COLLOID & INTERFACE ENGINEERING

CHE F 498

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 PART 1 : COLLOIDS

CHE F 498

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 STABILITY OF COLLOIDAL
SUSPENSIONS

2. STABILITY DUE TO CHARGE

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 COLLOIDAL STABILITY DUE TO CHARGE
Stabilization Colloidal entities in WATER The extent and sign of the CHARGE depend
Due to Charge : and in some other media on the properties of the COLLOIDS AND the
are usually CHARGED. properties of the MEDIUM

Double Layer Theory : - + + - - -

- -
Colloidal particles in a MEDIUM are surrounded
- + + - - -+ + - +
by a DIFFUSE CLOUD of ions which has higher - - - + -
number of Oppositely Charged COUNTER-IONS + + -- - -- + + -
+
- - + - -
This Cloud of Oppositely Charged Counter- + + -
ions is called the DIFFUSE DOUBLE LAYER
The Charge on the Colloid is typically balanced
These DOUBLE LAYERS prevent COLLOIDS from by the Charge in the Double layer. This Theory
coming close to each other OR Colloid Aggregation is also known as GOUY-CHAPMAN Theory

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 COLLOIDAL STABILITY DUE TO CHARGE
Why do Colloids acquire CHARGE in Polar Media:
Adsorption of Ionic Surfactants pH Dependent Ionization
on the Colloid Surface : of Surface Groups:
Surface Functional Groups such as
the R-COOH Group can undergo
IONIZATION to R-COO- depending
on the pH of the WATER.

The pH at which the Colloid

Surface potential changes SIGN
is called the ISO-ELECTRIC Point

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 COLLOIDAL STABILITY DUE TO CHARGE
Why do Colloids acquire CHARGE in Polar Media:
Preferential Adsorption of
Anions on the Colloid Surface :
Due to the Shape of WATER
MOLECULES the Water Di-poles
Orient better around CATIONS.
Thus HYDRATED CATIONS are
BIGGER Than HYDRATED ANIONS.
May Result in Higher Number of
attached ANIONS on a COLLOID
and hence a –ve charge
JAIDEEP CHATTERJEE
Unequal Dissolution
of Ions from Crystals:
Due to the presence of Ions from
another salt, the dissolution of
the common ion from Colloidal
Salt crystals can be lowered.
Hence surface charge of the colloidal
crystals depends on the conc. Of the
ions already present in solution. Ex:
Charge on AgI crystals
BITS Pilani, Hyderabad Campus
FUNDAMENTALS : CHARGE / POTENTIAL / CAPACITANCE
𝑬𝒏𝒆𝒓𝒈𝒚 𝑱 = 𝑷𝒐𝒕𝒆𝒏𝒕𝒊𝒂𝒍 × 𝑽𝒐𝒍𝒖𝒎𝒆
LOW CAPACITANCE

MECHANICAL SYSTEM
LOW CAPACITY OR

HIGH CAPACITY
(Volume / Height) POTENTIAL = PRESSURE or Height
VOLUME = Volume of fluid
OR ELECTRICAL SYSTEM
POTENTIAL = ELECTRIC POTENTIAL (Volts)
HIGH CAPACITANCE VOLUME ≡ CHARGE (Coulombs)
(Charge / Potential)
𝑬𝒍𝒆𝒄𝒕𝒓𝒊𝒄 𝑬𝒏𝒆𝒓𝒈𝒚 𝑱
= 𝑷𝒐𝒕𝒆𝒏𝒕𝒊𝒂𝒍 𝑽 × 𝑪𝒉𝒂𝒓𝒈𝒆 (𝑪)

𝑽𝒐𝒍𝒖𝒎𝒆 𝑬𝒍𝒆𝒄𝒕𝒓𝒊𝒄 𝑪𝒂𝒑𝒂𝒄𝒊𝒕𝒚

𝑰𝒏𝒅𝒊𝒄𝒂𝒕𝒐𝒓 𝒐𝒇 𝑪𝒂𝒑𝒂𝒄𝒊𝒕𝒚 = 𝑪𝑺 𝑨𝒓𝒆𝒂 = 𝑪𝒉𝒂𝒓𝒈𝒆 (𝑪)
𝑯𝒆𝒊𝒈𝒉𝒕 = 𝑪𝒂𝒑𝒂𝒄𝒊𝒕𝒂𝒏𝒄𝒆 =
𝑷𝒐𝒕𝒆𝒏𝒕𝒊𝒂𝒍 (𝑽)

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY
What is the thickness of Can we estimate POTENTIAL or CHARGE
the DOUBLE LAYER ? DENSITY near the COLLOIDS?
Definitions: 𝜓 𝑥
-
= 𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑖𝑛 𝑉𝑜𝑙𝑡𝑠
- 𝜎 𝑥 𝑎𝑡 𝑥 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑆𝑢𝑟𝑓𝑎𝑐𝑒
- = 𝑁𝑒𝑡 𝐶ℎ𝑎𝑟𝑔𝑒 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑎𝑡 𝑥
- 𝐶ℎ𝑎𝑟𝑔𝑒 N0 = Number of Ions/L in
= the Bulk Solution = c0 NA
- 𝑉𝑜𝑙𝑢𝑚𝑒

X=0 X→
N2 = Concentration of ions in State2
∆𝐸 N1 = Concentration of ions in State1
Boltzmann’s Law: −
𝑁2 = 𝑁1 𝑒 𝑘𝑇 E2 = Energy of ions in State2
E1 = Energy of ions in State1; ΔE = E2 - E1

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY
What is the thickness Applying Boltzmann’s Law to Applying Boltzmann’s Law to
find the Conc. Of + ve Ions at x : find the Conc. Of - ve Ions at x :
of the DOUBLE LAYER ?
𝑧 𝑒 𝜓(𝑥) 𝑧 𝑒 𝜓(𝑥)
𝑘𝑇 −
-- 𝑁+ (𝑥) = 𝑁0 𝑒 𝑁− (𝑥) = 𝑁0 𝑒 𝑘𝑇

-- z = Valency of the ions, T = Temperature, k = Boltzmann’s Constant,

-- e = Charge of an Electron in Coulombs, ψ(x=0) is –ve.
-- 𝑧 𝑒 𝜓(𝑥) 𝑧 𝑒 𝜓(𝑥)
−
-- 𝜎 𝑥 = 𝑧𝑒 𝑁0 𝑒 𝑘𝑇 − 𝑁0 𝑒 𝑘𝑇
--
𝑧𝑒𝜓(𝑥)
X=0 X→ 𝜎 𝑥 = −2𝑧𝑒𝑁0 sinh
𝑘𝑇
Poisson Equation: 𝒅𝟐 𝝍 𝝈 𝑑2 𝜓 2𝑧𝑒𝑁0 𝑧𝑒𝜓(𝑥)
𝟐
=− 2
= sinh
𝒅𝒙 𝝐 𝑑𝑥 𝜖 𝑘𝑇
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY
What is PERMITIVITY of a Medium ? 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑎𝑛𝑐𝑒 (𝐶/𝑉)
𝜖 = 𝑃𝑒𝑟𝑚𝑖𝑡𝑖𝑣𝑖𝑡𝑦 =
𝐿𝑒𝑛𝑔𝑡ℎ (𝑚)
It is the measure of the ability of a MEDIUM to
SHIELD the Electric Field (Due to a Charged Body). 𝐶ℎ𝑎𝑟𝑔𝑒 (𝐶)
𝜎 = 𝐶ℎ𝑎𝑟𝑔𝑒 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 =
𝑉𝑜𝑙𝑢𝑚𝑒 (𝑚3 )
Since SHIELDING occurs over a Length of the Medium
Permittivity is expressed as capacitance per unit length 𝜎 𝐶𝑜𝑢𝑙𝑜𝑚𝑏𝑠 𝑉𝑜𝑙𝑡𝑠 × 𝐿𝑒𝑛𝑔𝑡ℎ 𝑉𝑜𝑙𝑡𝑠
= × =
𝜖 𝑉𝑜𝑙𝑢𝑚𝑒 𝐶𝑜𝑢𝑙𝑜𝑚𝑏𝑠 𝐿𝑒𝑛𝑔𝑡ℎ2
𝑄1 𝑄1 𝑄2
𝐸= 𝐹=
4 𝜋 𝜖𝑀 𝑟 4 𝜋 𝜖𝑀 𝑟 2 𝝈 Slope of the Spatial Gradient of the
=
E = Electric Potential at distance r from Q1 𝝐 Potential Change over the medium
F = Electrical Force on Body 2 due to Body 1 𝒅𝟐 𝝍 𝝈 𝑪
Q2 = Charge on Body 2; Q1 = Charge on Body 1 =− 𝝐𝑽 = 𝟖. 𝟖𝟓𝟒 × 𝟏𝟎−𝟏𝟐
𝜖𝑀 = Permittivity of the Medium 𝒅𝒙 𝟐 𝝐 𝑽. 𝒎
r = Distance from the Charged Body OR between 𝐶
the 2 Charged Bodies 𝜖𝑊 = 80 × 8.854 × 10−12
𝑉. 𝑚
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY
Variation of Potential 𝑑2 𝜓 2𝑧𝑒𝑁0 𝑧𝑒𝜓(𝑥) 2𝑧𝑒𝑁0 𝑧 𝜓(𝑥)
near a Colloid with 2
= sinh = sinh
𝑑𝑥 𝜖 𝑘𝑇 𝜖 𝑘𝑇Τ𝑒
Distance from the same:
𝑘𝑇 𝐸𝑛𝑒𝑟𝑔𝑦 𝐽 𝑘𝑇 1.38 × 10−23 × 300 𝑘𝑇
≡ = 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 (𝑉) = = 0.0258 V = 25.8 mV
𝑒 𝐶ℎ𝑎𝑟𝑔𝑒 𝐶 𝑒 1.602 × 10 −19 𝑒

𝒛𝒆 𝝍(𝒙) 𝒛𝒆 𝝍(𝒙) 𝑧 𝜓(𝑥)

Simplification of 𝒔𝒊𝒏𝒉 𝒌𝑻
when 𝒌𝑻
≪𝟏 If ψ(0) ≪ 25.8 mV, then ≪1
𝑘𝑇Τ𝑒
𝑒 𝑥 − 𝑒 −𝑥 𝑥 2 𝑥 3
sinh 𝑥 = 𝑒𝑥 = 1 + 𝑥 + + + …. when x ≪ 1 𝑒𝑥 = 1 + 𝑥 𝑒 −𝑥 = 1 − 𝑥
2 2! 3!
𝑥2 𝑥3 1 + 𝑥 − (1 − 𝑥) 2𝑥
𝑒 −𝑥 = 1−𝑥+ − +.. sinh 𝑥 = = =𝑥
2! 3! 2 2

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY
What is the thickness When x ≪ 1: 𝑑2 𝜓 2𝑧𝑒𝑁0 𝑧𝑒𝜓(𝑥) 2𝑧𝑒𝑁0 𝑧𝑒𝜓(𝑥)
of the DOUBLE LAYER ? 2
= sinh =
sinh 𝑥 = 𝑥 𝑑𝑥 𝜖 𝑘𝑇 𝜖 𝑘𝑇
If ψ(0) ≪ 𝑑2 𝜓(𝑥) 2𝑧 2 𝑒 2 𝑐𝑁𝐴 2𝑧 2 2
𝑒 𝑐𝑁𝐴 𝑑 2 𝜓(𝑥)
2 2
25.8 mV 2
= 𝜓(𝑥) 𝜅 = 2
= 𝜅 𝜓(𝑥)
𝑑𝑥 𝜖𝑘𝑇 𝜖𝑘𝑇 𝑑𝑥
Solution for the above DE
𝑑2𝑌
2
= 𝜅 2
𝑌(𝑥) 𝑌 𝑥 = 𝐶𝑒 −𝜅 𝑥 𝑌 ′ 𝑥 = −𝐶𝜅𝑒 −𝜅 𝑥 𝑌" 𝑥 = 𝜅 2 𝐶𝑒 −𝜅 𝑥
𝑑𝑥
𝜓(𝑥) = 𝐶𝑒 −𝜅𝑥 Boundary Condition: 𝝍(𝒙) = 𝝍𝟎 𝒆−𝜿𝒙
𝟐𝒛𝟐 𝒆𝟐 𝒄𝑵𝑨
@ x = 0, ψ(0) = C 𝜿=
ψ(0) = ψ0 ; C = ψ0 𝝐𝒌𝑻

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY
What is the thickness of the DOUBLE LAYER ? 𝝍(𝒙) = 𝝍𝟎 𝒆−𝜿𝒙
For a Mono-valent Electrolyte with a Conc of 1 mM in water @ 300 K

𝟐𝒛𝟐 𝒆𝟐 𝒄𝑵𝑨 𝟐𝒛𝟐 𝒆𝟐 𝒄 𝑵𝟐𝑨 𝟐𝒛𝟐 𝑭𝟐 𝒄 𝐶 2 𝑀𝑜𝑙 𝑉. 𝑚 𝑀𝑜𝑙 1

𝜿= = 𝜿= 𝜅≡ ≡
𝝐𝒌𝑻 𝝐𝑹𝑻 𝝐𝑹𝑻 𝑀𝑜𝑙 2 𝑚3 𝐶 𝐽 𝑚

F = Faraday Constant 𝑭 = 𝒆 × 𝑵𝑨 𝟏
= Charge of 1 Mole of = 𝟏. 𝟔𝟎𝟐 × 𝟏𝟎−𝟏𝟗 × 𝟔. 𝟎𝟐𝟑 × 𝟏𝟎𝟐𝟑 = 𝑫𝒆𝒃𝒚 𝑳𝒆𝒏𝒈𝒕𝒉
= 𝟗𝟔𝟒𝟖𝟓 𝑪/𝑴𝒐𝒍 𝜿
Electrons in Coulombs
𝜿 = 𝟎. 𝟎𝟏 × 𝟏𝟎 𝟏𝟎 𝒎−𝟏
2 × 1 × (96485)2 × 10−3 × 103
𝜅= 𝟏
80 × 8.854 × 10−12 × 8.314 × 300 = 𝟏𝟎 𝒏𝒎
𝜿

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY
For a Mono-valent 𝐷𝑒𝑏𝑦 𝐿𝑒𝑛𝑔𝑡ℎ
Electrolyte with a Conc of = 10 𝑛𝑚
1 mM in water @ 300 K = 10−8 𝑚
𝑥
𝜓 𝑥 = 𝜓0 𝑒𝑥𝑝 − −8
10

Increase in Electrolyte concentration

causes the Double Layer to COLLAPSE

Increase in COUNTER-ION Valency

causes the Double Layer to COLLAPSE

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY
POISSON-BOLTZMANN’S EQUATION FOR SPHERES
1 𝑑 2
𝑑𝜓 2𝑧𝑒𝑁0 𝑧𝑒𝜓(𝑟)
2
𝑟 = sinh
𝑟 𝑑𝑟 𝑑𝑟 𝜖 𝑘𝑇
Applying the Deby-Huckel Approximation
2 𝑑𝜓 𝑑 2 𝜓 2 𝑧 2 𝑒 2 𝑁𝐴2 𝑐
+ 2 = 𝜓 𝑟 = 𝜅2𝜓
𝑟 𝑑𝑟 𝑑𝑟 𝜖𝑅𝑇
Boundary Conditions : Ψ(a) = ψ0 ;dψ/dr =0 @ r = ∞

𝒂 −𝜿(𝒓−𝒂)
𝝍 𝒓 = 𝝍𝟎 𝒆 𝟐𝒛𝟐 𝒆𝟐 𝒄 𝑵𝟐𝑨
𝒓 𝜿=
𝝐𝑹𝑻

JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY

ψ0 ψ0
--
--
-- ψ(x) 0V
-- ψ(x)
-- --
-- -- STERN LAYER
STERN LAYER
--
--
--
STERN LAYER --

STERN LAYER
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus
 DOUBLE LAYER THEORY
RELATION COLLOIDAL SURFACE CHARGE & POTENTIAL
Surface Charge Density = σ0 (Coulombs / Area) Surface Potential = ψ0 mV
Charge Balance : Poisson Equation:
-- ∞
∞
-- 𝜎0 = − න 𝜎 𝑑𝑥 𝑑2𝜓 𝜎 𝑑2𝜓
=− 𝜎0 = − න − 𝜖 2 𝑑𝑥
-- 0 𝑑𝑥 2 𝜖 0 𝑑𝑥
-- 𝑑𝜓 ∞
𝜎0 = 𝜖 ቤ 𝜎0 = 𝜖 0 − 𝜓′ 0
-- 𝑑𝑥 0
--
P-B Equation: 𝜓(𝑥) = 𝜓0 𝑒 −𝜅𝑥 𝜓 ′ 0 = −𝜓0 𝜅
X=0 X→
𝝈 𝟎 = 𝝐 𝜿 𝝍𝟎
JAIDEEP CHATTERJEE
BITS Pilani, Hyderabad Campus