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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)
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
components), then an unequal distribution occurs for the other species, for which
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
(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
ions of which are diffusible across the membrane, eg., NaCl, CaCl2 etc. This
We shall now consider four different types of cases to which Donnan membrane
equilibrium is applicable. _
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
Na+ A Cl : Na+
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
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.
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.
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
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),
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
OH
[Remembering that [H+] [0H ] =Kw, i.e.,
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
insoluble or weak.
In the above three cases, we have dealt with monovalent diffusible ions. In this case,
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
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.
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
+
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
Membrane Potential
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.
from right to left and of t_ n moles of Cr from left to right, where t+ and t_
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
z+
M l
z+
Em = M r
RT
log
zF
RT 1 RT 1
Hence,
Em = zF
log
= ()
zF ()
log
Donnan membrane equilibrium finds several applications in all the fields, such
discussed below.
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
cause an excess of O.P. in the gel, which would thus lead to the entry of water
Procter confirmed the above facts experimentally and showed that they
containing the gelatin salt separated by a membrane from the solution of HCI is
represented as;
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
=
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
(ii) Tanning of leather. The theory of tanning is due to Procter and Wilson and
constituent of the fibre for our purpose is the colloidal substance, collagen.
individual particles are negatively charged, so that the surface layer surrounding
+
M
N
+
M
N
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 )
immersed in an alkaline solution, the value of Em will have the same sign as in
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
(iii) Sorensen taking into account the Donnan theory and the
coarsening of the micelle, arrived at the result that the oval albumin sol in
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
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
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
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
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
electrochemical systems.
Experiment shows that when an impulse propagates along a nerve cell or
world through the senses of sight, hearing, touch, etc., our thought processes,
and our voluntary and involuntary muscular contractions are all intimately
they are changed. Our knowledge in this area is currently very fragmentary.
ELECTROCARDIOGRAPHY
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
These three ions are the main inorganic ions. Inside the cell, there is
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.
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.
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
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
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.