulse (Im). The shape of the actual
voltage response (red line) combines the properties of a purely
resistive element (dashed line a) and a purely capacitive
element (dashed line b). The time taken to reach 63% of the
final voltage defines the membrane time constant,  ( = RC).

The lower plot shows the two elements of the total membrane
Typical values of  for neurons range
current (Im) during the current pulse: the ionic current (Ii) across
from 20 to 50 ms.
the resistive elements of the membrane (ion channels) and the
capacitive current (Ic).
Using the Equivalent Circuit Model to
Calculate Resting Membrane Potential

The Na+, K+, and Cl−

resting channels can be
represented together by a
single conductance and
battery.

The total resting membrane conductance (gr ) and

the electromotive force or battery (Er ) give the
resting potential determined by
 Ion channels

From ‘Principles of Neural Science’, ed. Kandal et al., McGraw Hill Medical 5th edition (2013)
Nernst-Planck Equation

mobility

electrophoretic flux of ions:

after using Einstein Suppose we place the electrodes inside the

relation
What electric field would be
needed to get zero net flux?
container of salt water. To avoid ions piling up at
the electrodes, an AC field can be applied. The
Set j = 0 and solve to get system then continuously conducts electricity, at
the Nernst relation: a rate controlled by the steady-state ion fluxes.
=0

This equation predicts that positive charges will

pile up at x = 0 (see Figure). The same formula
applies to negative charge (q < 0), and the equation
says that they pile up at x = d.

both ions contribute to the current and hence the resistance.

Ions in a medium - I

The electric field is indicated by vectors pointing

Charges interact more weakly with each other when they are (a) away from a positive charge and
in liquids as liquids can be polarized to varying degrees. The (b) toward a negative charge.
medium is treated as a polarizable isotropic continuum. The field represents the force per unit charge that
By treating a medium as polarizable, we assume that the acts on a positive test charge put at each particular
charge redistributes in response to an electric field, even if position in space.
the medium is neutral overall.

The reduction factor is the dielectric

constant D, a scalar dimensionless quantity.

A useful quantity called the Bjerrum length is

defined as the charge separation at which the
Coulomb energy u(r) between a mole of ion pairs
just equals the thermal energy RT.

For a temperature T = 298.15K in vacuum or air (D = 1), it is about 560 Å.

This is a relatively long distance, many times the diameter of an atom.
 Dissociated mobile salt ions
move in the presence of a
Ions in a medium - II charged surface.
The counterions are attracted
Consider a charged molecule or object P. to the surface and the co-ions
P attracts the mobile salt ions that have the opposite are repelled.
charge to P, called the counterions. P repels the mobile
ions of the same sign, called the co-ions (see Figure).
In the simplest case, the surface of a charged colloidal particle is
described as a plane. Suppose that a charged particle P, which is fixed
in space, produces an electrostatic potential ψ(x), which you take to be
a function of a single spatial coordinate x. P is in a salt solution of
dissociated mobile ions.
The counterions distribute around P and act as a sort
Consider a salt in which the counterion
of electrostatic shield, reducing the electrostatic
and co-ion have the same valency; Let
potential from P that is felt by a charged particle
n+(x) represent the concentration of
distant from P. The interface between P and the
mobile positive ions (the number of ions
neighboring salt solution is called the electrical double
per unit volume) at a distance x from the
layer: the first layer is the charge on P and the second
plane. This quantity is given by the
layer is the adjacent diffuse sea of excess counterions.
Nernst or Boltzmann equation:

𝑬 = −𝜵
Poisson’s
𝜌 equation
𝜵 𝑬=
𝐷𝜀 n∞ is the concentration of positive or negative ions in the bulk solution, distant
from the particle P. Note that far from P, the potential is ψ(∞) = 0
Ions in a medium - III
The mobile ions not only experience the electrostatic field surrounding
P, they also contribute to it. We can compute the electrostatic potential
that arises both from the fixed charge of P and from the mobile charges
of the dissociated salt ions. First, compute the charge density ρ(x) as a
function of the number of ions at position x:
D is approximately equal to the
Use Poisson’s dielectric constant of the solvent,
equation to get because the ions themselves
Poisson–Boltzmann equation contribute little to D as long as
their concentration is low.

For small potentials,

linearized Poisson–Boltzmann
or the Debye-Hückel equation

The Debye length is a screening, or shielding, distance.

A charge that is closer to P than 1/κ ‘sees’ the charged plane
and interacts with it.
A charge that is further than 1/κ from P is shielded from it by
the intervening salt solution, which weakens the attraction or
repulsion between the charge and P.
Ions in a medium - IV
The spherical double layer. What is the electrostatic
potential ψ(r ) as a function of the radial distance from a
charged sphere in a salt solution?
The sphere has radius a, net charge Q, and a uniform surface charge
density σ = Q/(4πa2). The sphere is in a monovalent salt solution that
has a Debye length 1/κ. The potential changes only in the radial
direction (spherical symmetry)

For spherical coordinates, the linearized

Poisson–Boltzmann equation becomes

Need two boundary conditions to establish A1 and A2. It is conventional to choose

ψ(∞) = 0, so A1 = 0. The second boundary condition is at r = a, where ψ = ψa = A2e−κa/a.
Inverting this expression gives A2 = aψaeκa. Then the solution becomes

Now determine the surface

potential ψa from the total charge
Q by making use of Gauss’s law for
E(r = a) around a sphere.