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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 6rs. 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 zEvcFA zvcFA L I G R L zvcF . it can be shown that: zF . where F N A e Fully dissociated electrolyte: stA. vcN A J (ions) svcN A At J (ch arg e) zervcN A zrvcF zEvcF I J .

in aqueous solution.The Mobility of Ions and Conductivity In solution: zF 0 m ( z v z v ) F Example: 1.63x10-3 sm2 mol-1 . From the mobility of Cl. zF = 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 6r .

Thank You .

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