Synthesis of Aqueous Ferrofluid

Laboratory Exercise 3


Morley, Jacob
CHEM 314 TA: Gulsah Uygur
11 February 2014






Morley 1

Background and Introduction
Magnetic nanoparticles in colloidal suspensions are deemed ferrofluids. A colloidal
solution is a suspension in which particles are sufficiently small to remain in solution and not
gravitationally settle rapidly. Ferrofluids are capable of aligning themselves with magnetic fields.
This laboratory exercise aimed to prepare ferrofluid with Fe
3
O
4
(magnetite) nanoparticles, via a
mixture of Fe (II) and Fe (III) salts in a basic solution. A surfactant was added to prevent the
nanoparticles from folliculating. Fe (II) and Fe(III) are both paramagnetic materials that contain
unpaired d-block electrons. Specifically, the unpaired electrons cause the paramagnetic field, as
paramagnetic molecules results from partially unfilled orbitals and can respond to magnetic
fields. The unpaired electrons with the parallel spins create the magnetic field. The ferrofluids
exhibit spikes when acted upon by a strong magnet.
For synthesis, the relevant reaction is as follows:
2FeCl
3
+ FeCl
2
+ 8NH
3
+ 4H
2
O Fe
3
O
4
+ 8NH
4
Cl
The resulting magnetite is then mixed with aqueous tetramethylammonium hydroxide to
complex the magnetite with tetramethylammonium cations and hydroxide anions and to induce
repulsion between the magnetite (Fig 1.1).

Fig. 1.1. Role of tetramethylammonium hydroxide from [2].
Beyond the Curie temperature, a temperature at which solids begin to lose their magnetic
properties as heat prevents their electrons from aligning in magnetic domains, magnets are
suboptimal [3]. Accordingly, ferrofluids can serve to augment traditional magnet application in
environments in which traditional magnets are suboptimal [4].


Morley 2

Experimental Procedure
Four mL of 1M FeCl
3
and 5mL of 2M FeCl
2
were added to a clean 100mL beaker. A
glass stirring rod was used to stir the solution while a pipette was used to add 50mL of 1M
aqueous NH
3
dropwise from a 100mL beaker at a rate of approximately 10mL/minute. The
magnetite was allowed to settle, during which a strong magnet was placed beneath the solution
for settlement acceleration. With the magnet still beneath the solution, the solution was decanted
and the clear fluid was discarded. The solid magnetite was transferred into a weigh boat with the
magnet beneath to ensure efficient transfer. A wash bottle was used to remove additional
magnetite. This process was repeated to remove any additional liquid. Two mL of 25%
tetramethylammonium hydroxide were added to prevent aggregation (i.e. as a surfactant). After 1
minute of stirring, with a magnet beneath the weigh boat, the dark liquid was decanted and
discarded, with the solid preserved. The magnet was moved below the weigh boat to explore the
properties of the ferrofluid. Spiking was recorded.

Morley 3

Data and Observations
Procedural Step Observation
Associated Reaction/
Molecular Interaction
Mixing of FeCl
3
and
FeCl
2

Orange FeCl
3
and light green FeCl
2

mixture forms clear-orange mixture
2FeCl
3
+ FeCl
2
+ 8NH
3
+
4H
2
O Fe
3
O
4
+ 8NH
4
Cl Addition of aqueous
NH
3

Mixture turns a deeper orange.
Reaction mixture turns from orange
to brown-red to dark brown to black.
Solid black particles settle
gravitationally.
Decanting of solution
Extremely viscous liquid/nearly solid
black remains. Removed liquid is
clear (i.e. no black magnetite visible).
--
Addition of
N(CH
3
)
4
+
OH

,
decanting
Solution remains black, increases in
viscosity.
N(CH
3
)
4
+
OH

ionized and ions

surround magnetite to create
electrostatic repulsion between
the particles
Ferrofluid testing
Spiking occurs in alignment to
magnetic field lines, moves
dynamically. Spiking height appears
proportional to 1/r
2
, where r denotes
the distance of the magnet to the
weight boat.
--
Fig. 2.1. Procedural Observations
Results and Calculations
There are no quantitative calculations for this laboratory exercise. All observations were listed in
the Data and Observations section.


Morley 4

Conclusion and Discussion
This laboratory exercise aimed to recognize and explain the effects that magnetic field
has on paramagnetic materials using a ferrofluid synthesis. A colloidal suspension of Fe
3
O
4

nanoparticles was successfully generated by mixing Fe(II) and Fe(III) salts in a basic solution.
Slow addition of aqueous ammonia prevented folliculation of solutioni.e. prevents
aggregation. The black solid that gradually formed following addition of aqueous NH
3
was
magnetite precipitating out of the resultant ammonium chloride solution. Addition of
tetramethylammonium hydroxide, as a surfactant, created a dipole interaction with the magnetite
particles as ions surround magnetite to create electrostatic repulsion between the particles and
thereby prevented aggregation. The magnetic quality of the ferrofluid was assessed using a
strong magnet. The ferrofluid exhibited spiking in alignment with the magnetic field. The
magnitude of the spikes in the ferrofluid were inverse square proportional to the distance of the
magnet to the solution, e.g. moving the magnet twice as close appeared to result in a peak four
times the previous height.
The solutions began orange with FeCl
3
and light green with FeCl
2,
the mixture of which
formed a clear-orange mixture. The subsequent mixture turned a deeper orange with addition of
ammonia. With more ammonia addition, the reaction mixture turned from orange to brown-red
to dark brown to black. During the addition, solid black particles (magnetite) settled
gravitationally. After decanting, extremely viscous liquid remained. The removed liquid was
clear (i.e. no black magnetite visible). After the addition of and decanting of excess
N(CH
3
)
4
+
OH

, spiking occurred in alignment to magnetic field lines, moves dynamically.

Spiking height appeared proportional to 1/r
2
, where r denotes the distance of the magnet to the
weight boat.



Morley 5

Questions
Associated chemical reaction
Main: 2FeCl
3
+ FeCl
2
+ 8NH
3
+ 4H
2
O Fe
3
O
4
+ 8NH
4
Cl
Surfactant: Fe
3
O
4
+ nN(CH
3
)
4
OH Fe
3
O
4
nOH
-1
nN(CH
3
)
4
+

(complex)
Type of magnetism and other materials that exhibit it
CoFe
2
O
4
and MnFe
2
O
4
are also superparamagnetic, resulting from inverse spinel
structures [2]. Accordingly, these structures are also ferrimagnetic, which results from the
fact that opposing magnetic moments are unequal in magnitude. That is, there exists
spontaneous magnetization via paramagnetic tendencies due to nonpareil electrons
(partially filled orbitals).

What happens when magnet is moved?
Movement of the magnet results in the reorientation of the ferrofluid spikes. The spikes
realign with the field lines associated with magnetic field. Accordingly, continuous
movement of the magnet induces continuous movement of the spikes. When the magnet
is moved away from the sample (vertically), the height of the spikes appears to decrease
proportional to 1/d
2
, where d is the distance between the magnet and the ferrofluid.
Chemical reaction at each step
See Fig. 1.1 (Data and Observations) for full review of chemical reactions at each step.

Morley 6

References

[1] IMRA America (2012). "IColloid." Icolloid. N.p., n.d. Web. 28 Jan. 2014.
[2] Berger, P.; Adelman, N. B.; Beckman, K. J.; Campbell, D. J.; Ellis, A. B.; Lisensky, G. C.
Journal of Chemical Education 1999, 76, 943-8.
[3] Conde, J.; Rosa, J; Lima, J.C.; Baptista, P.V. (2012). "Nanophotonics for Molecular
Diagnostics and Therapy Applications". International Journal Photoenergy 2012.
[4] L. Li et al., Chemistry, (2010), 122, 895.