Beruflich Dokumente
Kultur Dokumente
(1 nm 10 m)
coalescence:
r
attraction potential between plate-like particles:
VA (x) =
Ar 12 x
VA (x) =
x
A 2 S 2 12 x
A132: particle(1)-particle(2) interaction through medium (3) A12: particle(1)-particle(2) interaction in vacuum
A132 ( A11 A 33 )( A 22 A 33 )
Dependence of the van der Waals pair potential VA between two colliding particles on the overall Hamaker constant A of the system
A 12 x 2
64 n kT x VR = e
VA =
between two spheres:
Ar 12 x
2 2
8 k T r x VR = e 2 2 e z
e 1 ze zkT e + 1
ze zkT
attraction potential
(van der Waals forces)
VA kT
total potential 0
VT kT
VT = VA + VR
Stability
Coagulation
Colloid stability/flocculation/coagulation/ are controlled by the relative magnitudes of the van der Waals and the Coulombic forces
repulsion
potential
total
aqueous As2S3 sol with increasing background electrolyte concentraion (1:1 electrolyte, mM)
Colloid stability/flocculation/coagulation/ are controlled by the relative magnitudes of the van der Waals and the Coulombic forces
stable emulsion stable suspension
unstable
For VT = 0, VR = -VA. In this case, the DLVO theory predicts the ccc ratio for 1:2:3 valence of charge of ions to be 1000:16:1.3.
1 Schulze-Hardy rule: ccc 6 z
electrolyte
1 1 1 : 6: 6 6 1 2 3
Schulze-Hardy-rule
5,1 10-2 5,0 10-2 7,2 10-4 6,5 10-4 9,3 10-5 1000 16 16 1,3
ccc
c increases
interaction energy / 10-19 J
c = 1 mM
23 mM
4 mM
90 mM
360 mM 1500 mM
ccc = 65 mM
ccc
Mechanisms of coagulation
perikinetic
differential settling
orthokinetic
perikinetic: collisions by Brownian motion differential settling (polydisperse suspensions) orthokinetic: induced collisions through stirring; shear
Fast coagulation (Smoluchowski): each collision leads to aggregation (high electrolyte concentration, Vmin . 0, rate constant: kf)
no n = 1 + 4 (2 r + x ) D n o t
Slow coagulation (Fuchs): only part of the collisions leads to aggregation (low/intermediate electrolyte concentration, Vmin ~ kT, rate constant: ks)
no n = 1 + W 4 (2 r + x ) D n o t
t s,1 / 2 kf W = = t f,1 / 2 ks
log W
2:2 e
turbidity measurements W
fast coagulation region
log c
ly tro
1:1
lec
c ele
tro lyt e
logW = a b log c
te
(x > )
interactions.
(a) polymer in solution; (b) chemisorbed (end-grafted) copolymer; (c) physisorbed homopolymer; (d) adsorption at low surface coverage with no neares neighbour overlap (mushrooms); (e) adsorption at high coverage (brush); (f) bridging
c K+ c
MW 3 MW3 MW 2 MW2 MW MW1 1
c (mg/L)
Typical thickness of the adsorption layer in case of electrostatic stabilization and steric stabilization
1:1 electrolyte c [mmol.dm-3] 0.01 0.1 1 10 100 1/ [nm] 100 30 10 3 1 (thickness of the electric double layer) polymer M [g.mol-1] 1,000,000 100,000 10,000 1,000 +ho,- [nm] 60 20 6 2 (end-to-end distance . polymer layer thickness)
Polymers at interfaces
cpolymer
bridging flocculation
Steric interaction
x/2
x = 2
~ coil diameter, rg
x
VA van der Waals attraction
electrolytes
polymers