COLLOID & INTERFACE ENGINEERING

CHE F 498

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 PART 1 : COLLOIDS

CHE F 498

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 STABILIZATION / DE-STABILISATION
OF COLLOIDAL DISPERSIONS

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 ZETA POTENTIAL
IMAGES FROM GOOGLE

A Colloidal Particle can be observed

to move in an Applied Electric Field
Zeta Potential (ζ) refers to the Potential
attributable to a colloidal particle based
on its Velocity in an Electric field

The Counter-ions in the STERN Layer are

thought to be “bound” to the colloid

The BOUNDARY of the fluid moving

with the colloidal particle is referred Zeta Potential (ζ) is the potential
to as the “Slipping plane” at the Slipping Plane

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
MEASUREMENT OF ZETA POTENTIAL
IMAGES FROM GOOGLE
Difference between Surface Potential, Velocity of the colloids is measured
Stern Potential and Zeta Potential in an applied Electric Field

Colloid Motion in an Applied electric

field is called Electrophoretic Mobility
imparting an Electrophoretic Velocity
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 MEASUREMENT OF ZETA POTENTIAL
TYPES OF ELECTROKINETIC PHENOMENA
Corrections
ELECTRO PHORETIC MOBILITY : Relevant to
Colloidal particles move due to Estimation of
an applied electric field Zeta Potential:
SEDIMENTATION POTENTIAL:
Movement of Charged colloids due to
gravity cause a Potential Difference For a Flat Measurement Cell the Stationary points
are at 0.2 and 0.8 of the Dia
ELECTRO-OSMOSIS: Fluid moves
due to the applied electric field For a Cylindrical Measurement Cell the Stationary
points are at 0.146 and 0.854 of the Dia
STREAMING POTENTIAL: Flow of Fluid
If the Wall and the Colloids have the same charge then
(due to an external driving force)
Measured Velocity is 2 times the Actual Colloid
produces a Potential Difference
Velocity (vE). (or 1.5 times for a Flat cell)
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 ESTIMATION OF ZETA POTENTIAL
Principle of Measurement:
At this point, the colloids
The Applied Electric Particles accelerate till the Drag
move with an Uniform
Field causes the Colloid force on the Colloid equals the
Velocity in the Direction
particles to accelerate Force due to the Electric Field
of the applied field
𝐴𝑝𝑝𝑙𝑖𝑒𝑑 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 (𝑉𝑜𝑙𝑡𝑎𝑔𝑒) 𝑉𝑜𝑙𝑡𝑠 Where :
𝐸 𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝐹𝑖𝑒𝑙𝑑 = ≡ FE = Force due to Applied
𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒𝑠 𝑐𝑚(𝑜𝑟 𝑚)
Electric Field
E Field Force on 𝑭𝑬 = 𝑸𝑪 𝑬 When the Colloid STOPS FD = Force Due to Drag
the COLLOID: accelerating QC = Colloid Charge (C)
vE = Colloid Velocity
𝑸𝑪 𝑬 = 𝟔𝝅𝝁𝒓 𝒗𝑬 R = Radius of Colloid
DRAG Force on 𝑭𝑫 = 𝟔𝝅𝝁𝒓 𝒗𝑬 µ = Viscosity of the Fluid
the COLLOID : 𝑸𝑪 = 𝟔𝝅𝝁𝒓 𝒖𝑬 uE = Colloid Velocity per
unit Applied field

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 ESTIMATION OF ZETA POTENTIAL
1
When the Double layer is >> Colloid Radius: 𝑟 ≪
𝜅
𝑄1 𝑄𝐶 𝑄𝐶
𝐸 𝑟 = 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑎𝑡 𝑟 = 𝜁= −
4 𝜋 𝜖 𝑀 𝑟 4 𝜋𝜖 𝑟 4 𝜋𝜖 (𝑟 + 1Τ𝜅)
1/κ
𝑄𝐶 1 𝜅 𝑄𝐶 1 𝑄𝐶
𝜁= − 𝜁= 𝜿𝒓 ≪𝟏 𝜁 =
4 𝜋𝜖 𝑟 (𝜅 𝑟 + 1) 4 𝜋𝜖𝑟 (𝜅 𝑟 + 1) 4𝜋𝜖𝑟
𝟔 𝝁 𝒗𝑬 𝝁
𝑄𝐶 𝐸 = 6𝜋𝜇𝑟 𝑣𝐸 𝟒 𝝅𝝐 𝒓 𝛇 𝑬 = 𝟔𝝅𝝁𝒓 𝒗𝑬 𝛇 = 𝛇 = 𝟏. 𝟓 𝒖𝑬
𝟒𝝐𝑬 𝝐
When the Double 1/κ
layer is << Colloid 𝝁 𝝁
r 𝛇 = 𝒖𝑬 𝛇 = 𝑭 𝒖𝑬 1 < F < 1.5
Radius: 𝝐 𝝐

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DESTABILISATION OF COLLOIDAL DISPERSIONS

MECHANISMS FOR STABILISATION MECHANISMS FOR DE-STABILIZATION

OF COLLOIDAL DISPERSIONS ARE: OF COLLOIDAL DISPERSIONS ARE:

Overlap of ELECTRIC STERIC DEPLETION BRIDGING

DOUBLE LAYERS STABILIZATION FLOCCULATION FLOCCULATION
causing REPULSION due to
SURFACTANTS, VAN DER
POLYMERS and WAALS FORCES
other surface of attraction
active molecules

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DE-STABILIZATION OF COLLOIDAL DISPERSIONS

A colloidal dispersion, The COUNTER-IONS in the added This ALLOWS the

Stabilized by Charge, can be ELECTROLYTE cause the DOUBLE COLLOIDAL PARTCLES to
completely destabilized by LAYER around the COLLOIDAL AGGREGATE & SETTLE. This
ADDING AN ELECTROLYTE. particles to COLLAPSE. is called COAGULATION

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 CRITICAL COAGULATION CONCENTRATION (CCC)
The Concentration of
Critical Coagulation Concentrations for
an Electrolyte required some –vely Charged Colloids :
to cause Colloid DE- Salt Conc Salt Conc 𝐶𝐶𝐶 𝑁𝑎𝐶𝑙 51
= ~1
STABILIZATION / mM mM 𝐶𝐶𝐶 𝐾𝐶𝑙 49.5
COAGULATION 𝐶𝐶𝐶 𝑁𝑎𝐶𝑙 51
NaCl 51 KNO3 50 = ~ 70.8
𝐶𝐶𝐶 𝑀𝑔𝐶𝑙2 0.72
KCl 49.5 MgSO4 0.81
It can be observed CaCl2 0.65 Al(NO3)3 0.095
𝐶𝐶𝐶 𝐾𝐶𝑙 49.5
= ~ 68.7
that the CCC is 𝐶𝐶𝐶 𝑀𝑔𝐶𝑙2 0.72
highly dependent MgCl2 0.72
𝐶𝐶𝐶 𝑁𝑎𝐶𝑙
on the VALENCY of AlCl3 0.093
𝐶𝐶𝐶 𝐴𝑙𝐶𝑙3 𝐶𝐶𝐶 𝐾𝐶𝑙 49.5
the Counter-ion 49.5 = ~ 532
= ~ 532 𝐶𝐶𝐶 𝐴𝑙𝐶𝑙3 0.093
0.093
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 CRITICAL COAGULATION CONCENTRATION (CCC)
Critical Coagulation Concentrations Schulze- The ability of a counter-ion to
for some +vely Charged Colloids : Hardy destabilize a Colloidal Dispersion
Rule: varies in proportion to ~ z6
Salt Conc mM
𝐶𝐶𝐶 KNO3 60 Thus the ccc for a DI Valent Counter-ion
NaCl 43.5 = ~ 1.3
𝐶𝐶𝐶 𝐾𝐶𝑙 46 is lower than the ccc of a MONO valent
KCl 46 counter-ion by a factor of ~ 26 = 64
𝐶𝐶𝐶 𝐾𝐶𝑙 46
KNO3 60 = ~ 73
𝐶𝐶𝐶 K2Cr2O7 0.63 Thus the ccc for a TRI-Valent Counter-ion
K2SO4 0.3 is lower than the ccc of a MONO valent
𝐶𝐶𝐶 𝐾𝐶𝑙 counter-ion by a factor of ~ 36 = 729
K2Cr2O7 0.63
𝐶𝐶𝐶 K3(Fe(CN)6)
K3(Fe(CN)6) 0.08 46 While NOT EXACT, this RULE gives an
= ~ 575 approximately correct estimate of ccc
0.08
and Hence is used as a “Rule of thumb”
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DLVO (DERIYAGIN-LANDAU VERWEY-OVERBEEK) THEORY
ELECTROSTATIC REPULSION: As 2 Colloid Particles (with same CHARGE sign) approach
each other, their DOUBLE LAYERS INTERACT leading to an INCREASE in Total Energy.
64 𝜋 𝜖 𝑟1 𝑟2 𝑘 2 𝑇 2 𝛾1 𝛾2 −𝜅𝑥
𝐸𝐸𝑆 = 2 2
𝑒
𝑟1 + 𝑟2 𝑒 𝑧
𝑧𝑒𝜓1 𝑧𝑒𝜓2
𝑒 2𝑘𝑇 −1 𝑒 2𝑘𝑇 −1
𝛾1 = 𝑧𝑒𝜓1
𝛾2 = 𝑧𝑒𝜓2
𝑒 2𝑘𝑇 +1 𝑒 2𝑘𝑇 +1
r1 = Radius of Colloid 1
2𝑧 2 𝐹 2 𝑐
𝜅= r2 = Radius of Colloid 2
𝜖𝑅𝑇 Ψ1 = Potential of Colloid 1
Ψ2 = Potential of Colloid 2
x = Separation Distance
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DLVO THEORY
VAN DER WAALS ATTRACTION: If 2 COLLOID particles in a medium come close enough
then the Van Der Waals force of attraction becomes DOMINANT which may lead to
attachment of the colloids
𝐴121 𝑦 𝑦 𝑧 2 + 𝑧𝑦 + 𝑥
𝐸𝑉𝑊 = − 2
+ 2 + 2 𝑙𝑛 2
12 𝑧 + 𝑧𝑦 + 𝑧 𝑧 + 𝑧𝑦 + 𝑧 + 𝑦 𝑧 + 𝑧𝑦 + 𝑧 + 𝑦

𝐴121 = 𝐴1 + 𝐴2 − 2 𝐴1 𝐴2
𝑥 A1 = Hammaker Const for Colloids
𝑧= A2 = Hammaker Const for Medium
𝑟1 + 𝑟2
r1 = Radius of Colloid 1
𝑟1 r2 = Radius of Colloid 2
𝑦= x = Separation Distance
𝑟2

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DLVO THEORY
The Interaction Energy between 2 COLLOIDS in a MEDIUM can 𝑬𝑻 = 𝑬𝑬𝑺 + 𝑬𝑽𝑾
be estimated by adding the Energy due to ELECTROSTATIC
REPULSION and VAN DER WAALS ATTRACTION

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DLVO THEORY
The Critical Coagulation concentration can be Estimated
from DLVO theory by finding the Electrolyte concentration
at which the MAXIMA in the Total Energy Curve Disappears

SECONDARY MINIMA

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 COLLOID AGGREGATION KINETICS
Population Balance on K sized aggregates (Smoluchowski’s Equation):
∞
𝑑𝑁𝐾 1 NK = Number of K sized aggregates
= ෍ 𝐾𝑖,𝑗 𝑁𝑖 𝑁𝑗 − ෍ 𝐾𝑖,𝑘 𝑁𝑖 𝑁𝐾
𝑑𝑡 2 Ki,j = Aggregation rate constant for
𝑖+𝑗=𝐾 𝑖=1
Agglomeration of aggregates of size i and size k
∞
𝑁𝑘
𝑁0 = ෍ 𝑘 𝑁𝑘 𝑋𝑘 = N0 = Total Number of Colloids in dispersion
𝑁0
𝑘 =1
(Initial Monomer Population)
∞
1 𝑑𝑋𝐾 1 XK = Number Fraction of K sized aggregates
= ෍ 𝐾𝑖,𝑗 𝑋𝑖 𝑋𝑗 − ෍ 𝐾𝑖,𝑘 𝑋𝑖 𝑋𝐾
𝑁0 𝑑𝑡 2
𝑖+𝑗=𝐾 𝑖=1 Assumption: Ki,j = K1,1 for all i, j
∞
𝑑𝑋𝐾 𝑁0 𝐾11 2 𝒕
= ෍ 𝑋𝑖 𝑋𝑗 − 𝑁0 𝐾11 ෍ 𝑋𝑖 𝑋𝐾 Defining : 𝑻=
𝑑𝑡 2 𝑡𝑎𝑔𝑔 =
𝑖+𝑗=𝐾 𝑖=1 𝑁0 𝐾11 𝒕𝒂𝒈𝒈
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 COLLOID AGGREGATION KINETICS
𝑻𝒏−𝟏
𝑿𝒏 𝑻 =
(𝑻 + 𝟏)𝒏+𝟏

Kinetics of Aggregation is extremely

dependent on Aggregation rate constant K,
and the Initial Colloid Concentration
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus