Presentation is loading. Please wait.

Presentation is loading. Please wait.

Version 2012 Updated on 030212 Copyright © All rights reserved Dong-Sun Lee, Prof., Ph.D. Chemistry, Seoul Women’s University Chapter 9 Effect of Electrolytes.

Similar presentations


Presentation on theme: "Version 2012 Updated on 030212 Copyright © All rights reserved Dong-Sun Lee, Prof., Ph.D. Chemistry, Seoul Women’s University Chapter 9 Effect of Electrolytes."— Presentation transcript:

1 Version 2012 Updated on Copyright © All rights reserved Dong-Sun Lee, Prof., Ph.D. Chemistry, Seoul Women’s University Chapter 9 Effect of Electrolytes on Chemical Equilibria

2 Concentration-based equilibrium constant: At low electrolyte (ex. NaCl), concentration-based equilibrium constant becomes independent of the electrolyte concentration and is equal to thermodynamic equilibrium constant. concentration-based equilibrium constant : K w ’, K sp ’, K a ’ … thermodynamic equilibrium constant : K w, K sp, K a If [NaCl] = 10  4 M : K w ’= K w = 10  14 If [NaCl] = 10  1 M : K w ’= Effect of electrolyte concentration on concentration-based equilibrium constants.

3 Limiting law : A relationship that approaches a constant value as some parameter (ex. the electrolyte concentration) approaches zero. Limiting value : The constant numerical value observed at limit.

4 Ionic strength Ionic strength,  is a measure of the average electrostatic interactions among ions in an electrolyte ; it is equal to one-half the sum of the terms obtained by multiplying the molarity of each ion by its valence squared.  = (1/2)  ([C i ]Z i 2 ) where C i = molarity of the ith species, Z i = its charge Ex. 0.1M Na 2 SO M KCl  = (1/2){(0.1×2)(+1) 2 +(0.1)(–2) 2 +(0.1)(+1) 2 +(0.1)(–1) 2 } = 0.4M

5 Effect of electrolyte concentration on the solubility of some salts. The Effect of Ionic Charges on Equilibria With ionic participants, the magnitude of the electrolyte effect increases with charge.

6 The effect of ionic strength on solubility of salts Ex. Mercurous iodate in distilled water Hg 2 (IO 3 ) 2 = Hg IO 3 – K sp =1.3 ×10 –18 K sp = [Hg 2 2+ ][IO 3 – ] 2 = x(2x) 2 = 1.3 ×10 –18 x = [Hg 2 2+ ] =6.9 ×10 –7 M 0.050M KNO 3 + saturated soln of mercurous iodate [Hg 2 2+ ] =1.0 ×10 –6 M  Ion dissociation is increased by increasing the ionic strength

7

8 The salt effect (also called the electrolyte effect) Influence of ions on the activities of reagents. The electrolyte effect results from the electrostatic attractive and repulsive forces that exist between the ions of an electrolyte and the ions involved in an equilibrium. These forces cause each ion from the dissociated reactant to be surrounded by a sheath of solution that contains a slight excess of electrolyte ions of opposite charge.

9 Activity and activity coefficient activity : a thermodynamic quantity which measures the effective concentration or intensity of a particular substance in a given chemical system. For dilute, ideal solutions the activity is directly proportional to the concentration ; for ideal gases, activity is proportional to the partial pressure of the gas. The absolute activity, A :  = RT nl A where  = chemical potential A C = [C]f c  cf fugacity A G = P G f G where [C] = molarity of species C, f c = activity coefficient P = atm. General form of equilibrium constant : aA + bB = cC + dD K o = A C c A D d / A A a A B b = [C] c [D] d f C c f D d / [A] a [B] b f A a f B b At low ionic strength, activity coefficients approach unity, and the thermodynamic equilibrium constant approaches the concentration equilibrium constant.

10 Activity coefficient of ions Estimated Debye-Hückel equation : log f = [ – 0.51 Z 2  ] / [1+(3.3  )] where f = activity coefficient of an ion of charge ±Z and size  (10 –9 m)in an aqueous medium of ionic strength .  = 0~0.1 M range 1)   f ,  0  f  1 2) Z   f  (when  ) 3)  1 >  2   1  2

11 Effect of ionic strength on activity coefficient

12 Peter Debye ( ) was born and educated in Europe but became Professor of Chemistry at Cornell University in He received the 1936 Nobel Prize in Chemistry.

13

14 Ex. Interpolation  x  y Unknown y interval Known x interval x1x1 x2x2 y2y2 y1y1 x3x3 y3y3 x 2 –x 1 =  x x 2 –x 3 = known x interval y 2 –y 1 =  y y 2 –y 3 = ? Unknown y interval (y 2 –y 3 )/(y 2 –y 1 ) = (x 2 –x 3 )/(x 2 –x 1 )  y 3 = y 2 – [(y 2 –y 1 )(x 2 –x 3 )/(x 2 –x 1 )] Ex. H + :  = f = ? 0.86 f = –[(0.914 –0.86)(0.05–0.01) / (0.05–0.025)] = 0.894

15 Solubility using activity coefficients [Ca 2+ ] =? M MgSO 4 soln saturated with CaF M MgSO 4   =(1/2)[(0.0125)(+2) 2 +(0.0125)(–2) 2 ] f Ca 2+ = 0.485, f F – = 0.81 CaF 2 (s) = Ca F – K sp = 3.9 ×10 –11 Initial solid 0 0 Final solid x 2x K sp 0 =[Ca 2+ ] f Ca 2+ [F – ] 2 f F– 2 = (x)(0.485)(2x) 2 (0.81) 2 = 3.9 ×10 –11 x = [Ca 2+ ] = 3.1 ×10 –4 M

16 Solubility of LiF in distilled water (approximation) Ksp  [Li + ][F – ] =x 2 = 1.7 ×10 –3 x = [Li + ] = [F – ] = M 1) assume  =  f Li + = 0.851, f F – = Ksp =[Li + ] f Li + [F – ] f F – = (x)(0.851)(x)(0.830) = 1.7 ×10 –3 x = [Li + ] = 0.049M 2) assume  =  f Li + = 0.837, f F – = Ksp =[Li + ] f Li + [F – ] f F – = (x)(0.837)(x)(0.812) = 1.7 ×10 –3 x = [Li + ] = 0.050M 3) assume  =  f Li + = 0.835, f F – = 0.81 Ksp =[Li + ] f Li + [F – ] f F – = (x)(0.835)(x)(0.81) = 1.7 ×10 –3 x = [Li + ] = 0.050M    solubility 

17 Fe 3+ + SCN – = Fe(SCN) 2+ Pale yellow colorless Red K = [Fe(SCN) 2+ ] / [Fe 3+ ][SCN – ] The equilibrium quotient of concentrations for the reaction Fe 3+ + SCN – = Fe(SCN) 2+ decreases as potassium nitrate (KNO 3 ) is added to the solution.

18 Summary Concentration-based equilibrium constant, K sp ’, K a ’, K b ’, K w ’ Ionic strength Activity, activity coefficient Fugacity, fugacity coefficient Thermodynamic equilibrium constant Electrolyte effect : salt effect Debye-Hückel equation Interpolation Solubility using activity coefficient Approximation


Download ppt "Version 2012 Updated on 030212 Copyright © All rights reserved Dong-Sun Lee, Prof., Ph.D. Chemistry, Seoul Women’s University Chapter 9 Effect of Electrolytes."

Similar presentations


Ads by Google