Chapter 7
Activity
• activity
• Activity coefficient
• extended Debye-Huckel eq
• hydrated radius
• ionic atmosphere
• ionic strength
• fugacity
• fugacity coefficient
Hydrated Radii
The Effect of Ionic Strength on Solubility of Salts
2+
[ Fe( SCN ) ]
Fe3+ + SCN- Fe(SCN)2+ K= 3+ -
[ Fe ][ SCN ]
• Ionic strength
Addition of an “inert” salt increases
the solubility of an ionic compound
• Why?
• Net charge of ionic atmospheres < the charge of the ion at the center
• The greater the ionic strength, the higher the charge in ionic atmosphere
• Each (ion + atomosphere) contains less net charge
• there is less attraction b/w + ion and – ion
• thereby increasing the solubility of salt
Rayleigh Light-Scattering of Nanocrystals:
Shape, Size, and Composition Matter
Ag Nanoprisms Au Sphere Au Sphere Ag Sphere Ag Spheres Ag Spheres
~100 nm ~100 nm ~50 nm ~120 nm ~80 nm ~40 nm
200nm
200 nm
* The scale bar is the same for all the images.
From C.A. Mirkin group
Stability of Particles?
Kinetically stable,
n=55
Energy n=147 not thermodynamically
n=309
Bulk metal
Particle Size
–
– +– – – +– –
–+ + –+ +
++ + – ++ + –
– – –
– – –
(a) (b)
Electrostatic repulsion Steric hindrance
Zeta Potential
• The sign of the surface charge of the composite microsphere-
multilayer is typically determined by Zeta potential measurements.
From [Link]
• Ionic strength? a measure of the total concentration of ions
1 2 2 1 2
m = (c1 z1 + c2 z 2 + ...) = å ci zi
2 2 i
0.10 M NaNO3, Na+, NO3-
0.010 M Na2SO4 2Na+, SO42-
0.020 M KBr and 0.010 M Na2SO4 K+, Br-, 2Na+, SO42-
Activity Coefficients
2+
[ Fe( SCN ) ]
Fe3+ + SCN- Fe(SCN)2+ K= 3+ -
[ Fe ][ SCN ]
without any ionic strength effect
A c = [C ]g c
Activity coefficient
2+
g Fe ( SCN ) [ Fe( SCN ) ]
2+
K=
g Fe [ Fe3+ ]g SCN [ SCN - ]
3+ -
with ionic strength effect
• concentration ionic strength
AgI(s) à I- + Ag+ Ksp= 8.3 x 10-17
K sp = A I - A Ag + = [ I - ]g I - [ Ag + ]g Ag +
If ionic strength increases,
à then activity coefficient must decrease
At low ionic strength, the activity coefficient à1
• Activity Coefficient of Ions: the extended Debye-Huckel Eq.
(at 25°C, when μ<0.1 M)
2
- 0.51z m
log g =
a m
1+ ( )
305
Hydrated radius
Page 147: interpolation
• Effect of Ionic Strength, Ion Charge, and Ion Size on the Activity Coefficient
Ionic strength Activity coefficient
Ionic strength = 0 Activity coefficient = 1
Ion charge Activity coefficient
The smaller the hydrated radius,
the more important activity effects
Page 146
• When μ >0.1 M
Systematic Treatment of Equilibrium
To write as many independent algebraic equations
as there are unknown species in the problem
Balances of charge and of mass
Charge balance: there is only one!
Charges must balance in every solution.
Otherwise, a beaker with excess positive charge would glide across
the lab bench and smash into a beaker with excess negative charge.
Write the charge balance for a solution containing
H2O, H+, OH-, ClO4-, Fe(CN)3-6, CN-, Fe3+, Mg2+,
CH3OH, HCN, NH3, NH4+
Mass balance: read by yourself! summarize it, and
submit it to me
We will usually omit activity coefficients
because the complexity of manipulating activity coefficients is
a nuisance.