17.02.

2012

ANALYTICAL CHEMISTRY IONIC STRENGHT - ACTIVITY

Assisst. Prof. Ebru TRKZ ACAR

Fe3+ + SCNYellow Clear

Fe(SCN)2+
Red

Adding KNO3 to the media red colour turns to the clear.

Where is KNO3 in equilibrium? Why does equilibrium changes?

Ex. Mercurous iodate in distilled water

Hg2(IO3)2 = Hg22+ + 2IO3 Ksp =1.3 1018

Ksp = [Hg22+][IO3]2 = x(2x)2 = 1.3 1018 x = [Hg22+] =6.9 107M 0.050M KNO3 + saturated solution of mercurous iodate [Hg22+] =1.0 106M Ion dissociation is increased by increasing the ionic strength

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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.

Ex. Calculate the ionic strenght of 0.1M KCl

= (1/2){(0.1)(+1)2+(0.1)(1)2} = 0.1M

Ex. Calculate the ionic strenght of 0.02M NaBr

where Ci = molarity of the ith species, Zi= its charge

: Ba2+

Ex. Calculate the ionic strenght of 0.1M Na2SO4

: IO32-

After adding KNO3

: Ba2+ : IO32: K+ : NO3-

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Activity and Activity Coefficient

Every ion shows different affect according to its hydrate radius. 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.
F-

I-

Ai = [C]i
where [C] = molarity of species C,
i = activity

350 pm

300 pm

coefficient

Debye Hckel Equation

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How is the hydrate radius of hydrogen ion?

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Ex: In 0.033 M Hg2(NO3)2 solution calculate the activity coefficient and activity
for Hg2
2+ .

Ex: In 0.042 M BaCl2 solution calculate the activity coefficient and activity for
Ba2+ .

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Equilibrium Calculations Using Activity Coefficients Ex: Find the relative error introduced by neglecting activities in calculating the Ex: Find the solubility of Ba(IO3)2 in 0.033 M solution of MgCl.
solubility of Ba(IO3)2 in 0.033 M solution of Mg(IO3)2.

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Ex: Use activities to calculate the molar solubility of Zn(OH)2 in 0.010 M KCl. Ksp=3.0x10-16

Ex: Use activities to calculate the pH of the 0.100 M CH3COOH solution. Ka= 1.75x10-5

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Ex: What is the pH of 0.0200 M Benzoic acid a) in water b) in 0.10 M CaCl2. Ka=6.28x10-5

H.W. : When mixing 20.0 mL 0.250 M KOH and 80.0 mL 0.0220 M ZnCl2 calculate the
solubility of Zn(OH)2 using activities. Ksp = 3.0x10-16

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