Homework set-Transport in electrochemical systems

Due in class: Feb. 23rd

1) In the class, we addressed transport due to migration of ions and we assumed that the
concentration of the ions is such that the solution is dilute. At this very dilute concentration, ions can
be assumed to migrate independently. Given these features, find out the equivalent conductance
(o) of NaNO3 (Given: o (in Ohms -1CM2) of KCl=130, KNO3=126, NaCl=108.9).

2) In the class, we analyzed transport via migration and derived the following equations:
2
= Zi Di Ci 2 Di Ci

2.1) We also analyzed the generation of the potential even when = 0 and interpreted the reason
for generation of the potential mechanistically/qualitatively. Rearrange the above equation
appropriately and elaborate the mechanistic/qualitative reasons for the generation of the potential.
2.2) Are there conditions, when both and = 0? If so, what are these conditions? Support your
conclusions both qualitatively/mechanistically and quantitatively/mathematically.

3) Almost all eukaryotic cells consume metabolic energy to maintain ion concentration gradients
across their cell membranes. Typically, Na+ is continually transported outward by macromolecular
ion pumps and K+ is transported inward, in what is called active transport. Such a transport
keeps intracellular concentration of Na+ low and that of K+ high, relative to the extracellular fluid.
Opposing the active transport is passive transport of these and other ions (principally Cl - & HCO3-)
through channels in the cell membrane. All this active and passive transport causes the intercellular
potential to be negative relative to that outside. These potentials are critical to neural and
neuromuscular functions and it is possible to measure these potential rather accurately. To get make
sense of these potentials, we first analyze a simple model below that lacks active transport, but has
passive transport.

Consider steady, one-dimensional transport of a univalent-univalent salt (for which + = | | = 1)

along a channel that extends from x=0 to x=L. As both ions are univalent, + () = () =
()=concentration of salt at position at position x. Let the diffusion constant of the cation and
anion be + and respectively. Assume there is no convection, no current and the salt
concentration at the channel ends are held constant at (0) = 0 and () = .

3.1) Derive an expression for ()- (0) in terms of + , , 0 , , R, T & F.

3.2) Suppose the electrolyte is NaCl, KCl or HCl. The infinite-dilution diffusivities in water at
25C are
2.032 x 10-5 cm 2/s (Cl-), 1.334 x 10-5 cm 2/s (Na+), 1.957 x 10-5 cm 2/s (K+) and 9.312 x 10-5 cm 2/s

(H+). Assuming 0 =10, find out the values for ()- (0) for NaCl, KCl & HCl respectively. In each

of the three systems, there is only one binary electrolyte in water (i.e NaCl or KCl or HCl)

3.3) Qualitatively, can you interpret the sign and relative magnitude of ()- (0) for the three
systems-NaCl, KCl & HCl obtained in question 3.2.

4) In order to rationalize the nature of potentials in Eukaryotic biological cells, we had analyzed
a model system in an earlier quiz. We considered a steady, one-dimensional transport of a univalent-
univalent salt (for which + = | | = 1) at infinite dilution in water 25C along a channel that
extends from x=0 to x=L. + () = () = () represented concentrations of salt at position x.
The diffusion constant of the cation and anion were + and respectively. There was no
convection, no current and the salt concentration at the channel ends are held constant at (0) = 0
D D+ 0
and () = . The following expression was derived: =( )( ) . Assuming =10,
D + D+
the values for ()- (0) were computed and was found to be non-zero.
Let L=1 cm. For many of the derivations, we have used the local electroneutrality condition,
Zi Ci = 0. While electroneutrality is considered a good approximation, the Poissons equation is
an exact result.

4.1) Obtain a general analytical expression for 2 for the above model system (Note: Expression
being asked for is NOT Poissons equation!).
4.2) Based on the above expression from question 1, for this model system, under what condition
would 2 be zero?
2
4.3) Using the condition for steady, unidirectional diffusion of a binary electrolyte =0 and the
2
()
boundary conditions, obtain a general expression for () and .

4.4) Using the above results from question 3 and the expression for 2 , obtain an analytical
expression for + () ().
4.5) Using the above results from question 4, write down the conditions for deviation from
electroneutrality.
4.6) Assuming 0 , derive an approximate analytical expression for |+ |
4.7) Using the approximate analytical expression obtained in question 6, compute quantitatively
|+ | for the above mentioned model system. Is this a small number? (you have to get the
quantitative order of magnitude correct to obtain any points, just answering Yes! It is a small
number! does not suffice)
4.8) In general (not necessarily for the above model system under consideration), under what ion
concentration profile will Laplace equation be valid?
4.9) Under general conditions when Laplace equation is valid, is steady-state a requirement? (give
reasons)
4.10) Under general conditions when Laplace equation is valid, is convection allowed? (give
reasons)
4.11) Under general conditions when Laplace equation is valid, what are the conditions on mixing?
4.12) Observe carefully the equation for electroneutrality and Poissons equation. Because of what
quantitative features, we cannot simultaneously use both these equations?