COLLOID CHEMISTRY

Dr. Ngo Thanh An

Email: ngothanhan@gmail.com
1
1. Effect of radius on equilibrium

Assume a droplet in vapor, using Young-Laplace

equation:
P  P l  P v    
In general, dG   SdT  VdP
dG l   S l dT  V l dP l
dG v   S v dT  V v dP v
At equilibrium, we have conditions: dG(L)= dG(V)

S v

 S l dT  V v dP v  V l dP l
Assuming Pv = const, S v l  dT  V l dP l
1. Effect of radius on equilibrium

  l v

d P  d P  P  dP  d    
 l

l v
  dT
 d    
S
dP 
l
l
V
P  P l  P v    

S l v S v l
T T

0 d  V l T dT   V l  dT
To
o

V l
 
T
v l T
S 1
   To  T  
1
0 d    T dT  
o

Gibbs – Thomson coefficient

1. Effect of radius on equilibrium

T    
2
For a sphere T   
r

Change to equilibrium as a function of radius expressed as an undercooling.

Thus during nucleation, the phase diagram is altered. The actual equilibrium
point is lower than that shown on the phase diagram due to curvature. There is
always undercooling during homogeneous nucleation!!!
2. Nucleation

4 3
G  GS  GV  4r   r  Gv 2

3
G: overall excess free energy between a small solid particle of solute and
the solute in the solution
GS: excess free energy between the surface of the particle and the bulk of
the particle
GV: volume excess free energy: the excess free energy between a very
large particle (r = ) and the solute in the solution.
Gv: free energy change of the transformation per unit volume
GS: a positive quantity: (enlargement of area need supplying work, that
means, work is negative  dG = - dA > 0)
GV: a negative quantity: (increase of volume generate work, that means,
work is positive  dG = - dA < 0)
: interfacial tension between the developing crystalline surface and the
supersaturated in which it is located.
2. Nucleation

dG
 8r  4r 2  Gv  0
dr

2
rc 
Gv

16 3 4rc2
Gcrit  
3  Gv 
2
3
2. Nucleation

p'
RT RT p'
Gv   vvapour dP   d ln P  ln o
po
v v p

  molarvolume 
Mw 2 2v
rc  
Gv p'
RT ln o
16 v 2 3 p
Gc 
3 [ RT ln S ]2 2M w

RT ln S
3. Droplet in gas

Convention
Symbol “: is use to denote the phase on the concave side of a
meniscus
Symbol ‘: is use to denote the phase on the convex side of a
meniscus

Thus, for a droplet in a gas, symbol “ is for the liquid and ‘ for the gas
For a droplet in gas, the centre is inside the liquid phase  this is the convex meniscus?

2
P = P"  P' =
r

------
Concave meniscus (r < 0): the centre is outside of the liquid phase?????
Convex meniscus (r > 0): the centre is inside of the liquid phase????
3. Droplet in gas

 2  1
dP  dP"dP '  d    2d  
 r  r
Phase condition:

d G"  d G '
P ' 2 V "
ln 
Po RTr
 P '  P o and equilibrium vapor pressure
is higher for a droplet than a flat surface
3. Droplet in gas

Kelvin Equation

P' 2 V"
ln o 
P RTr
Implication of Kelvin Equation:
1. In a mist containing various droplet
sizes, large droplets will grow at the
expense of small and average
droplet size will increase with time.
Ostwald Ripening.
2. A droplet in equilibrium with its All droplets are of uniform radius, r* ,
vapor is unstable.
pressure is P',

Is this system stable?

3. Droplet in gas

dG '  dG"
S 'dT  V 'dP '  S "dT  V "dP"
Assume P’ = const

S'  S"dT  V "dP"  0 where S'  S"  H vap

T
 2 
dP"dP '  dP"  d  
 r 
1 1

T
H vap r r
 2  T 2 V "

To
T
dT   V "d 
1  r
0

ln  
To H vap r
0
r
T < To
4. Bubble in liquid

 2  V "  V ' V ' RT

d  dP"  dP"   d ln P"
 r  V' V' V'
as"isthe gas

P" 2 V '
ln 
Po RTr

P"  Po
4. Bubble in liquid

H RT 2
dT  V "dP"  0, V"  ; P"  P ' ;
T P" r
 2 
dP"  d  
 r 
1 1

T T
H  2 
r r
R
 T 2
dT   2
d 
 r
0

T To  0 P '
1
r r

1 1

T T
H  2 
r r


T To
T 2
dT  1 Rd ln 
 r
 P ' 0

0
r
4. Bubble in liquid

 2 
 P' 
T  T0 R  r
 ln 
TTo H  P ' 
 
 

T  To
for bubbles to exist