Sie sind auf Seite 1von 20

CHEM 397

Experiment Q: Contact Angle and Zeta Potential


Measurements with Surface Modified Gold
Alexander Cohen and Alex Zheng
Student #: 10095341, 10092648
T.A. Yaoting Zheng

Introduction:
Self-assembled monolayers (SAMs) are ordered molecular assemblies formed
by the adsorption of an active surfactant on a solid surface [1]. SAMs are formed
when a thin film of an organic molecule is applied to the surface of a material, in the
case of this experiment, the material is gold and the organic molecules are
alkanethiols. Long-chain thiols, HS(CH2)nX adsorb from solution onto gold and form
densely packed, self-oriented monolayers[2]. The overall process is produced by a
spontaneous chemical synthesis at the interface, as the system approaches
equilibrium. This process is very simple and usually involves simply soaking a clean
surface material (eg. Gold plate) in a dilute solution for several minutes or several
days depending on the system. By varying the terminal functional group, X, of the
thiol, a wide range of SAMs can be created having different surface structures and
properties, while maintain the same bulk properties of the adsorbing material.
The determination of zeta potential, , and particle size will allow us to
analyse the effect alkanethiol SAMs have on the electrokinetic properties of gold
(Au) colloids. Two electrokinetic phenomena will be studied to give further insight on
surface properties of Au colloids: electrophoresis and electro-osmosis.
Electrophoresis occurs when there are charged particles suspended in solution.
These particles will be forced to move by applying an electric field across the
system[4]. By measuring the velocity of the particles under a known field, it is
possible to deduct their net electric charge or their surface potential with respect to
the bulk of the suspending phase. Electro-osmosis is the motion of liquid induced by
an applied electric field across a porous material so the solid is stationary. By
measuring the velocity of the liquid or the volume of liquid transported, it is possible
to obtain information about the net surface charge or electrical potential in the area
of the wall.
The overall charge and potential distribution of colloid particles in solution
can be seen in figure 1. The ion distribution creates an electrical double layer
around the particle. A double layer is thought to consist of a layer of electrons, a
layer of adsorbed ions, and a diffuse double layer consisting of an ionic atmosphere
containing an excess amount ions of one sign, and a lacking amount of ions with the
opposite sign of charge5]. Lastly there may exist a thin layer of neutral molecules
which do not exert an influence on the thermodynamic properties of the interface [5].
Looking at the diagram (figure 1[3]), it is possible to distinguish the individual layers
of the electrical double layer. The inner layer is known as the Stern layer. Here, the
ions are strongly bound to the surface of the particle and Stern proposed that these
particles were immobile[5]. The outer layer is made up of the diffuse ions
surrounding the stern layer. Within this outer layer, there is a boundary that
separates the tightly bound Stern layer from the diffuse outer layer. This boundary
is called the slipping plane. The potential that exists at this boundary is known as
the Zeta potential. Zeta potential is the potential difference between the interior of
the liquid phase and a certain plane in the interfacial region (slipping plane). In this
region, dipole orientation and polarization effects are small, and therefore the
potential is considered to originate from a distribution of free charges [6]. Zeta
potential greatly affects the stability of colloidal solutions.

Figure 1[3]. Overall charge and potential distribution of colloid particles in


solution

For any charged interface, the Debye length, K -1, is an important parameter
that describes electrokinetic environments. Looking at Figure 1, it is possible to see
that there is a net negative charge on the surface of the particle. Therefore the ions
in the solution form a net surplus of positive charges to counter the negative
charge, making the overall charge zero. The length of the second layer is the Debye
length. This length can be used to find the Debye-Huckel parameter, which allows
one to approximate the ionic distribution in the double layer [7]. The equation to find
the Debye length under low potential sand solute concentrations can be determined
by the following equation:
Equation 1[9].

K1=

r 0k B T
2e 2c N A I

Where ec is the unit charge on an electron (-1.602e 19C), NA is Avagadros


number (6.022e23 mole-1), kB is Boltmanns constant, T is temperature in degrees
Kelvin, 0 is the permittivity of free space, r is the dialectric constant of the medium
(water), and I is the ionic strength of the solution in mol/m 3
In this experiment, the ionic strength of the solution must first be calculated
by using the following equation:
Equation 2[9].

1
I = z2i [i]
2
Where [i] is the concentaration of ion species I and zi is the charge number on
species i.
Equations 1 and 2 show that the relationship between Debye length and ionic
strength are inversely dependent of each other. The higher the concentration, the
shorter the Debye length. Under extremely high ionic strength conditions, the
electrical double layer collapses.
The stability of colloidal solutions can be characterized as a system in which
the forces of repulsion acting to keep the particles separated exceed the Van der
Waal forces of attraction that would cause particles to adhere on contact and begin
flocculating[7]. Systems with large values of zeta potential (positive or negative) are
more stable as the zeta potential causes the ionic particles to repel each other more
and inversely, a system with a low value of zeta potential (typically >30mV[9])
would tend to flocculate more and become less stable. When the attractive forces
exceed the repulsive potential, the flocculation tends to cause the colloid solution to
coagulate. To quantitatively predict the conditions under which particles will
coagulate, the DLVO theorem is used. The DLVO theorem shows the systems energy
as a function of the distance separating the colloidal particles. The DLVO equation is
as follows:
Equation 3[9].

repulsive Eattractive=

2
B

32 r 0 a k T g
2 2
c

e z

ekH

z ec
2k BT

Aa
e 1
; g= z e
12 H
e 2 k +1
c

BT

E ( H ) =E
Where a is the radius of the colloid particle (assumed to be 20nm for this
experiment), z is the charge of the counter ions, A is the Hamaker constant (1.4e -19
for this experiment), is the measured zeta potential in V, and g is a term defined
to help simplify the equation.
By plotting the DLVO equation on a spreadsheet, it is possible to explore the
effect of changing various parameters from the energy-distance (E-H) plots, mainly
the zeta potential. In this experiment, the electrophoretic mobility of the colloids will
be observed by measuring their zeta potential as a function of pH, which will give
both the sign and magnitude of the charge on the colloid particles. This will allow for
a qualitative analysis of how zeta potential effects colloid stability. The analytical
instrument used in this lab is a Zetasizer Nanoseries ZS90. This instrument uses a
combination of Dynamic Light Scattering, Laser Doppler, Anemometry, and Static
Light Scattering to calculate precise measurements of different sample types [8]. This
instrument will also use Dynamic Light Scattering to measure the size and size
distribution of nanoparticles, which will be required in equation 3 to determine the
DLVO.

In part 2 of the experiment[9], the effect of wettability of different modified


gold surfaces will be observed. Wettability is the major macroscopic property
studied in this experiment. Wettability is a physical property that describes the
interaction between a fluid and a solid surface and is quantified by the
measurement of the contact angle, , between the tangent to a drop of liquid
where it meets the surface and the surface itself. This property is affected by
polarity or dispersive forces, depending on the fluid, and can be studied to provide
deeper insight to the structures of SAMs[2]. Previous studies[1][2] have shown that
thiols with highly polar tail groups, such as carboxylic acids, form monolayers that
are wet by water and thiols with unpolar tail groups will be water repellent. The
general trend observed in all these experiments is that the lower the surface
tension, v, of the liquid, the lower the contact angle. The equation to calculate the
contact angle according to Youngs Equation is:
Equation 4[9].

LV cos= SV SL
Where SV, LV, and SL are surface tensions of the solid-vapour, liquid-vapour,
and solid-liquid interfaces, respectively. This equation relies on several assumptions
such as the droplet volume being constant, and the solid is smooth on a molecular
scale[9]. Additionally, according to Youngs equation, it is impossible to measure SV,
LV independent of one another. Lastly, in real conditions, the physical phenomenon
known as hysteresis occurs. Hysteresis is when a material does not immediately
respond to the forces acting on it. To counter some of these problems, the contact
angle experiments in this lab will be carried out by measuring advancing and
receding angles made by adding or removing the volume of a drop without
changing the area of contacting the surface and perform only simple
measurements.

Observations:
Table 1. Table of values for the major observations made during the preparation
process of this experiment.
Parts of the experiment
Preparation of Gold Solution

Preparation of the dilute alkanethiol


solutions

Preparation of COOH-, and CH3derivatized gold nanoparticles

HACl4*3H2O is initially a gold coloured


solution, upon addition of Sodium
Citrate, solution turns dark purple-red
color.
Both prepared thiol solutions appear
clear, however 1-undecanethiol is more
opaque and purple, and 11thioundecanoic acid is blue.
Upon vibration of thiol solutions, a
change occurs for 11-thioundecanoic
from light blue to clear. Upon vibration
of 1-undecanetiol solution, it turns to a
lighter purple color.

Preparation of COOH-, and CH3derivatized gold nanoparticles

Upon addition of water and buffer to 1undecanetiol, turns completely clear

Procedure:
Refer to the CHEM/ENCH 397/398/399 Lab Manual for in depth details for the
procedure.
Table for the changes made to the experimental procedure

Results:
Equation 1: Calculating the ion concentrations of Gold Chloride/Sodium Acetate.
First Dilution (25mL):

C1 V 1=C 2 V 2
mL
1.137E-03 g /(5 mL)

2.274E-4 g/mL=C 2
Second Dilution (20mL):

( 2.274E-04 g/mL )( 2 mL )=C2 (20 mL)


2.274E-05 g /mL=C2
Equation 2: Calculating concentration in mol/m3 of HAuCl4*3H2O.

2.274E-05 g
1000 mL
mL
1000 L
1L
1 mol
m3
=5.774E-03 mol /m3
393.8 g
Equation 3: Calculating the ionic concentration of Cl - for AuCl4*H2O.

+ HAu3 H 2 O
HAu Cl 43 H 2 O 4 Cl

Cl

Cl

Equation 4: Calculating the Ionic concentration of base buffer using HendersonHasselback equation.

NH 4

pH= pKa+ log

[NH 3 ]

+
NH 4

[3.98E-09 mol /L]


8.4=9.25+ log

+
NH 4

Equation 5: Calculating the total Ionic concentration for R-CH 3 solution.

I=
3

1
z 2i [ i ]

2
2

m + 1 3.98E-06 mol /m
m3+123.98E-06 mol/
m3+123.98E-05 mol/
m3+3 21.93E-01 mol/
3
2
m + 1 5.78E-01 mol/
122.31E-01 mol /
1
I=
2

I =1.27 mol /m

Equation 6: Calculating the inverse Debye-Huckel term.

1=

1=

r 0 k BT
2 e 2c N A I
3

1 4

78.5(8.854E-12 m kg s A )(1.381E-23 m kg s K )(298 K)


2
1
3
2 (1.602E-19 C ) (6.022E+23 mol )(1.27 mol /m )

1=8.53E-09
Equation 7: Calculating the g term.

g=

e
e

g=

e
e

zec
2 B T
ze c
2 B T

1
+1

1(1.602E-19C )(2.99E-02V )
2
1 1
2(1.381E-23 m Kgs K )(298 K)
1(1.602E-19 C)(2.99E-02 V )
2
1
1
2(1.381E-23 m Kgs K )(298 K)

1
+1
g=2.83E-01

Equation 7: Calculating the W-term.

32 0 r a k 2B T 2 g 2
W
e 2c z 2
2

(8.854E-12 m3 kg1 s 4 A2 ) ( 1.381E-23 m 2 kg s2 K 1 ) ( 298 K )2 (2.83E-01)2


W=
(1.602E-19C )2 (1)2
W =5.80E-19
Equation 7: Calculating the X term.


(1)1
X=
X =1.17E+08
Equation 8: Calculating the Y term.

Y=

Aa
12

Y=

(1.4E-19)(1.57E-09 m)
12

Y =1.83E-27
Equation 9: Calculating the Erepulsive for 0.1 nm distance from particle surface of R-CH 3
solution.

Erepulsive=W e XH
Erepulsive=(5.80E-19) e(1.17E08)(1E-10 m)
Erepulsive=5.74E-19
Equation 10: Calculating Eattractive for 0.1 nm distance from particle surface of R-CH 3
solution.

Eattractive=
Eattractive=
Eattractive=1.83E-17

Equation 11: Calculating the E(H) value.

E ( H )=Erepulsive Eattractive
E ( H )=5.74E-191.83E-17

Y
H

1.83E-27 m
1E-10 m

E ( H )=1.78E-17
Equation 12: Calculating the E/KbT

E(H)
KB T
1.78E-17
2
2 1
(1.381E-23 m kg s K )(298 K )
4.31E+03

Equation 13: Calculating the -1/2 for decanol.

LV =28.5 mN /m
1/ 2=28.5

1/ 2

1
2

mN /m

=1.75E-02 m/mN

Equation 14: Calculating the SV surface tension from slope of figure hhh

slope=1.06E+02

SV =

1.06E+02
2

SV =2.809 E +03 mN /m
Equation 15: Calculating the SL value for decanol.

SL = LV + SV 2 ( LV SV )1 /2
SL =28.5 mN /m+1.06 E+ 03 mN /m2 ( 28.5 mN /m1.06 E+03 mN /m )1/ 2
SL =1.29E+03

Table 2. Table of values for the measured pH values of each test solution.

Compound
Au-Base
R-CH3
R-COOH
Au-acid

pH
8.36
8.40
8.27
4.17

Temp (C)
24.0
24.0
24.0
24.3

Table 3. Table of values for the various ionic concentrations of species in solution
for the R-CH3 solution.
Concentration (mol/m3)

Ion

ClNa+
C6H5O73NH4+
Cl- (from buffer)
H+
Table 4. Table of values for calculating
terms.
Colloid
Radius (m)
1.57E-07

Zeta
Potential
(V)
-2.99E-02

Charge

2.31E-01
+1
5.78E-01
+1
1.93E-01
-3
2.82E-05
+1
3.98E-06
-1
3.98E-06
+1
the gold colloid in R-CH 3 solution energy

I (mol/m3)

-1

G term

W term

1.27

8.53E-09

2.83E-01

5.80E-19

X Term

1.17E+08

Table 5. Table of values for the gold colloid in R-CH 3 solution with varying
separation distances.
H (m)

E-repulsive

E-attractive

E(H)

E/KbT

1.00E-10

5.7E-19

-1.8E-17

-1.8E-17

-4.3E+03

2.00E-10

5.7E-19

-9.2E-18

-8.6E-18

-2.1E+03

4.00E-10

5.5E-19

-4.6E-18

-4.0E-18

-9.8E+02

6.00E-10

5.4E-19

-3.1E-18

-2.5E-18

-6.1E+02

8.00E-10

5.3E-19

-2.3E-18

-1.8E-18

-4.3E+02

1.00E-09

5.2E-19

-1.8E-18

-1.3E-18

-3.2E+02

2.00E-09

4.6E-19

-9.2E-19

-4.6E-19

-1.1E+02

4.00E-09

3.6E-19

-4.6E-19

-9.5E-20

-2.3E+01

6.00E-09

2.9E-19

-3.1E-19

-1.8E-20

-4.4E+00

8.00E-09

2.3E-19

-2.3E-19

-1.9E-21

-4.5E-01

Y Term

1.83E-27

1.00E-08

1.8E-19

-1.8E-19

-3.5E-21

-8.5E-01

2.00E-08

5.6E-20

-9.2E-20

-3.6E-20

-8.7E+00

4.00E-08

5.3E-21

-4.6E-20

-4.0E-20

-9.8E+00

6.00E-08

5.1E-22

-3.1E-20

-3.0E-20

-7.3E+00

8.00E-08

4.9E-23

-2.3E-20

-2.3E-20

-5.6E+00

1.00E-07

4.7E-24

-1.8E-20

-1.8E-20

-4.5E+00

Q6.

Figure 1. Plot for gold colloid in R-CH3 solution demonstrates a correlation in curve trend with
acoagulation activation energy barrier at -4.5 KbT and flocculation energy at 87 KbT.

DLVO Plot for Separation Distance from Gold Colloid in R-CH3 Solution
0.00E+00
-5.00E+00

0 10 20 30 40 50 60 70 80

-1.00E+01
-1.50E+01
-2.00E+01

Net Potential Energy E/KBT -2.50E+01


-3.00E+01
-3.50E+01
-4.00E+01
-4.50E+01
-5.00E+01

Separation Distance H (nm)

DLVO Plot for the -48 mV Zeta Potential Respective to the Separation Distance
1.1E+02
9.0E+01
7.0E+01
5.0E+01

Potential Energy, H/KB*T 3.0E+01


1.0E+01
-1.0E+010

20

40

60

80

100 120

-3.0E+01
-5.0E+01

Separation Distance, H (nm)

Figure 2. Figure below describes the lowering in potential energy (increase in thermodynamic
stability) of colloid flocculation with respect to increasing colloid size from 1 nm to 20 nm.

DLVO Plot for Varying Gold Colloid Radii in R-CH3 Solution


1.0E+00
0.0E+00

20

40

60

80

100

-1.0E+00
1 nm
5 nm -2.0E+0010 nm
Potential
Energy, H/KB*T

15 nm

20 nm

-3.0E+00
-4.0E+00
-5.0E+00
Separation Distance, H (nm)

Figure 3. Figure below describes the drop in coagulation energy barrier with respect to the
increasing solution ionic strength from 1mol/m3 to 20 mol/m3.

DLVO Plot for the for Varying Ionic Concentrations of Gold Colloid in R-CH3 Solution
1.00E+01
0.00E+00
10
5 mol/m3
100 mol/m3
-1.00E+01

1 mol/m3

Potential Energy, E/KB*T

25 mol/m3

2015 mol/m3
30
40

50 mol/m3
60
20

-2.00E+01
-3.00E+01
-4.00E+01
-5.00E+01
-6.00E+01

Separation Distance, H (nm)

DLVO Plot for -48 mV Zeta Potential for Varying Gold Colloid Radii in R-CH3 Solution
1.50E+01
1.00E+01
5.00E+00

Potential Energy,H/KB*T
0.00E+00

10

20

30

40

50

-5.00E+00
-1.00E+01

Separation Distance, H(nm)


1 nm

5 nm

10 nm

15 nm

20 nm

60

70

DLVO Plot for - 48mV Zeta Potential for Varying Ionic Concentrations for Gold Colloid in R-CH3 Solution
1.5E+02
1.0E+02
5 mol/m3
10 mol/m3

1 mol/m3

15 mol/m3

20 mol/m3

5.0E+01

Potential Energy, H/KB*T 0.0E+00

10

20

30

40

50

60

-5.0E+01
25 mol/m3

-1.0E+02
-1.5E+02

Separation distance, H (nm)

Young's Equation Plot for the Contact Angles of each Respective droplet's Surface Tension
1

f(x) = 106.41x - 1
R = 0.97

0.8
0.6

Cos

0.4
0.2
0
0.01

0.01

0.01

0.01

0.01

0.02

0.02

0.02

0.02

(YLV)^-1/2 m/mN

Table 6. Table of values for the measured droplet angles on the methyl terminated gold surface
with corresponding YLV surface tension values.
Compound
Droplets

Left
Angle
(Degrees
)

Right Angle
(Degrees)

Cos Avg. Angle


(Radians)

SV

LV
Surface
Tension
(mN/m)

Decane

2.14E+0
1
3.56E+0
1

2.31E+01

9.25E-01

1.06E+02

23.9

Inverse
Root LV
Surface
Tension
(mN/m)
2.09E-02

4.19E+01

7.85E-01

1.06E+02

28.5

1.75E-02

Decanol

SL

1.29E+0
2
1.34E+0
2

Diethylene
glycol
Ethylene
glycol
Glycerol

5.99E+0
1
7.30E+0
1
7.93E+0
1

5.73E+01

5.21E-01

1.06E+02

44.8

1.12E-02

7.15E+01

3.04E-01

1.06E+02

47.7

1.05E-02

9.02E+01

9.16E-02

1.06E+02

64.0

7.81E-03

150E+02

Table 7. Table of values for the measured droplet angles on the acid terminated gold surface.
COOH
Ethanol
COOH
CH3
HCl
NaOH

Left Angle (Degrees)


6.59E+01
4.16E+01
8.80E+01
6.42E+01
2.74E+01

Right Angle (Degrees)


6.57E+01
5.18E+01
8.48E+01
6.26E+01
2.87E+01

Mean Angle (Degrees)


6.58E+01
4.67E+01
8.64E+01
6.34E+01
2.81E+01

Discussion:
Q1.
One recent application of colloid chemistry and self-assembled monolayers (SAMs) was
performed in 2014 at queens university by professor Cruddens research group. The project
involved using N-heterocyclic carbenes as ligands for gold surfaces. N-heterocyclic carbine
based SAMs on gold exhibit a large resistance to heat and chemical compounds in comparison
with thiol-based SAMs used in this experiment. This is due to the increased stability of gold
carbon bonds in comparison with gold-sulfur bonds. There are many applications for the use of
SAMs on gold, such as electrochemistry, drug delivery, surface protection, microelectronic, and
microelectromechanical systems.

C.M. Crudden, J.H. Horton, I.I. Ebralidze, O.V. Zenkina, A.B. McLean, B. Drevniok, Z. She, H.-

B. Kraatz, N.J. Mosey, T. Seki, E.C. Keske, J.D. Leake, A. Rousina-Webb, G. Wu, Ultra Stable
Self-Assembled Monolayers of N-Heterocyclic Carbenes on Gold Nature
Chemistry, 2014, 6,409-414.
Q2.
a.
The R-CH3 monolayer terminal methyl group is has mostly covalent bonding between the
hydrogens and carbon group and therefore exhibits a non-polar (not net dipole) properties.
Therefore when the droplets are added to theR-CH3 surface, the polarity of the compounds will

affect the interaction between the surface and the droplet. A greater interaction between the
surface and the droplet, signifies a greater wettability of the surface and therefore, a decreasing
contact angle between the droplet and the surface. It is expected that the contact angle between
the non-polar droplets would be smaller as a result of greater wettability of solid surface from the
droplet. Therefore the SL-SV value will be greater for the non-polar droplets. However as the
compound droplets become more polar, it is expected that the adhesive interaction between the
droplet and surface will decrease, and therefore cohesive forces take over and the resulting angle
is larger, and the SL-SV value will be smaller.
For the R-COOH terminated monolayer, the opposite trend is expected as the carboxylic
acid end has a net polarity, therefore as the compounds become more polar, the adhesive
interactions between the droplet and the surface are greater and therefore greater wettability
occurs and the resulting droplet angle decreases, and the SL-SV value will be progressively
larger.

b.
The effect on pH with the R-COOH terminated monolayer is quite simple, as the lower the pH is
for droplet, the greater the adhesion (and therefore lower contact angle) of the surface monolayer
to the droplet. This is due to simple acid base interactions between the surface and the droplet.
The low pH droplet interacts with the R-COOH by deprotonation. This reaction is described as
an acid-base equilibrium.
+ H 2 O K deprotonation K protonation
RC O2
RC O2 H +OH
Thermodynamically, the strong base has a greater stability as conjugate acid (H2O) in solution
because it no longer contains a free charge in solution. Furthermore the acetate anion is stabilized
by its resonance structure, and therefore the deprotonation is favoured and the adhesive
interaction occurs between the base droplet and acid terminated layer.
However as the pH is increased, the species becomes more acidic and thereby the equilibrium
shifts, and the deprotonation is no longer favoured thermodynamically, since the product has a
double charge that is very unstable.
Therefore as the pH increase the adhesive forces droplet to the surface are minimal and the
cohesive forces take over, the resulting droplet angle is significantly larger and the SL-SV value
will be less.
c.
Referring to table 6 and figure 6 in the results section for the CH3 terminated alkene agree with
the predicted trend made earlier on in the discussion for the contact angle, however the SL-SV
values are progressively increased as the droplet compounds increase in polarity.

d.
The relevance of setting the cos=1 represents is the critical surface tension (LV-critical ) of the
surface monolayer. This simply describes the characteristics of the solid only, and the cohesive
forces between the monolayers. This relationship makes sense because the contact angle =0,
and is assumed that the surface being ideally flat exhibits no interactions with a liquid droplet
that would form an angle greater than 0 with the surface.
3.
Figure 1 DLVO plot for the R-CH3 base colloid solution demonstrates at sharp peak near the xaxis that is indicative of the coagulation region of the colloid, when colloid precipitates out of
solution. This denotes the distance of colloid separation where the attractive potential is greater
than the repulsive potential and the colloid particles become destabilized. Following the
destabilization of the colloid, flocculation occurs whereby the destabilized colloid particles come
together to form flocs (precipitate) in solution. This can be seen in figure 1, as the maximum is
followed by a local minimum, which represents the flocculation region as the particles come
together and opposite charges negate each other and are more stabilized.
4.
The figure 3 DLVO plot in the CHEM 397 lab manual (page Q-5) source for a zeta
potential of -48 mV considering the ionic concentration of 1.6 mol/m3 in comparison to the ionic
concentration of 1.27 mol/m3 (-29.9mV) from the DLVO plot in this experiment, the colloid
solution is very stable, as there is a high potential energy barrier to overcome in order to
coagulate. This suggests that the solution will coagulate at a slower rate in comparison with the
results from figure 1 in this experiment, where the potential energy barrier is significantly lower.
Furthermore the distance required for flocculation from the coagulation region is larger for this
solution (~40-45 nm) in comparison with the results obtained for the solution in this experiment
(~10 nm). This indicates that the higher zeta potential unstable colloids require a larger
separation distance in order to flocculate.
5. The minimum separation distance for a colloid solution represents the distance at which the
interactions between colloids is so large that the forces of interaction become no longer
dominant. In the case for this experiment, based off figure 1, the minimum separation distance to
maintain the stability of the RCH3 base colloidal solution is approximately 70 +/- 10 nm.
However for the plotted figure replacing the experimental zeta potential with a potential of -48
mV, the minimum separation distance is thereby ~100+/- 10 nm. This may be due to the greater
repulsion effects from the resulting larger zeta potential values that effect potential energy
between colloids.
6.
Figure 2 DLVO plot for the varying colloid radii in solution at the experimental zeta potential
value, the observed trend is that the flocculation minima potential energy decreases as the radius
of the colloid increases. This may be attributed to the larger charge distribution among the
colloid that minimizes the coulombic repulsion between like charges and therefore is more stable

in energy as an aggregate. However the trend for the DLVO plot for figure 4 (-48 mV) is vastly
different from that of figure 2. Not only does the flocculation region decrease, but the
coagulation activation energy barrier increases significantly, and at a much lower separation
distance, which might signify that at larger zeta potential values the increase in colloidal radius
has a stronger force of attraction. However the rate at which the solution coagulates, is slower
due to steric hindrance as a results of larger colloid size, this makes sense in the trend for figure
4, as the increase in colloid radius increases the activation energy and therefore affects the rate.
7.
Figure 3 DLVO plot for the varying ionic concentrations at the experimental zeta potential value,
the observed trend is that coagulation activation energy barrier significantly decreases with
increasing ionic concentration, and therefore the rate of coagulation is kinetically faster. The
increase in concentration of ions in solution, the electrical double layer increases in density and
therefore Debye length is smaller as the charged colloid particles are more shielded. The increase
in ion concentration eventually leads to the collapse of the colloid double layer, as a result of the
Van der Waals attractive forces overcoming charge repulsion. Therefore the trend is decrease in
colloid stability as the ionic strength increases. Figure 5 DLVO plot for -48 mV varying ionic
concentrations demonstrates a very similar trend, however the drop in coagulation energy barrier
is more uniform in comparison with the figure 3 plot. The -value represents the viscosity of the
solution, and is what governs colloid coagulation due to Brownian motion. Brownian motion is
the bombardmenet of solute moleulces by the solvent in order to prevent the solvent from
settling out. Solvent bombardement is largely dependent on viscosity. As the viscosity increases
the solvent bombardement decreases and coagulation occurs.
Conclusion:

http://www.owlnet.rice.edu/~ceng402/proj02/cwynot/402project.htm
http://www.brookhaveninstruments.com/literature/library/colloidal-stability-in-aqueoussuspensions
http://pubs.acs.org/doi/pdf/10.1021/i360036a005
http://www.particles.org.uk/particle_technology_book/chapter_13.pdf
Sharfrin, E.; Zisman, William A. (1960). "Constitutive relations in the wetting of low energy surfaces and the
theory of the retraction method of preparing monolayers". The Journal of Physical Chemistry 64 (5): 519
524.doi:10.1021/j100834a002.

References:
1 Ulman, A. Formation And Structure of Self-Assembled Monolayers.Chemical
Reviews Chem. Rev. 15331554.

2 Bain, C. D. ; Whitesides, G. M. Modelling Organic Surfaces with SelfAssembled Monolayers. Harvard University of Cambridge Department of Chemistry.
May 1989.
3 Karim, A. Electrical Double Layer & Zeta Potential.
http://image.slidesharecdn.com/emulsionstability-130803053556phpapp02/95/emulsion-stability-10-638.jpg?cb=1375508255 (accessed Oct. 10,
2015). Copyright 2013 by Abd Karim.
4 Ali Hassanali and Sherwin J. Singer, ``A model for the water/amorphous
silica interface: the undissociated surface'', J. Phys. Chem. B111(38):11181 (2007).
5 Grahame, D. C. The Electrical Double Layer And the Theory of
Electrocapillarity. Chemical Reviews Chem. Rev. 441501.
[6] Hunter, R. J. Zeta Potential in Colloid Science: Principles and Applications,
New paperback.; Academic Press, 2013.
[7] Paul. Sennett and J. P. Olivier. COLLOIDAL DISPERSIONS, ELECTROKINETIC
EFFECTS, AND
THE CONCEPT OF ZETA POTENTIAL. Industrial & Engineering
Chemistry 1965 57 (8), 32-50
[8] http://www.malvern.com/en/products/product-range/zetasizerrange/zetasizer-nano-range/zetasizer-nano-zs90/

Das könnte Ihnen auch gefallen