MEMBRANE PHENOMENON

Donnan and Harris (1911) while measuring the osmotic pressure of solutions of

the dyestuff Congo red (Congo red is a sodium salt of a complex sulphonic acid)

observed that if sodium-chloride dissolved in an aqueous solution of Congo red is

brought in contact with water through a membrane, then it was seen that Congo

red was impermeable through the membrane, While sodium chloride readily

passed through it. It was also' found that sodium chloride was present in greater

amount in the solution free from the dyestuff than in the other. In other words, if

two solutions are separated by a membrane (impermeable to one of the

components), then an unequal distribution occurs for the other species, for which

the membrane is permeable. At equilibrium, the osmotic pressures of the two

solutions are different, and if two reference electrodes (say calomel electrodes)

are connected to the two solutions by means of a salt bridge, then a difference of

potential between the two electrodes is noticed. This type of equilibrium as first

seen by Donnan, is known as Donnan membrane equilibrium. The potential

developed between the two solutions is thus known as Donnan potential.

The two components of Donnan membrane equilibrium are :

(i) Internal solution. This solution may be of any protein, Congo red etc. One of

the ions is generally non-diffusible and approaches the colloidal dimensions. The

other ion is small enough and is diffusible across the membrane. This solution is

taken as the left? solution.

(ii) External solution. This solution is generally a solution of an electrolyte, both

ions of which are diffusible across the membrane, eg., NaCl, CaCl2 etc. This

solution is taken as the right solution.

We shall now consider four different types of cases to which Donnan membrane

equilibrium is applicable. _

CASE I. The electrolytes in the two solutions. have an ion in colpmgn.

Suppose the initial condition is represented as :

Ion A- represents the non-diffusible ion, c1 and c2 are the respective

concentrations of the ions, the dotted line represents the semipermeable

membrane. As the left hand solution does not contain chloride ions, therefore,

some will diffuse into it from the right hand solution. Suppose x moles per litre of

chloride ions move from right to left solution. Since the two solutions must be

electrically neutral, x moles per litre of sodium ions must also diffuse from the

right to left solution. The equilibrium concentrations will thus be as follows :

Na+ A Cl : Na+

Since the system is in equilibrium, a small change made reversibly at constant

temperature and volume, will not bring any change in the free energy, i.e., no

work will be done. The change here is the transfer of a small amount, say Sri

moles of Na+ and Sn moles Of from right to left. The work done will thus be equal

to zero. So,
[Ne]nght + Sr/ . RT log [alright Stt. RT log - 0 [Nat]left 1C1-]left [Nall EClir [Nair

Ecni or [Nall [CV]i = (Nair [Cllr

Substituting the respective concentrations, we get, (cl+x)x=(c2_x)2 X - C1 + 2c2

C2 - X Cl + C2 Or -x C2

c2 - x The quantity represents the distribution ratio of NaC1 between right and

left

solutions. Case II. The electrolytes on both the sides have no common ions.

Suppose the initial condition is represented as : Na+ A K+ Cl-c1 Cl C2 C2 Let x

mole per litre of Kt ions and y mole per litre of ions diffuse from right to left

solution. During this change, let z moles per litre of Na+ ions diffuse from left to

right solution.

The condition at equilibrium is then represented as :

For au infinitesimal change, the following amounts are transferred :

8n moles of Na' from left to right, and 8n moles of Cl- from right to left.
 2+
Na

2+
N


Cl r
Therefore,

Cl r





n . RT log

Or
[ Na+ ] 1 [ Cl - ]1 = [Na+] r [Cl-]r

Similarly, [ K+ ] 1 [ Cl - ]1 = [K+] r [Cl-]r

Substituting the respective concentrations in expression (1), we get,

(ci - z) y z (c2- y)
(ci + c2)
or x= [As z = x y]
C2
From (2), xy = (c2 -x)(c2 -y)
or x = c2 y

From equations (3) and (4), we get

y ( c 1+ c 2 )
=c 2 y
c2

c 2 y c 1c 2
=
or y c2
 2
c
2
or y=
c 1+2 c 2

Once the value of y is thus known, the value of x can be calculated equation (4),

and that of z from the expression z = x y .

CASE Ill. One of the solutions is water alone. Suppose the initial
condition is represented as :
Na+ A- H2O
c1

The sodium ions will migrate from left to right solution and do so when
equivalent
amount of OW ions, furnished by water in left solution, can migrate through it in
order to maintain electrical neutrality.
The condition at equilibrium is then represented as :

-
Na+ H+ A- : Na+ OH
(c1-x) x c1 x x

The value x represents the number of moles per litre of Na + ions which
migrate. The solution on left is acidic, whereas on the right the solution is
alkaline.
By applyingthe principle of virtual work, for the distribution of NaOH, we have

for the transfer of n moles of Na+ from left to right and 8n moles of OH - from

left to right,
 +
Na 1

+
Na r


OH 1
Therefore,

OH r





n . RT log

+
Na 1

+
Na r


OH 1


OH r

+
Na


OH

+

OH r
Na r

Substituting the respective concentrations, we get,

 Kw
( c 1x ) =x 2
x

OH
[Remembering that [H+] [0H ] =Kw, i.e.,

where IC, is the ionic product of water]

So, (ci - x) Kw = x3
This process of producing an excess of hydroxyl ions in the right solution is also

known as 'membrane hydrolysis'. As Kw is very small (10 -14 ), it means that 100x/ci,

i.e., the percentage of hydrolysis of NaA will be very small. The value of x increases

slowly relative to the increase in ci. The hydrolysis is also favoured by increasing the

volume of the liquid in the right solution. Hydrolysis is also greater, if HA is

insoluble or weak.

CASE IV. When one of the electrolytes contains polyvalent ions.

In the above three cases, we have dealt with monovalent diffusible ions. In this case,

the case of ion with unequal valencies will be considered.

Consider the initial condition to be represented as :

Na+ A- : Ca2+ A-
c1 c1 : c2 c2

The calcium ions will migrate, but in order to pass, two sodium ions

must simultaneously strike the other side of the membrane. The equilibrium

concentrations may thus be represented as,

Na+ A- Ca2+ :
Na+ Ca2+ A-
(c1 -2x) c1 x : c2 (c2 -x) c2
when x moles per litre of Ca2+ ions have migrated from the right to left solution.

Electrical equivalence will be present if 8n moles of Ca 2+ are transferred from

right to left and twice the quantity of Na+ from left to right. Thus,

+
Na 1

+
Na r

2+

Ca r
RT 2
2+
Ca 1





n . RT log

2+
Ca r

2+
+
2
Hence Na .
1

+

Substituting the respective concentrations, we get

c 2 y ( c 12 x ) 2
=
y ( 2 x )2
From the above equation, the value of x can be determined by knowing the

values of c1 and c2.

Membrane Potential

As already described, a difference of potential is developed between the two

solutions separated by a membrane, as a result of unequal distribution of ions

on the two sides of the membrane. The potential difference thus developed is

known as 'membrane potential'. Its value can be determined in any case, but we

shall take only the first case in which the equilibrium was represented as.

Na+ A- Cl- :
Na+ Cl-
Let E1 be the potential for positive electricity of left solution and E2 be that of
right side. Suppose a very small quantity F. on of positive electricity is reversibly
transferred at constant temperature from right to left: The following terms are
involved, if we consider - this virtual variation of equilibrium.

(a) The decrease in electrical free energy equal to F: n (E1 - E2).

(a) The work obtained by the simultaneous transfer of t+ On moles of Na +

from right to left and of t_ n moles of Cr from left to right, where t+ and t_

are the transport numbers of the respective ions.

The work done in the second step is given by :
 +
Na r

+
Na r

++
C l l
t+ 2

Cl r




n . RT log

Since the system is in equilibrium, the quantities given in steps (a) and (b) are
equal. Thus,
E
+
Na r

+
Na r

++
Cl l
F.

Cl r




( 1E 2)=t + n RT log
n .
 +
Na r

+
Na r

++
Cl l
But t+ + t_ = 1

Cl r

The equation (6) is also valid when polyvalent ions are present.

In the general case of the diffusible chloride possessing the ion M2+ of valency z, the

potential, Em is given by,

z+

M l

z+

Em = M r


RT
log
zF

But, we know from case, IV), that

 z+
M l

z+

M r


z
Cl .
r z


z
Cl .
r

RT 1 RT 1
Hence,
Em = zF
log

= ()
zF ()
log

So, the value of Em will always be given by expression (6), howsoever

complicated the system may be. The value of 0 is given by,

= Concentration of any species of ion in the right solution

Concentration of any species of ion in the left solution

Applications of Donnan Membrane Equilibrium -

Donnan membrane equilibrium finds several applications in all the fields, such

as biological, technical, chemical, physico-chemical etc., some applications are

discussed below.

(i) Swelling of gels. Isoelectric gelatin swells to a considerable extent by

immersing it in a solution of acid or alkali of suitable concentration. Lloyd

showed that gelatin undergoes a seven-fold increase of volume in water, but in

HC1 (pH = 2.3), the increase is 40 fold. Procter (1914) -first suggested that the

effect of acid might be explained on the basis of Donnan equilibrium.

Procter assumed that there is an interaction between the gelatin and the

acid, to produce ionisable salts, and colloidal gelatin ions thus produced were

unable to diffuse qut of the gel. As the gel is freely permeable to the H + and

ions present, it is assumed, therefore, that these ions must be distributed

between the gel and the surrounding solution in accordance with

Donnan's equation. He further assumed that these distributions might

cause an excess of O.P. in the gel, which would thus lead to the entry of water

into the gel and will cause swelling.

Procter confirmed the above facts experimentally and showed that they

are in accordance with the Donnan equation. The distribution of a solution

containing the gelatin salt separated by a membrane from the solution of HCI is

represented as;

GH+ H+ Cl- : H+ Cl-

z y y+z : x x
where z is the concentration of gelatin ion, i.e., of combined H+ . Procter's
data, thus obtained experimentally, conforms to the Donnan equation :

x 2 y ( y + z)

x2
+ z=
y y
 Procter and Wilson (1916) assumed that the swelling of gels due to acid is
due to an excess of 0.P. in the gel, which arises from the difference in
concentration of diffusible ions According to this, the amount of swelling would
be maximum, when the difference in concentration of diffusible ions is maximum.

= 2y+ z - 2x.

x 2 y 2
= 2y+ 2x [From equation (7)]
y

Or

x

. y 2
=

If we plot the value of X, thus found experimentally, against the pH of the

right. solution, then it will be seen that X will be maximum at pH between 2.44

and 2.65.

According to the theory of Procter and Wilson, the degree of swelling of pure

gelatin should depend only on the final pH of the solution in which it is placed. It

should thus be independent of the volume of the solution. But in the case_ of

gelatin containing salt impurities, the degree of swelling will then not only depend

on the final pH of the solution, but also on the volume of acid added, as finally

confirmed by Nordrop and Kunitz (1927-29).

(ii) Tanning of leather. The theory of tanning is due to Procter and Wilson and

is an application of Donnan's theory of membrane potential. The process of

tanning is regarded as a combination of tannins with hide fibre. The main

constituent of the fibre for our purpose is the colloidal substance, collagen.

The object of the theory is to offer an explanation of the influence of acids,

bases and salts upon the tanning process.

The tannins dissolve in water forming colloidal solution, in which the

individual particles are negatively charged, so that the surface layer surrounding

the particles must contain a definite concentration of positive ions bound by

electrochemical attraction to the negatively charged tannin. Suppose the

concentration of tannin particles is [T1] and that of positive ions bound by

electrical attraction to tannins is [M+]. Consider that some of the electrolyte MN is

added to the solution.

According to Donnan's theory,

+
M


N

+
M



N

where the subscripts I and II represent the respective concentrations in the

surface layer and bulk of solution, respectively.
 Suppose x is the concentration of positive or negative ions in the bulk of the
solution. Let y be the concentration of negative diffusible ions and z be' the
concentration of positively charged ions bound by attraction to tannin in the
surface layer. Then, according to equation (8), we get,

x 2 = y (y + z)
Doan put forward a formula for membrane potential and is given by,

RT 1
Em = F
log ()

y z 4 x 2+ z2
Where = =
x 2x

RT 2 x
log
Em = F z (4 x 2+ z 2 )

If the hide is immersed in an acid solution, a highly ionisable salt of collagen is

formed in which collagen is positively charged and,
RT z (4 x 2+ z 2 )
Em = log
F 2x

where Em, is obviously of opposite sign to that of tannin. If the hide is

immersed in an alkaline solution, the value of Em will have the same sign as in

the case of tannin.

Tannins, in which z is large, would combine with the hide rapidly and form the

most stable leather. The rate of tanning will be maximum for a given

concentration of liquor, when the potential differences are of opposite sign and
the absolute value of each is maximum. If the hide is immersed in an acid

solution of tannin, then as the tannin particles approach the substance of the

hide, electrical neutralisation with the resulting co-precipitation of the colloids

must follow. This is the fundamental principle of vegetable tanning according to

Procter and Wilson.

(iii) Sorensen taking into account the Donnan theory and the

coarsening of the micelle, arrived at the result that the oval albumin sol in

NH4NO:, solution (15%) has a definite osmotic pressure. He thus

calculated the molecular weight of water-free egg albumin to be 35,000.

(iii)Donnan equilibrium is also applicable to the dyeing of animal fibres

by acid dyes. It provides a method for the measurement of adsorption of

ions by the particle in inorganic colloidal systems. In biological field,

Donnan's theory relates to the distribution of diffusible ions between the

red blood corpuscles and the serum of the blood. It explains the origin of

fluids occurring in the cavities of the eyes. This theory also helps us

in determining the cataphoretic velocity.

BIOELECTRONICS
Electrochemistry, as we have come -to know, Metal consists in the
study of ionic solutions, and electrodes where ions and electrons combine
and separate. It seems a far cry from biology which is, surely, all about flesh and
blood and bone. Yet, right from the beginning with Galvani in that laboratory in
Bologna, Italy, in 1791, bio electrochemistry has been a part of
electrochemistry. Historically, in fact, electrochemistry came out of it.
670 ADVANCED PHYSICAL CHEMISTRY

Cytoplasm (the fluid in cells of living organisms) and the extracellular fluid that
surrounds cells contain significant amounts of dissolved electrolytes. The total
electrolyte molarity is typically 0.3 mol/dm3 for mammalian fluids.

Figure (1) shows a piece of animal tissue pinned to the bottom of a chamber

filled with a solution having the same composition as the extracellular fluid of the

organism. By penetrating the membrane of a single cell with a micro salt

bridge one sets up the electrochemical cell where phase [3 is the interior of

the biological cell, the membrane is the cell's plasma membrane and phase a is

the bathing solution. The potential difference measured is that between the

interior and exterior of the biological cell and is the transmembrane

potential. The membrane potential is displayed on an oscilloscope or a chart

recorder. The micro salt bridge (often inaccurately called a microelectrode)

consists

of glass drawn to a fine tip about 5 x 10_5 cmin diameter and filled with

concentrated aqueous KC1. When the tip penetrates the cell membrane, the

membrane seals around the glass.

It is found that cells show a potential difference tint text of - 30 to - 100

mV across their membranes, the cell's interior being at a lower potential than

the exterior. Typical values are - 90 mV for resting muscle cells, - 70 mV for

resting nerve -cells and - 40 mV for liver cells. Since interphase potential

differences exist in living organisms, living organisms meet the definition of

electrochemical systems.
 Experiment shows that when an impulse propagates along a nerve cell or

when a muscle cell contracts, the transmembrane potential mint text

changes, becoming momentarily positive. Nerve impulses are transmitted by

changes in nerve-cell membrane potentials. Muscles are caused to contract by

changes in muscle-cell membrane potentials. Our perception of the external

world through the senses of sight, hearing, touch, etc., our thought processes,

and our voluntary and involuntary muscular contractions are all intimately

connected to interphase potential differences. An understanding of life requires

an understanding of how these potential differences are maintained and how

they are changed. Our knowledge in this area is currently very fragmentary.

ELECTROCARDIOGRAPHY

The existence of trans membrane potential differences means that there is an

e l e c t r i c a l d o u b l e l a y e r a t t h e membrane of each cell. The double layer_is
approximately equivalent to a distribution of electric dipoles at the cell's
surface. Consider the heart muscles. As these mu4sc16s undergo their'
various cycles of contraction and relaxation, the potential differences across
their cell membranes are continuously changing, and hence the tots dipole
moment of the heart is cli ig as are the electric field and ell it lc potential
produced by the heart. An electrocardiogram (ECG) measures the difference in
electric potential between several pairs of points on the surface of the body as a
function of time. Changes in these potential differences arise from the changes in
the heart dipole moment.

An electromyogram (EMG) is similar to an ECG except that it is the electrical

activity in skeletal muscles that is monitored.
 An electroencephalogram (EEG) records the time-varying potential
difference between two points on the scalp and reflects the electrical activity
of nerve cells in the brain. Its interpretation is not simple, since the signal results
from the activity of a huge number of nerve cells.

Consider the tratismembrane potential of a nerve cell. We noted that the

equilibrium Nernst equation is insufficient - to describe the no equilibrium
situation in living organisms. In 1943, Goldman used a no equilibrium
approach together with the assumption of a linear variation of within the
membrane to derive an expression for the trans membrane potential. This
equation- (in modified form) was subsequently used by Hodgkin and Katz in
studies of nerve impulses. The Goldman-Hodgkin-Katz equation is.
 K

+
+
K

+
Na

+
Na



K

+
+
K

+
Na

+
Na



Cl ext
Cl
P

Cl


Cl
P

RT
int ext =
F

where [K + ]ext and [K + ]int are the K + concentrations outside and inside the
cell and P(K+) is the permeability of the membrane to K + ions. [P(K+)] is defined
as D(K+)/T, where D(K+) is the diffusion coefficient of K+ through the membrane of
thickness T.
The six concentrations in equation (1) should actually be replaced by
activities, but since the ionic strengths inside and outside the cell are
approximately equal, all six activity coefficients are approximately equal and
672 ADVANCED PHYSICAL CHEMISTRY

have been omitted. Note that if P(K +) were much greater than both P(Na+) and
P(Cl1, equation (1) would reduce to the concentration-scale version of the Nernst
equation,

RT RT m
= =
zF zF m

where a and are two solution of KCl of different concentrations for K +

and similarly for the other two ions.

Tracer experiments show that a nerve-cell membrane is permeable to all
three ions K+ , N a + , a n d C F. F o r a r e s t i n g n e r v e c e l l o f a s q u i d ,
o n e f i n d s P(1C+)1P(C1-) 2 and P(K+)//)(Na+) 25. for squid nerve cells, the
observed concentrations in mmol/dm3 are
[K+]int = 410 [Na+]int= 49 [Cl]int = 40
[K+]ext = 10 [Na+]ext= 460 [Cl]ext = 540

These three ions are the main inorganic ions. Inside the cell, there is

also a substantial concentration of organic anions (charged proteins, organic

phosphates, and anions of organic acids); these have quite low permeabilities.

We can use the Nernst equation with activity coefficients omitted to see
which ions are in electrochemical equilibrium across the membrane. The
concentrations in equation (3) give the following equilibrium A4) values at 25C.
iVeq (K+) = - 95mV, Atlieq (Nat) = + 57mV, Aclieq(C1-) = - 67mV
The observed transmembrane potential for a resting squid nerve cell is
about - 70 mV at 25C. Hence, Cl is in electrochemical equilibrium, but lc +
and especially Nat are not.
For the - 70mV membrane potential, equation (2) gives the following
equilibrium concentration ratios at 25 C.

cextictnt = 1 : 15 for z 1 ions; cext/cint = 15 for z =- 1

ions
The actual concentration ratios are 1 : 41 for K +, 9 : 1 for Na +, and 14 : 1
for CV. Hence, Na + continuously flows spontaneously into the cell and K + flows
spontaneously out. [We have Ft ext(Na + ) > i int (Na + ).] To maintain the
observed steady- state concentrations of Na+ and K+, there must be some sort
of active-transport process that
uses some of the cell's metabolic energy to continually pump Na + out of the cell
and 1C+ into it. The mechanism of this pump is unknown.

A nerve impulse is a brief (1 ms) change in the transmembrane potential. This

change travels along the nerve fibre at a constant speed of 103 to 104 cm,'s
depending on the species and the kind of nerve. The change in AO is initiated by
a local increase in the
membrane's permeability to Nat, with P(Na+)//)(K+) reaching perhaps 20. With
P(Na+) much greater than both P(K +) and P(C1-) in equation (1), the membrane
potential moves towards the Act)eq(Na+) value of + 60mV. The observed peak
value of Ad is + 40 or 50 mV during the passage of a nerve impulse. After this
peak is reached, P(Na+) decreases and P(K+) temporarily increases; hence, the
potential returns towards its resting value of
- 70mV. Because of the temporary increase in P(K +), the potential somewhat
overshoots the resting value, ultimately returning to - 70 mV as the ion
permeabilities return to their resting values. The mechanism of the permeability
changes is unknown.
A cell derives its energy from a complex series of metabolic reactions whose
net result is to convert glucose (C6H1206) into CO2 and H20. These reactions
are redox reactions and occur at structures within the cell called
mitochondria. A mitochondrion is surrounded by a double membrane.
Whether a mitochondrial membrane potential is involved in met .ibolism is
unknown.

USEFUL PRELIMINARIES

Ulla now the ions and molecules that have been actors on our stage have been
exemplified by H + . 02, ZnO, and the metal hydrides or chelating oxides, such
as CuO. I lowever, this is an inadequate introduction to the molecules that make
up the cells of 1)11(165d systems. The amino acids, glycine (i.e., NHA - CH 2 -
C00-) would be the example (excluding, of course, H30 4- . H20, and 02) of an
entity that takes part in stations. A structural element within the amino acids is
the peptide group.

-N - C-
I I
H O
which is important because when many of these groups occur in a chain, and
such chains form a polymer, one has a protein. Proteins form skin, nails, and
skeletal structures. Enzymes, biocatalysts, are proteins. Hemoglobin, which
carries 02 around the body, is a protein. Proteins can have molecular weights as
low as 10,000 but some are really very large, with molecular weights of 50 x 10 6.
The corresponding radii of the larger of these entities (if they were formed
spherically), would be in the hundreds of angstroms. -Examples of some
amino acids are shown in fig. (3). Structures that would form a protein would be,
for example, glycine.
The proteins found in nature are made up of only about 20 different, individual
amino acids. On the other hand, a typical protein consists of several
hundred of these 20 distinguishable amino acids. If one calculates the number
of ways in which, say. 500 things, 20 of which are different entities can be
arranged, the answer is which is 20!
about 101227. Some cosmologists have presented calculations for the number of
particles in the universe as being in the region of 1093.
These proteins (containing several hundred of the 20 special amino acids
might be thought at first to be long, long chains containing repeated peptide
groups (see above), which can be written more explicitly as

where the R's may be hydrocarbon chains on other peptide elements and the
shaded area denotes the bond between the two peptides. However, these long,
flexible chains are neither linear nor random in shape. They coil and stretch in a
way that greatly affects the properties of the proteinhow it does its work.
Among the most important of these structures is an arrangement called the a-
helix (Pauling and Corey, 1951), but it would take up too far away from our
main theme to describe its chemical properties (Fig. 4.)
The great importance of this structure is that it was the forerunner to the
elucidation of the structure of DNA, deoxyribonucleic acid, in which two a-helix
coils are joined together in a double stranded helical structure containing a
number of units of a sugar called deoxyribose, to which is attached one of four
organic bases [Fig. (5)] We must forego further material on the structure and
implications of this very remarkable and important protein, the molecular
weight of which is in the region of 10 6. Its discovery by Crick and Watson in
1953 is regarded as one of the greatest discoveries in the history of science
because the structure occurs in various forms in the cells of all living organisms.
Its detailsed structure is species specific.

[II] Cells, Membranes, and Mitochondria

Robert Hooke (of Hocke's law) was the first to discern (in 1665) a central
fact of biology, namely, that biological structures consist of honeycomb like
structures, which he called cells. In fact, such cells are to biological systems
what crystallites are to metals or sand to beaches.
By the middle of the twentieth century, the constituents of cells were known
and could be seen in electron microscopes. Each cell contains a number of
structures (organelles), the names and approximate shapes of which are
shown in figure.

The question of what surrounds the liquid inside cells, with all the -objects
floating in it, was: clarified by the 1920s. Cells are contained in what might
rather loosely be called bags. These bags, membranes, turned out (Gordon
and Grendell, 1925) to consist of a layer of phospholipids. Some
membranes have single walls and some double. As time went on, this
structure was found to be a universal thing; living organisms consi st of
cells and the cel l s t h e m s e l v e s a r e h e l d i n s i d e membranes.
From the century's beginning, through its midpoint,
t h e electrochemistry of electrodes was
based upon the treatment given by Nernst. This had been derived first, for an
interface between a metal and its ions in solution, but the treatment had
spread (Planck and Henderson, 1890-1907) to the potential difference
between two liquids containing different concentrations of electrolytes. The
first of these two treatments yields an equation (Nernst equation) identical in
form to the well known equation derived in thermodynamics of the electrical
potential difference between the electrodes of galvanic . cells :
 RT c 2

Em = F c1

where the c's refer to concentration of an entity in the solution and on the

electrode, and in the second,

RT c 2

E=(t1 t_ ) F c1

The terms t+ and 1_ represent the transport number of cations and

anions, respectively. Taking the difference in concentration of the potential
determining entities (2 and 1) as 10 times and t t_. as 0.15 the two equations
give nearly 57 and 9 mV, respectively and cover very approximately the normal
range of the measured values of potential across membranes.

There is one more thing to note and that is the nature and function of just one
of the elements in cells, the mitochondrion. It has been known for about a
generation that mitochondria are the entities in cells where energy is made from
the oxidation of organics derived from intake of food and oxygen. Much more
will be said about how they may function later but the fact is that, as suggested
by J. Koryta in 1991, the mitochondria are well described as floating power
stations.
UMEMBRANE POTENTIALS

The measurement and interpretation of the potentials across biological

membranes has been going on for about a century. A remarkably, prescient
suggestion was that of du Bois Reymond (1868), who put forward the concept
that a cell surface could well be looked at as though it were an electrode. The
principal elements in biological cells are shown in fig.
Typical biological membrane structures. A liquid-mosaic model in the
formproposed by A. Kortya with different types of disposition of membrane protein
(phospholipids are shown as dark circles with two wavy tails),
Ill', integral, membrane bridging protein, with a single Ipolypeptide span; lB2
I
the same with several spans. IN and IC, integral noncytoplasmic and cytoplasmic
proteins; IM, integral buried proteins; P,
Membranes, which are the subject of this section, I can
I

be relatively' thick (0.1 mm) if made chemically Biological H.C-0C

R membranes are very much thinner (50-100A), of the same (3-5 mm) range
as that of passive oxides. Of what do biological membranes consist?
Figure (7) shows the essential consituents. They are lipids and proteins.
How much there is of one and how much of 0 the other varies
widely. Thus, in a myelin membrane the lipid content is 80%, while at the
other end of the range, in mitochondria, there is an inner membrane
containing only about 20% lipid. There are many kinds of lipids (as well as very
many kinds of protr,ins), but those in membranes are usually phospholipids and
are represented in fig. (8). The structure often contains an H atom and this
allows the phosphoric acid element to ionize. In the membrane structure, alkyl
groups (R and R') are directed inward, while the polar groups are on the
surface ("fixed charges")

Although many measurements of potentials have been mad with membranes

obtained from animals, one needs simMfication if one is to understand the
function of various
entities of a cell. The most common model system to act as a simplified
biological membrane is the "bilayer lipid membrane" (BLM), first prepared by
Mueller in 1962. It consists of two lipid molecules tail to tail (Fig. 9) with the
polar groups oriented to face the solution. In the basic BLM (individual),
compounds of a biological system can be built and examined.
These BLMs although very thin show very high resistance, up to 1010 ohms.
Nevertheless, some pores do develop in these membranes and water, followed
by ions, enters there and reduces the resistance. Application of a potential
increases- the flow of ions through the pores and the number -of pores; this
further reduces the resistance.
The method for measuring a membrane potential is simple. One places an
electrode (e.g., a calomel electrode solution

if the solution contains CF) on either side of the

(c)
membrane, which usually occupies a hole about 1 mm in
Fig. 9. Preparation of a bilayer lipid
diameter in a Teflon sheet. Since the potential of the membrane.
calomel electrode is accurately known and varies according to the Nernst
potential with log IC11 the difference in potential arising from the two different
concentrations on each side of the membrane is easily known and can be
subtracted from the total potential differences recorded between the two
electrodes to give the value due to the membrane. Most of the membrane
potentials recorded in the literature lie within values of tens to hundreds of
milivolts.

EXERCISES
1. . What is Donnan membrane equilibrium? Explain it when:
(a) Only water is present on one side?
(a) If solutions do not contain any common ion?
2. What is membrane potential? How it is measured?
3. Discuss the applications of Donnan equilibrium
4. Explain the terms cells and membranes.
5. Explain the principle of electrocardiography.