EXPERIMENT 5

TITLE : Preparation and Precipitation of Lyophobic Colloid

OBJECTIVE :

i. To prepare manganum dioxide (MnO2) sol.

ii. To test the Schulze – Hardy rule.

THEORY

The term “colloid” was first introduced by Thomas Graham (1861) A colloid
system consists of a dispersion phase and a dispersion medium. If the diameter of the
dispersed particles is in a range between 20 A to 2000 A, then a colloid is formed.

There are eight classes of common colloidal systems. These colloids are made-up
of solids, liquid and gases. A colloid formed by the dispersion of a solid in a liquid is
called a sol. Sols exhibit several physical properties such as Tyndall effect, electrical
effect and molecular-collision effect.

In general, sol can be classified into two types; The terms lyophilic (liquid-loving)
and lyophobic (liquid-hating) are frequently used to describe the tendency of a surface or
functional group to become wetted or solvated. If the liquid medium is aqueous, the terms
hydrophilic and hydrophobic are used.

Lyophilic surfaces can be made lyophobic, and vice versa. For example, clean glass
surfaces, which are hydrophilic, can be made hydrophobic by a coating of wax;
conversely, the droplets in a hydrocarbon oil-in-water emulsion, which are hydrophobic,
can be made hydrophilic by the addition of protein to the emulsion, the protein molecules
adsorbing on to the droplet surfaces.

Lyophilic sol can be prepared by dispersion (normally by vigorous stirring of a

solid in the form of gel or resin in a liquid), and condensation. During dispersion, solids
are disintegrated into particles of suitable sizes to form a colloid in a dispersion medium.
During condensation however, molecules or atoms are condensed into clusters / particles
of suitable sizes to form a colloid.

Lyophobic colloids are very sensitive to the presence of electrolytes, in which a

small amount of added electrolytes resulted in precipitation. The precipitation of sol by
electrolytes can be predicted using Schulze – Hardy rule, which stated that “The effect of
precipitation by a given ion on a (lyophobic) dispersed phase of opposite charge increases
by the increase of the valency of the ion”.
METHODOLOGY

Part A: Preparation of manganum dioxide, MnO2

3 ml of 30% H2O2
+
50 ml of distilled water

Solution prepared filled into the burette

50 ml of 0.02M KMnO4 solution introduced into a clean and dry conical flask

The diluted H2O2 solution added into the 0.02M KMnO4 solution drop-by-drop while
swirling the conical flask.

H2O2 solution added until the color of the KMnO4 solution turns brown.

A drop of the brown-colored solution taken and tested using 1.0ml of BaCl2 solution.

If a pinkish solution is observed, some more of H2O2 added into the KMnO4 solution until
a pinkish solution CANNOT be further observed.

DO NOT ADD too much H2O2 to avoid precipitate formed.

Part B: Verification of the Schulze – Hardy Rule.

1 2 3 4
Clean test tubes labeled

10 ml of 0.10M NaCl solution added into test tube number 1.

1 ml of the same solution and 9 ml of distilled water added into test tube number 2, and
then homogenize the solution by swirling.

1 ml of the NaCl solution from the test tube number 2 transferred into the test tube
number 3, and then 9 ml of distilled water added.

Further dilution performed on the NaCl solution in the test tube number 4.

1 ml of the MnO2 sol added into each test tube containing the NaCl solutions.

The test tubes mildly swirled and in 2 minutes time, the one which form a precipitate
observed. The concentration of the NaCl solution recorded.

After the results obtained, further tests performed using NaCl solutions with
concentrations lower than the lowest concentration that yielded a precipitate.

Steps repeated using CaCl2 and AlCl3 solutions.

DATA / RESULTS

A) Preparation of manganum dioxide (MnO2) sol.

Initial reading (cm 3) 1.9

final reading (cm 3) 5.1
Volume of H2O2 solution used (cm 3) 3.2

B) Verification of the Schulze - Hardy rule.

Guideline:
√ = precipitate exist
Х = precipitate do not exist

Concentration of Volume of NaCl Volume of distilled Observation of

NaCl (M) (ml) water (ml) precipitate (√ / Х)
0.1 10.0 0.0 √
0.08 8.0 2.0 √
0.06 7.5 2.5 √
0.04 6.7 3.3 √
0.02 5.0 5.0 Х
0.01 1.0 9.0 Х
0.001 1.0 9.0 Х
0.0001 1.0 9.0 Х

Minimum concentration: 0.04 M

Concentration of Volume of CaCl2 Volume of distilled Observation of

CaCl2 (M) (ml) water (ml) precipitate (√ / Х)
0.1 10.0 0.0 √
0.01 1.0 9.0 √
0.001 1.0 9.0 √
0.0008 8.0 2.0 √
0.0006 7.5 2.5 √
0.0004 6.7 3.3 √
0.0002 5.0 5.0 Х
0.0001 1.0 9.0 Х

Minimum concentration: 0.0004 M

 Concentration of Volume of AlCl3 Volume of distilled Observation of
AlCl3 (M) (ml) water (ml) precipitate (√ / Х)
0.1 10.0 0.0 √
0.008 8.0 2.0 Х
0.006 7.5 2.5 Х
0.004 6.7 3.3 Х
0.002 5.0 5.0 Х
0.01 1.0 9.0 √
0.001 1.0 9.0 Х
0.0001 1.0 9.0 Х

Minimum concentration: 0.01 M

CALCULATION
Dilution of NaCl solution:

Used the equation: M1V1 = M2V2

From the equation,
M1V1 = M2V2
(0.1 M) V1 = (0.04 M) (10.0 ml)
V1 = 4.0 ml
Volume of 0.1 M NaCl solution been used = 4.0 ml
Volume of distilled water been used = 6.0 ml
So, the minimum concentration of NaCl solution = 0.04 M
By using the same method, we can determine the volume of NaCl (ml) to use for
preparing the concentration of NaCl (M).

1) For 0.08 M NaCl

M1V1 = M2V2
(0.1 M) V1 = (0.08 M) (10.0 ml)
V1 = 8.0 ml

2) For 0.06 M NaCl

M1V1 = M2V2
(0.08 M) V1 = (0.06 M) (10.0 ml)
V1 = 7.5 ml

3) For 0.04 M NaCl

M1V1 = M2V2
(0.06 M) V1 = (0.04 M) (10.0 ml)
V1 = 6.7 m

4) For 0.02 M NaCl

M1V1 = M2V2
(0.04 M) V1 = (0.02 M) (10.0 ml)
V1 = 5.0 ml

5) For 0.01 M NaCl

M1V1 = M2V2
(0.1 M) V1 = (0.01 M) (10.0 ml)
V1 = 1.0 ml

6) For 0.001 M NaCl

M1V1 = M2V2
(0.01 M) V1 = (0.001 M) (10.0 ml)
V1 = 1.0 ml

7) For 0.0001 M NaCl

M1V1 = M2V2
(0.001 M) V1 = (0.0001 M) (10.0 ml)
V1 = 1.0 ml
Dilution of CaCl2 solution:

Used the equation: M1V1 = M2V2

From the equation,
M1V1 = M2V2
(0.001 M) V1 = (0.0004 M) (10.0 ml)
V1 = 4.0 ml
Volume of 0.001 M CaCl2 solution been used = 4.0 ml
Volume of distilled water been used = 6.0 ml
So, the minimum concentration of CaCl2 solution = 0.0004 M

By using the same method, we can determine the volume of CaCl2 (ml) to use for
preparing the concentration of CaCl2 (M).

1) For 0.0008 M CaCl2

M1V1 = M2V2
(0.001 M) V1 = (0.0008 M) (10.0 ml)
V1 = 8.0 ml

2) For 0.0006 M CaCl2

M1V1 = M2V2
(0.0008 M) V1 = (0.0006 M) (10.0 ml)
V1 = 7.5 ml

3) For 0.0004 M CaCl2

M1V1 = M2V2
(0.0006 M) V1 = (0.0004 M) (10.0 ml)
V1 = 6.7 ml

4) For 0.0002 M CaCl2

M1V1 = M2V2
(0.0004 M) V1 = (0.0002 M) (10.0 ml)
V1 = 5.0 ml

5) For 0.01 M CaCl2

M1V1 = M2V2
(0.1 M) V1 = (0.01 M) (10.0 ml)
V1 = 1.0 ml

6) For 0.001 M CaCl2

M1V1 = M2V2
 (0.01 M) V1 = (0.001 M) (10.0 ml)
V1 = 1.0 ml

7) For 0.0001 M CaCl2

M1V1 = M2V2
(0.001 M) V1 = (0.0001 M) (10.0 ml)
V1 = 1.0 ml

Dilution of AlCl3 solution:

Used the equation: M1V1 = M2V2

From the equation,
M1V1 = M2V2
(0.1 M) V1 = (0.01 M) (10.0 ml)
V1 = 1.0 ml
Volume of 0.001 M AlCl3 solution been used = 1.0 ml
Volume of distilled water been used = 9.0 ml
So, the minimum concentration of AlCl3 solution = 0.01 M

By using the same method, we can determine the volume of AlCl 3 (ml) to use for
preparing the concentration of AlCl3 (M).

1) For 0.08 M AlCl3

M1V1 = M2V2
(0.1 M) V1 = (0.08 M) (10.0 ml)
V1 = 8.0 ml

2) For 0.06 M AlCl3

M1V1 = M2V2
(0.08 M) V1 = (0.06 M) (10.0 ml)
V1 = 7.5 ml

3) For 0.04 M AlCl3

M1V1 = M2V2
(0.06 M) V1 = (0.04 M) (10.0 ml)
 V1 = 6.7 ml

4) For 0.02 M AlCl3

M1V1 = M2V2
(0.04 M) V1 = (0.02 M) (10.0 ml)
V1 = 5.0 ml

5) For 0.01 M AlCl3

M1V1 = M2V2
(0.1 M) V1 = (0.01 M) (10.0 ml)
V1 = 1.0 ml

6) For 0.001 M AlCl3

M1V1 = M2V2
(0.01 M) V1 = (0.001 M) (10.0 ml)
V1 = 1.0 ml

7) For 0.0001 M AlCl3

M1V1 = M2V2
(0.001 M) V1 = (0.0001 M) (10.0 ml)
V1 = 1.0 ml

The minimum concentrations for the salt solution (NaCl, CaCl2 and AlCl3) are needed to
precipitate MnO2 sol in 2 minutes.
[NaCl] : [CaCl2] : [AlCl3]
0.04 M : 0.0004 M : 0.01 M
100 : 1 : 25
DISCUSSION

Colloid and interface science deals with multi-phase systems in which one or
more phases are dispersed in a continuous phase of different composition or state.
Classical colloid science deals with dispersions for which at least one dimension of a
dispersed phase falls within about 1 and 1000 nm. In applied colloid science the upper
size limit is commonly extended to at least 10 000 to 100 000 nm. Interface science deals
with dispersions in which there is an extremely large interfacial area between two of the
phases. The dispersed phases may be particles, droplets or bubbles.

Colloidal particles are larger than molecules but too small to be observed directly
with a microscope; however, their shape and size can be determined by electron
microscopy. In a true solution the particles of dissolved substance are of molecular size
and are thus smaller than colloidal particles; in a course mixture the particles are much
larger than colloidal particles. Although there are no precise boundaries of size between
the particles in mixtures, colloids or solutions, colloidal particles are usually on the order
of 10-7 to 10-5 cm in size.

The tendency of colloidal dispersions in a fluid state not to separate is aided by

the collisions that the dispersed particles experience from the constantly moving
molecules of the ‘solvent’. The erratic movement of colloidally dispersed particles caused
by such uneven buffeting is called Brownian movement after Scottish botanist, Robert
Brown (1773 – 1858). Colloidal dispersions that do eventually separate are those in
which the dispersed particles, over time, grow too large. Evidently, to prepare a stable
colloidal dispersion, we must not only make the dispersed particles initially small enough
but must also keep them from joining together. The dispersed particles will not coalesce if
they carry the same kind of electrical charge, either all positive or all negative. Ions of the
opposite charge are in the solvent, keeping the whole system electrically neutral. Some of
the most stable dispersions form when the surfaces of their colloidal particles have
preferentially attracted ions of just one kind of charge from a dissolved salt. The
dispersed particles of most sols, which are colloidal dispersions of solids in a fluid.
Alternatively, dispersions may form when extremely large, like-charged ions, such as
those of proteins, are involved.

Colloidal dispersions of one liquid in another are called emulsions. They are often
relatively stable provided that a third component called an emulsifying agent is also
present. Its molecules act to give an electrically charged surface to each microdroplet of
the oil, which keeps the microdroplets from coalescing. Water-in-oil emulsions are also
possible. Even when a beam of light is focused on a starch dispersion so dilute as to look
as clear as water, the path of the beam is revealed by the light scattered to the side. Light
scattering by colloidal dispersions is called the Tyndall effect, after John Tyndall (1820 –
1893), a British scientist. Solutes in true solutions, however, involve species too small to
scatter light, so solutions do not give the Tyndall effect.

From the experiment, there are some errors that may effects the results. Errors
while using apparatus such as the measuring cylinder and pipette. KMnO4 is dark in
colours that may cause to inaccurate value while measuring it. We also did not observe
the changes within 2 minutes. Some of the precipitate formed dissolve after 2 minutes.

Precaution Steps;
1. Use dry an clean conical flask.
2. Avoid overtitration with H2O2 to avoid precipitate form.
3. Observe the changes occurred within 2 minutes only.
4. Calculate the volume using the concentrations.

CONCLUSION
NaCl = Minimum concentration: 0.04 M
CaCl2 = Minimum concentration: 0.0004 M
AlCl3 = Minimum concentration: 0.01 M

The minimum concentrations for the salt solution (NaCl, CaCl2 and AlCl3) are needed to
precipitate MnO2 sol in 2 minutes.
[NaCl] : [CaCl2] : [AlCl3]
0.04 M : 0.0004 M : 0.01 M
100 : 1 : 25

REFERENCES

1. Chemistry matter and Its Changes, 3rd Edition

Brady, Russel and Holum
Pages 558 – 560

2. Atkins’ Physical Chemistry, 7th Edition

Atkins de Paula
Page 752
QUESTIONS

1. From the results of this experiment, determine whether the MnO2 sol is of
positively or negatively charged.

The MnO2 sol is negatively charged because the solution used contains some
cation such as Cl-, and other anion Al3+, Ca2+ and Na+.

2. By what method the MnO2 sol was prepared?

2MnO4- + 5H2O2 + 6H+ 2Mn2+ + 8H2O + MnO2-

2
The MnO sol was prepared by condensation method. It refers to the formation of
particles by precipitation reaction chemistry.

3. Supposed a soluble lyophilic sol was added into an MnO 2 sol prior to the addition
of an electrolyte, what would be the effect? Explain your answer.

By adding electrolyte after lyophilic are added to MnO2. so the precipitation are
MnO2 sol as we expect. Using H2O2 30% lyophilic sol charges positive. It can
not occur between MnO2 sols that are in negative charge with lyophilic sol that is
in charge positive. Complete precipitation will done during isoelectronic point are
reach.