Debye huckle theory
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1) Three major factors that increase the conductance of strong electrolytes are the relaxation effect, electrophoretic effect, and frictional resistance of the medium. 2) The relaxation effect occurs when an ion moves and has to rebuild its ionic atmosphere around it, slowing its motion. The electrophoretic effect occurs when ions move against the stream of oppositely charged solvent molecules in their ionic atmosphere. 3) The Debye-Hückel-Onsager equation mathematically relates equivalent conductance to concentration, taking into account these factors. It indicates equivalent conductance decreases with increasing concentration.
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The fraction of the amount of the electrolyte in
solution present as free ions is called the degree of
dissociation.
A + B A+ + B_
x =
𝒂𝒎𝒐𝒖𝒏𝒕 𝒅𝒊𝒔𝒔𝒐𝒄𝒊𝒂𝒕𝒆𝒅 ( 𝒎𝒐𝒍
𝑳)
𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝒄𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 ( 𝒎𝒐𝒍
𝑳)
K =
𝑨+ [𝑩−]
[𝑨𝑩]
Definition](https://image.slidesharecdn.com/debye-huckletheory-171025110841/85/Debye-huckle-theory-17-320.jpg)
Debye huckle theory
- 2. Equivalent conductance increases with dilution in the case of weak electrolytes. In case of weak electrolytes increase in conduction is due to increase of dissociation of weak electrolyte. But strong electrolytes are completely dissociated even at moderate concentration. In this theory we have to explore those factors which increase the conductance of strong electrolytes INTRODUCTION
- 3. 1. Relaxation effect or asymmetry effect. 2. Electrophoretic effect. 3. Frictional resistance of the medium. Three major factors are:
- 4. Electrolytes dissociate in solutions state to give positive and negative ions. Each ion is surrounded by an ionic atmosphere of opposite charge. This ionic atmosphere is spherically symmetrical. When a current is passed through the solution, the center of ion of the ionic atmosphere moves towards the oppositely charged electrode. During this movement it has to rebuild an ionic atmosphere of opposite charge around it. At this time the old ionic atmosphere dies out. These two processes do not take place simultaneously. There is a some time lag which is called time of relaxation. During this time, old ionic atmosphere pulls the moving ion backward and so motion is retarted. Due to this the effect is called relaxation effect. RELAXATION EFFECT
- 6. During the application of electromotive force, the central ions moves in one direction and the oppositely charged ions present in their ionic atmosphere move in opposite direction. Solvent molecules are also there in the ionic atmosphere. It means that the central ion is moving against the stream , hence the motion of the central ion is retarted. The effect is called electrophoretic effect. ELECTROPHORETIC EFFECT
- 8. Whenever an ion with its ionic atmosphere travels in the solution, then the medium of the solution offers the frictional resistance. This force depends upon viscosity of the medium and its dielectric constant. FRICTIONAL RESISTANCE OF THE MEDIUM
- 10. Debye and Huckle derived a mathematical expression in 1923. The equation derived by them was further improved by Osangar in 1926. The equation is called DEBYE-HUCKLE- OSANGAR equation.
- 11. ∧=∧∘ − 82.4 𝐷𝑇 1 2 𝜂 + 8.20 × 105 𝐷𝑇 3 2 .∧∘ 𝐶 …….(1) ∧ = Equivalent conductance at any concentration ∧∘= Equivalent conductance at infinite dilution D = Dielectric constant of medium 𝜂 =Viscosity of the medium T = Temperature of solution C= Conc. Of solution
- 12. D, T and 𝜂 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑠𝑜 82.4 𝐷𝑇 1 2 𝜂 = 𝐴 ............(2) 8.20 × 105 𝐷𝑇 3 2 = 𝐵 ………(3) So, eq(1) can be written as ∧=∧∘ −( 𝐴 + 𝐵 ∧∘) 𝐶 …………(4)
- 13. ∧= 𝐴 + 𝐵 ∧ 0 𝐶 +∧∘ ∧=∧∘ (−𝐴 𝐶 − 𝐵 𝐶 ∧∘) ∧∘−∧= (𝐴 𝐶 − 𝐵 𝐶 ∧∘) ………(5) When solution is infinitely dilute, then C=0 and ∧=∧∘ ………(6) Greater the value of A and B, lesser the value of ∧ 𝑎𝑛𝑑 ∧∘
- 15. (a)Situation when current is (b) Situation when current is not applied applied +_ Cu (Blue) CuCr2O7 (Yellow) (a) (b)
- 17. The fraction of the amount of the electrolyte in solution present as free ions is called the degree of dissociation. A + B A+ + B_ x = 𝒂𝒎𝒐𝒖𝒏𝒕 𝒅𝒊𝒔𝒔𝒐𝒄𝒊𝒂𝒕𝒆𝒅 ( 𝒎𝒐𝒍 𝑳) 𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝒄𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 ( 𝒎𝒐𝒍 𝑳) K = 𝑨+ [𝑩−] [𝑨𝑩] Definition
- 19. The reduction of the degree of dissociation of a salt by the addition of a common ion is called the Common ion effect. Definition
- 20. FACTORS Influencing the degree of dissociation
- 21. (1) Nature of solute. (2) Nature of the solvent. (3) Concentration. (4)Temperature. The degree of dissociation of an electrolyte in solution depend on following factors
- 22. Strong acids , strong bases and salts obtained by their interaction are almost completely dissociated. Week acids , week bases and their salts are feebly dissociated. Nature of solute
- 23. Dielectric constant: The capacity of solvent to weaken the force of attraction between the electrical charges immersed in the solvent. The higher the value of dielectric constant the greater is the dissociation of the electrolyte dissolved in it. Nature of solvent
- 24. Dissociation of an electrolyte is inversely proportional to the concentration of its solution. This is due to the fact that in a dilute solution the ratio of solvent molecules to the solute molecule is large and the greater number of solvent molecule will separate more molecules of the solute into ions Concentration
- 25. Higher the temperature greater is the dissociation. At high temperature the increased molecular velocities overcome the force of attraction between the ions and consequently the dissociation increases. Temperature