Activity coefficient, ionic

strength

Lecture No.4.

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

 “Adjustments” to Equilibrium
Theory
There are two areas where the general
chemistry equilibrium theory can give wrong
results:
- When the solution has high concentrations
of ions;

-When multiple, interacting equilibria occur.

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

 Demonstration

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

 Demonstration
Why did the solution containing NaCl need
more HCl?

How many mL of HCl were expected?

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

2021 spring semester, Vilnius
Lecturer Ingrida Bružaitė
tech
 Ionic Strength Effects
Spheres Surrounding Ions

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

 Hydrated ions

2021 spring semester, Vilnius

Lecturer Ingrida Bružaitė
tech
 Hydrated ions

2021 spring semester, Vilnius

Lecturer Ingrida Bružaitė
tech
 Effect of Ionic Strength on Solubility of
Salts
CaSO4(s) ↔Ca2+ + SO42-, Ksp= 2.4 x 10-5
Solubility of CaSO4 is 0.015M. The dissolved species are mainly 0.010 M
Ca2+, 0.010 M SO42- and 0.005 M CaSO4(aq) (an ion pair).

2021 spring semester, Vilnius

Lecturer Ingrida Bružaitė
tech
 Ionic strength

2021 spring semester, Vilnius

Lecturer Ingrida Bružaitė
tech
 Ionic strength

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

 What is ionic strength?
Ionic strength (I or μ) measure of the total
concentration of ions in solution.

- Ions with more charge are counted more due to

stringer electrostatic interactions with other ions,
i.e. can influence the increase ”ionic atmosphere”
greater than singly charged ions.

2021 spring semester, Vilnius

Lecturer Ingrida Bružaitė
tech
 Ionic strength

2021 spring semester, Vilnius

Lecturer Ingrida Bružaitė
tech
Exercise No.1.
What is the ionic strength of:

(a)0.10 M NaNO3;
(b)0.010M Na2SO4;
(c) 0.020M KBr plus 0.010M Na2SO4.

Note: If you have several salts you need to

sum all ions using ionic strength formula.

2021 spring semester, Vilnius

Lecturer Ingrida Bružaitė
tech
2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė
 Activity

- To account for the effects of ionic strength, concentrations

are replaced by activities in equilibrium formula;
- The activity of species C is equal to the concentration of C
multiplied by its activity coefficient (γ gama);
- The activity coefficient measures the deviation of
behaviour form ideality.

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

 Activity coefficient

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

 Activity coefficient

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

 Calculating activity coefficient
Use of Debye-Hückel equation

Where: Zx – ion charge;

μ – ionic strength;
γ – activity coefficient;
αx – size of hydrated ion in nm (nanometers)
This equation works well for μ ≤ 0.1M

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

 Activity coefficient trend

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė
Exercise No.2.
Calculate the solubility of Pb(IO3)2 in matrix
of 0.020M Mg(NO3)2.
Ksp (Pb(IO3)2) = 2.5 x 10-13

Pb(IO3)2 – Lead(II) Iodate

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė
Exercise No.3.
Calculate the activity coefficients for K+ and
SO42- in a 0.020M solution of K2SO4.

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė

2021 spring semester, Vilnius tech Lecturer Ingrida Bružaitė
Exercise No. 4.

Calculate the molar solubility of PbI2

(Ksp = 5.0x10-7) in 0.2M KI.

2021 spring semester, Vilnius

Lecturer Ingrida Bružaitė
tech