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TRANSPORT OF IONS IN SOLUTION

 Conductivity of

electrolyte

solutions
 Strong and weak electrolyte
 Ion Mobility
 Ion mobility and conductivity,
 Transport number
 Diffusion
Jaslin Ikhsan, Ph.D.
Chemistry Ed. Department
State University of Yogyakarta

Conductivity of Electrolyte Solution
 Ions in solution can be set in motion by applying a
potential difference between two electrodes.
 The conductance (G) of a solution is defined as the
inverse of the resistance (R):

1
G  , in units of  1
R

 For parallel plate electrodes with area A, it
follows:
A

G

Where,

L

Κ: the conductivity,
L : the distance separating the plates
Units:

G → S (siemens)
R→Ω
κ → S m-1

Λm depends on the concentration of the electrolyte. This could be due to:  Ion-ion interactions  γ  1  The concentration dependence of conductance indicates that there are 2 classes of electrolyte  Strong electrolyte: molar conductivity depends slightly on the molar concentration  Weak electrolyte: molar concentration falls sharply as the concentration increases . the molar conductivity Λm is used m   C  C is molar concentration of electrolyte and unit of Λm is S m2 mol-1 In real solutions.Conductivity of Electrolyte Solution  The conductivity of a solution depends on the number of ions present. Consequently.

Incomplete dissociation of electrolyte strong electrolyte.Conductivity of Electrolyte Solution In real solutions. This could be due to: 1. Λm depends on the concentration of the electrolyte. Ion-ion interactions  γ  1 2. strong dependence of Λm on C . weak dependence of Λm on C weak electrolyte.

.Strong Electrolyte  Fully ionized in solution  Kohlrausch’s law  m  0 m  KC1/ 2 Λ0m is the limiting molar conductivity  K is a constant which typically depends on the stoichiometry of the electrolyte  C1/2 arises from ion-ion interactions as estimated by the Debye-Hückel theory.

Strong Electrolyte  Law of the independent migration of ions: limiting molar conductivity can be expressed as a sum of ions contribution 0 m        ions migrate independently in the zero concentration limi .

1  1   1  2 c  K a K a  c  Ka   Ka  0 2  Ka  Ka  4 Ka c 2   Ka   2c 2c Ka  4 Ka c 2 2c c Ka c  is degree of ionisation  K a K a  4c    1  2c 2c  K a  1/ 2 1/ 2   Ka  4c   1     1 2c  Ka    .Weak Electrolyte  Not fully ionized in solution H3O  (aq)  A  (aq) HA(aq)  H2 O(l ) (1   ) c c  2c Ka  .

the weak acid is fully dissociated (α = 100%)  It can be proven by the Ostwald dilution law which allows estimating limiting molar conductance: c m 1 1  0   m  m Ka ( 0 m ) 2  m  0 m 1 1   m 0 m 1 1 1  0 x m  m  1 1  0 m  m  c  x 1   Ka   m 1 1 c  0  x 0 0  m  m Ka  m  m .Weak Electrolyte  The molar Conductivity (at higher concentrations) can be expressed as:  m   0 m  At infinite dilution.

Weak Electrolyte  The limiting molar conductance: c m 1 1  0   m  m Ka ( 0 m ) 2 Graph to determine the limiting value of the molar conductivity of a solution by extrapolation to zero concentration .

However. ions experience a frictional force in the opposite direction. ( for ions with raidus r and velocity v) .The Mobility of Ions  Ion movement in solution is random. Taking the expression derived by Stoke relating friction and the viscosity of the solvent (). it follows: Ffric  6rs. E    L F  zeE  ze L  is the potential difference between 2 electrodes separated by a distance L F accelerates cations to the negatively charged electrode and anions in the opposite direction. Through this motion. a migrating flow can be onset upon applying an electric field .

and r is hydrodynamic radius.The Mobility of Ions  When the accelerating and retarding forces balance each other. s is defined by: zeE ze s  E . where   6 r 6 r  u is mobility of ions. Mobility in water at 298 K. that might be different from the ionic radius. Viscosity of liquids at 298 K . small ions are more solvated than the bulk ones.

The Mobility of Ions and Conductivity  Finally. A  zEvcFA  zvcFA L   I  G   R L   zvcF . it can be shown that:   zF . where F  N A e  Fully dissociated electrolyte: stA. vcN A J (ions)   svcN A At J (ch arg e)  zervcN A  zrvcF  zEvcF  I  J .

in aqueous solution.The Mobility of Ions and Conductivity  In solution:   zF 0 m  ( z   v   z   v  ) F Example: 1.63x10-3 sm2 mol-1 . From the mobility of Cl.   zF  = 7. Λ=10mS m2 mol-1.91 x 10-8 m2 s-1V-1 x 96485 Cmol-1 = 7. calculate the molar ionic conductivity. if =5x10-8 m2/Vs and z=1. 2.

.891 x 10  3 kgm 1 s 1 x 170 x 10 12 m ze   5 x 10  8 m2V 1 s 1 1V  E L  0. x10 19 C   6 r 6 x 31416 . calculate the drift speed in water at 298 K.23 x10-8 m2 s-1 V-1. H+=36.891x10-3 kg m-1 s-1 1602 .The Mobility of Ions and Conductivity • Taking a conductimetre cell with electrodes separated by 1 cm and an applied voltage of 1 V. it will take 276 s. x 0.01m  100Vm 1 s  E  5 x 10  8 m 2V 1 s 1 x 100Vm 1  5 x 10  6 ms 1  It will take a Cs+ ion 2000 s to go from one electrode to another. rCs = 170 pm H2O = 0.  For H+ ion.

Transport Numbers .

Diffusion .

Diffusion .

Diffusion .

Diffusion .

Diffusion .

Diffusion .

Solution of Diffusion Equation .

Diffusion Probablities .

Random Walk .

Problems .

Summary  Migration: Transport of ions induced by an electric field. The concentration dependence of the molar conductivity strongly differs for strong and weak electrolytes.  Diffusion: Mass transport generated by a gradient of concentration. 2 F 0 m  ( z  v  D  z  v  D ) RT m   0 m  KC 1/ 2 D RT zF kBT D 6r .

Thank You .