COLLOID CHEMISTRY

Dr. Ngo Thanh An

1. Surface excess

• The presence of an interface influences

generally all thermodynamic parameters of a
system
• To consider the thermodynamic of a system
with an interface, we divide that system into
three parts: The two bulk phases with volumes
Vα and Vβ and the interface σ
1. Surface excess

• In Gibbs convention the two phases are thought

to be separated by an infinitesimal thin boundary
layer, the Gibbs dividing plane (this is of course
an idealization)
• Gibbs dividing plane also called an ideal
interface
• In Gibbs model the interface is ideally thin (Vσ =
0) and the total volume is
V = Vα + Vβ
 1. Surface excess

∞ 𝑧𝑒
Γ= 𝜌 𝑧 − 𝜌𝑏 𝑑𝑧 − 𝜌𝑎 − 𝜌 𝑧 𝑑𝑧 = 0
𝑧𝑒 0

• In Gibbs convention the two phases α and β are separated by an ideal interface σ which is infinitely thin:
Guggenheim explicitly treated an extended interphase with a volume
1. Surface excess

N i  N i  ciV   ci V 

Ni
i 
A

V   V V 
 
 
N i  N i  ci V  ci  ci V 
 
 1. Surface excess
 

N1  N1  c1 V  c1  c1 V  
 
(1)

N2  N2  c V  c

2

2  c2 
V 
(2)
 c2  c2 
Multiply both sides of equation (1) by   
 
 c1  c1 

   
c2  c2    
c2  c2    c2  c2 
 
N1      N1   
 
  c1 V   
 

 
 c1  c1   c1  c1   c1  c1 
 c2  c2 
 

  
 c1  c1 V    
 
(3)
 c1  c1 
1. Surface excess
Equation (2) – equation (3)

 c2  c2 
 
N 2  N1   


 
 N 2  c 
2 V  c 
2  
c 
2 
V 

 1
c c1 

 c2  c2    c2  c2 

 N1      c1 V   
 

 
 c1  c1   c1  c1 
 c2  c2 
  

 c1  c1 V   

 
 c1  c1 
 
 
   
  

  c
N 2  N1    2 c 2
 
 
  

c
  N 2  c2 V   N1  c1 V    2 c 2

 
 c1  c1    c1  c1 
   
 c
 i  c   c  c
N i  N1  i
 N  c V  ( N  c V ) i i
c1  c1 c1  c1
i i 1 1
 1. Surface excess

Finally, dividing through by the interfacial area A, gives:

N 2 N1  c2  c2  1    

  
 
    
 
 c
   N 2  c2 V   N1  c1 V   
 
A  c1  c1  A 
2
 c 2

  
A   c1  c1  

N 2 N1  c2  c2  1    

  
 
 
  
 
A  c1  c1  A 

 
 

c
  N 2  c2 V   N1  c1 V    2

c

  
2
A   c1  c1  

 
c  c
2(1)  2  1 2 1
c1  c1
 
 ci  ci

 (1)
 i  1 
c1  c1
i
1. Surface excess

• The right side of the equation does not depend on the position of the Gibbs
dividing plane and thus, also the left side is invariant. We divide this quantity
by the surface area and obtain the invariant quantity
 
c  c
i(1)  i  1 i i
c1  c1
 It is called relative adsorption of component i with respect to
component 1.
 This is an important quantity because it can be determined
experimentally and it can be measured by determinig the surface
tension of liquid versus the concentration of the solute
2. Fundamentals of thermodynamic relations


V  V V 
dV  dV   dV  
dV  dV  dV 

U  U  U  U 
  
Ni  Ni  Ni  Ni
  
S S S S
2. Fundamentals of thermodynamic relations

dU  TdS  PdV   i dN i  dW
dU  dU   dU   dU 
dU  TdS   P dV    i dN i
 TdS   P  dV    i dN i
 TdS   i dN i  dA
  
2. Fundamentals of thermodynamic relations

 
dU  T dS  dS  dS  
 P   
dV  P dV 

  i dN i   i dN i   i dN i  dA



dU  TdS  P dV  P  P dV  
 

  i dN i   i dN i   i dN i  dA

2. Fundamentals of thermodynamic relations

 
dF   SdT  P dV  P   P dV 
  i dN i   i dN i   i dN i  dA
     
2. Fundamentals of thermodynamic relations

  
Ni  Ni  Ni  Ni
dN i  0
dN i  dN i  dN i

   
dF   P   P dV   dA   i  i dN i
   
i

 i dN 
i
2. Fundamentals of thermodynamic relations
2. Fundamentals of thermodynamic relations

  

dF   P  P dV  dA   i dN i

2. Fundamentals of thermodynamic relations

dG   SdT  V  dP  V  dP    i dN i  dA

dG   SdT  VdP   i dN i  dA

G

A T , P , N i
2. Fundamentals of thermodynamic relations

dU   TdS    i dN i  dA

U   TS    i N i  A

F  A   i N i
 

dF    S  dT   i dN i  dA

S  
 
A T , N i
T A, N i
2. Fundamentals of thermodynamic relations

A two-variable homogenous function: f = f(x,y)

Exact differential for f:
𝜕𝑓 𝜕𝑓
𝑑𝑓 = × 𝑑𝑥 + × 𝑑𝑦
𝜕𝑥 𝑦
𝜕𝑦 𝑥

Integrate both sides of equation:

𝜕𝑓 𝜕𝑓
𝑑𝑓 = × 𝑑𝑥 + × 𝑑𝑦
𝜕𝑥 𝑦
𝜕𝑦 𝑥

Thefore, we have:
𝜕𝑓 𝜕𝑓
𝑓= ×𝑥+ ×𝑦
𝜕𝑥 𝑦
𝜕𝑦 𝑥
2. Fundamentals of thermodynamic relations

Application of Euler’s theorem

On the interface, we have:

𝑑𝑈 𝜎 = 𝑇𝑑𝑆 𝜎 + 𝜇𝑖 𝑑𝑛𝑖𝜎 + 𝛾𝑑𝐴

Integrate both sides of the above equation:

𝑑𝑈 𝜎 = 𝑇 𝑑𝑆 𝜎 + 𝜇𝑖 𝑑𝑛𝑖𝜎 + 𝛾 𝑑𝐴

𝑈 𝜎 = 𝑇𝑆 𝜎 + 𝜇𝑖 𝑛𝑖𝜎 + 𝛾𝐴
3. Gibbs adsorption isotherm

From equation:
𝑈 𝜎 = 𝑇𝑆 𝜎 + 𝜇𝑖 𝑛𝑖𝜎 + 𝛾𝐴

Derivative this equation,

𝑑𝑈 𝜎 = 𝑇𝑑𝑆 𝜎 + 𝑆 𝜎 𝑑𝑇 + 𝜇𝑖 𝑑𝑛𝑖𝜎 + 𝑛𝑖𝜎 𝑑𝜇𝑖 + 𝛾𝑑𝐴 + 𝐴𝑑𝛾

Also,
𝑑𝑈 𝜎 = 𝑇𝑑𝑆 𝜎 + 𝜇𝑖 𝑑𝑛𝑖𝜎 + 𝛾𝑑𝐴

Therefore: 𝑆 𝜎 𝑑𝑇 + 𝑛𝑖𝜎 𝑑𝜇𝑖 + 𝐴𝑑𝛾 = 0

3. Gibbs adsorption isotherm

If dT = 0, then: 𝑛𝑖𝜎 𝑑𝜇𝑖 = −𝐴𝑑𝛾

𝑛𝑖𝜎
Or: 𝑑𝛾 = − 𝑑𝜇𝑖
𝐴
𝑛𝑖𝜎
If = Γ𝑖 , then:
𝐴
𝑑𝛾 = − Γ𝑖 𝑑𝜇𝑖
4. Application of Gibbs adsorption isotherm

𝑑𝛾 = −Γ1 𝑑𝜇1 − Γ2 𝑑𝜇2

1
𝑑𝛾 = −Γ2 𝑑𝜇2

𝑎
𝜇2 = 𝜇2𝑜 + 𝑅𝑇 × 𝑙𝑛
𝑎𝑜
4. Application of Gibbs adsorption isotherm

𝑑 𝑎 𝑎𝑜 𝑑𝑎
𝑑𝜇2 = 𝑅𝑇 × 𝑎 = 𝑅𝑇 ×
𝑎𝑜 𝑎

(1) 𝑅𝑇𝑑𝑎
𝑑𝛾 = −Γ2 ×
𝑎
Therefore,
(1) 𝑎 𝑑𝛾
Γ2 =− ×
𝑅𝑇 𝑑𝑎
4. Application of Gibbs adsorption isotherm
 4. Application of Gibbs adsorption isotherm

∞ 𝑧𝑒
Γ= 𝜌 𝑧 − 𝜌𝑏 𝑑𝑧 − 𝜌𝑎 − 𝜌 𝑧 𝑑𝑧 = 0
𝑧𝑒 0
5. Surfactant

Traube’s rule:
In homologous series
each additional CH2
group increases the
surface tension reduction
effect three fold.
5. Surfactant
5. Surfactant
6. Equation of Szyszkowski