You are on page 1of 4

In the Classroom

edited by

Todd P. Silverstein
Willamette University
Salem, OR 97301-3922

Salting Effects as an Illustration of the Relative


Strength of Intermolecular Forces
Eric C. Person* and Donnie R. Golden
Department of Chemistry, California State University, Fresno, Fresno, California 93740-8034,
United States
*eperson@csufresno.edu
Brenda R. Royce
University High School, Fresno, California 93740, United States

Understanding intermolecular forces and their relative


strengths is an essential learning objective for any high school
or general chemistry course. There are a wide variety of demonstrations illustrating the impact of intermolecular forces on the
properties of materials including viscosity (1), surface tension (2),
and vapor pressure (3), but few look at the relative strength of
these forces. Solubility offers another way to illustrate these
concepts and introduce the important role that solubility will
play in upper-division chemistry courses.
In the simplest terms, a solute will be soluble in a solvent
if the strength of the intermolecular forces formed between the
solute and solvent molecules are stronger, resulting in a lower
total potential energy, than the intermolecular forces found in
the pure substances. In this way, the relative solubility of species
can be used as a means to compare the strength of intermolecular
forces that are formed in solutions.
An example of this relative solubility is the salting out
of nonelectrolytes from aqueous solutions upon the addition of
electrolytes. In this demonstration isopropyl alcohol, a nonelectrolyte, becomes immiscible with water after the addition of
ammonium sulfate, a strong electrolyte. At a simple level, once a
sufficient quantity of the electrolyte is added to the solution,
water molecules must choose between forming ion-dipole interactions with the dissolved electrolytes and weaker dipole-dipole
or hydrogen-bonding interactions with the nonelectrolytes. As
the water molecules solvate the ions, the nonelectrolytes are
pushed out of solution and will transfer to or form separate
phases.
Several demonstrations of these salting effects have been
described in the literature. Shakhashiri describes salting of
methanol from an aqueous solution using potassium carbonate
leading to a discussion of phase diagrams and the Gibbs phase
rule (4). Smith modified this procedure using ethanol, sodium
carbonate, and bromthymol blue to help visualize the formation
of separate phases in a classroom setting (5). This demonstration
modifies Smith's procedure in three substantive ways. First, the
acid-base color change is removed, as the concept may not have
been covered in lecture prior to the discussion of intermolecular forces. Second, the demonstration uses materials students
are already familiar with: rubbing alcohol, food coloring, and
fertilizer. Third, an additional portion of water is added reforming a single phase to emphasize that the separation of layers is the
result of a competition of the relative strength of the intermolecular forces that can form between two solutes and a limited
number of solvent molecules.
1332

Journal of Chemical Education

Demonstrations of salting interactions can provide a useful connection to organic chemistry, as salting effects are used
extensively in liquid-liquid and acid-base extractions. For
example, the use of saturated salt solutions (brine) to wash
organic extracts stems in part from two effects related to salting:
first, the brine solution partially dries the organic layer by
drawing dissolved water out to form more favorable interactions
with dissolved ions, and second, the high salt concentration significantly reduces the solubility of any organic solutes
dissolved in the aqueous phase.
Procedure
Add 15 mL of water and one drop of food coloring to a
50 mL test tube (25  200 mm), cap with a rubber stopper, and
mix by inverting. Though most colors of food coloring can work
for this demonstration, green or blue food coloring are recommended as they provide a nice contrast and partition more
completely than yellow and red colors. Add 15 mL of rubbing
alcohol (70% isopropyl alcohol), cap, and mix by inverting
(Figure 1A). Add 7 g of ammonium sulfate that has been ground
to a powder (Figure 1B), cap, and mix by shaking vigorously
for 5-10 s (Figure 1C). Two distinct layers should form in
approximately 10-20 s on standing (Figure 2). A colorless layer
is observed forming from the bottom and increasing in size until
it is approximately 70% of the total solution volume. The food
coloring is dissolved in the top alcohol layer while the bottom

Figure 1. Images showing the steps of the main procedure described:


(A) 30 mL of the 35% isopropyl alcohol solution with one drop of blue
food coloring, (B) the alcohol solution after adding 7 g of powdered
ammonium sulfate, (C) the solution after shaking vigorously to aid the salt
in dissolving, (D) the solution after the layers have settled, and (E) the
solution after adding an additional 15 mL of water.

Vol. 87 No. 12 December 2010


pubs.acs.org/jchemeduc
r 2010 American Chemical Society and Division of Chemical Education, Inc.
10.1021/ed100315r Published on Web 10/08/2010

In the Classroom

Figure 2. Images showing the rapid separation of the aqueous and


isopropyl alcohol layers. The time required for the separation varies
between approximately 10 and 20 s after vigorous shaking of the
alcohol solution and added ammonium sulfate.

aqueous layer is nearly colorless (Figure 1D). If desired, use a


transfer pipet to remove approximately 1 mL of each layer and
place each layer in separate watch glasses for testing by conductivity or flammability. Add another 15 mL of water to the
remaining alcohol and water in the test tube, cap, and mix by
inverting the tube. A single, uniformly colored layer will be
observed immediately and persist indefinitely (Figure 1E). A
document camera system can be effectively used to visualize the
separation of layers if visibility of the demonstration is a concern
in larger classrooms.
The identity of the two layers formed after salting can easily
be determined using either a conductivity measurement or a
simple flammability test. To test for conductivity, use a simple
low voltage (9 V) conductivity indicator (e.g., Lab-Aids Kit
300) or an ohmmeter after cleaning the electrodes with steel
wool or emery paper to ensure good contact with the solution. A
document camera or other projection method may be required to
make the conductivity indicator visible in a large classroom. High
voltage conductivity indicators such as the conventional light
bulb apparatus may present a fire hazard if used with the alcohol
fraction. The colored alcohol layer will show low but nonzero
conductance. The colorless aqueous layer will show relatively
high conductivity. The layers can then be tested for flammability
with a match or a butane grill lighter. We generally ignite the
isopropyl alcohol layer first and then put the match out in the
aqueous layer. The alcohol layer should burn for at least 1 min
with sufficient yellow color to be easily visible in a classroom. The
flame can be easily extinguished by covering with another watch
glass if desired.
Variation
A variation on this procedure using sodium chloride in place
of ammonium sulfate creates some interesting effects with the
partitioning of the food coloring, which would facilitate discussion of relative solubility of organic molecules.
Prepare three large test tubes with 15 mL of water and
15 mL of 70% isopropyl alcohol. Add one drop of yellow food
coloring in the first test tube, one drop of green food coloring
in the second test tube, and one drop of blue food coloring to
the third test tube. Add 4.5 g of sodium chloride to each tube
and shake vigorously. The sodium chloride will take longer to
dissolve, but as it dissolves, two layers will appear in each of the
tubes (Figure 3). The green solution will split into a blue-green
top alcohol layer and a bright green aqueous layer. Both layers in

r 2010 American Chemical Society and Division of Chemical Education, Inc.

Figure 3. Images showing the colors formed by yellow, green, and blue
food coloring in 35% isopropyl alcohol before (A) and after (B) adding
sodium chloride as described in the variation. The blue-green color
formed in the alcohol layer for the green coloring results from the different
extent of partitioning of the blue and yellow dyes that make up the green
coloring.

the blue tube will be relatively evenly colored, while the yellow
tube will not show even color distribution. An additional 15 mL
of water can be added to each tube to restore the sample to a
single, uniformly colored layer.
Commonly Available Reagents
The reagents for this demonstration are inexpensive and
readily available in commercial products. Common rubbing
alcohol is a convenient source of 70% isopropyl alcohol. Ammonium sulfate fertilizer (21-0-0), which is essentially pure, is a
potential source of the salt for this demonstration. Food coloring
is available in most grocery stores. If reagent grade isopropyl
alcohol (99%) is used in place of rubbing alcohol, use 20 mL of
water and 10 mL of isopropyl alcohol instead of the volumes
listed above.
Hazards
As with all laboratory experiments and instructional
demonstrations utilizing chemicals and other hazardous materials, proper personal safety equipment including protective eyewear should always be used. Ammonium sulfate (CAS # 778320-2) is recognized as a mild irritant to human eyes and skin.
Caution should be taken when exposed because it can be
absorbed through the skin. Inhalation of the compound may
lead to respiratory tract infection. Isopropyl alcohol, also known
as isopropanol, does have some notable hazards associated with
its use. Isopropyl alcohol (CAS # 67-63-0) is a highly flammable
liquid having a flash point of only 12 C. Breathing of vapors
should be avoided. Inhalation can cause drowsiness, dizziness, and
respiratory infection. Isopropyl alcohol can also cause skin irritation, be absorbed through the skin, and may be harmful if
swallowed. Target organs include the kidneys, liver, nervous, cardiovascular and gastrointestinal systems. Appropriate care should
be taken to avoid fire hazards if using the flammability test on the
separate layers. At a minimum, the area should be free of other
combustible or flammable materials, the experiment should be
performed in an area with adequate ventilation, and fire suppression equipment such as fire extinguishers should be available.
Discussion
In general, a solute will be soluble in a solvent if the strength
of the intermolecular forces between the solute and solvent

pubs.acs.org/jchemeduc

Vol. 87 No. 12 December 2010

Journal of Chemical Education

1333

In the Classroom

particles is stronger than that of the interactions between the


separate pure substances. In this case, hydrogen bonds between
the alcohol and water are sufficiently strong to allow isopropyl
alcohol and water to be miscible in all proportions. Most waterbased food coloring dyes contain polar functional groups that
form strong dipole-dipole interactions with water including
hydrogen bonds that allow them to be quite soluble in water.
Take time before adding the salt to emphasize these solubility
properties. Adding food coloring to water before adding the
isopropyl alcohol demonstrates the solubility of the visible food
coloring dye in both water and alcohol, creating an opportunity
for a deeper discussion surrounding which layer is colored after
salting.
Ammonium sulfate is also soluble in water due to the
strength of the ion-dipole attractions between ammonium
and sulfate ions with the water molecules. Small quantities of
ammonium sulfate (3 g for the 30 mL volume described) will
dissolve in the 35% isopropyl alcohol solution formed in the
demonstration without forming a second layer. As additional salt
is added, there is insufficient water to completely solvate both the
ammonium sulfate and the isopropyl alcohol. In this situation,
water will favor the interactions with the lower potential energy
resulting from stronger intermolecular forces. The displacement
of isopropyl alcohol to form a separate layer while the ammonium sulfate dissolves completely illustrates that the ion-dipole
interactions formed between water and ammonium sulfate are
stronger than the hydrogen bonds formed between water and
isopropyl alcohol. The significant reduction of solubility of
nonelectrolytes such as isopropyl alcohol on the addition of high
salt concentrations is typically referred to as salting. The solubility of the salt in the solution is also significantly reduced by the
presence of isopropyl alcohol in the aqueous layer. Food coloring
provides a convenient way to visualize the formation of these
layers in part because it is also subject to the salting effects
pushing it out of the aqueous layer. The isopropyl alcohol layer
will have a density of approximately 0.87 g/mL causing it to sit
on top of the aqueous layer with a density of approximately
1.16 g/mL. The addition of a second portion of water provides
sufficient water to solvate both the ammonium sulfate and
isopropyl alcohol allowing a single layer to form again.
The quantity of ammonium sulfate recommended is below its
solubility limit in the alcohol solution so that it will all dissolve
quickly and so that a single layer can be formed upon addition of
the second portion of water. If too much color is still evident in the
aqueous layer for the instructor's preference, additional ammonium
sulfate will essentially eliminate any detectable color in the aqueous
layer. Blue food coloring will show more complete transfer to the
alcohol fraction than the green coloring and significantly more
than the red or yellow coloring in a typical box of McCormick
brand food coloring. If more salt is added, more water may be
required to reform a single layer and some solid ammonium sulfate
may appear as a third layer at the bottom of the tube.
The type of salt added to this demonstration is not critical
and can have interesting effects on the partitioning of the color.
All electrolytes may show salting effects to some degree. Ammonium sulfate was used in this demonstration because it is
inexpensive, dissolves rapidly, and has the relatively strong salting
effects necessary to displace the hydrogen bonding of isopropyl
alcohol. The strength of the salting effects depends on the ionic
strength of the electrolyte solution. This in turn depends on the
charges of the ions and the overall solubility of the salt. As shown
1334

Journal of Chemical Education

Vol. 87 No. 12 December 2010

Figure 4. The chemical structures of FD&C Yellow #5 and FD&C


Blue #1, the two dyes used in McCormick green food coloring.

in the described variation, sodium chloride also shows salting


effects and will form separate layers, but concentrations near
saturation are necessary and do not form as quickly as the
demonstration with ammonium sulfate.
The described variation using sodium chloride takes slightly
more time to form separate layers, but illustrates an interesting
difference in the effect of salt on the two dyes that make up
McCormick's green food coloring: FD&C Blue 1 and FD&C
Yellow 5 (6). The chemical structures of these two dyes are
shown in Figure 4. Whereas the sodium chloride is able to
sufficiently displace the isopropyl alcohol to form two layers, it
has different effects on these two dyes as observed in Figure 3.
The top layer of the center tube appears blue instead of green
because the alcohol layer contains significantly more of the blue
dye than the yellow dye due to differences in their partitioning
between the brine and alcohol layers, likely caused by a combination of differences in their relative hydrophobic character and
hydrogen bonding potential. FD&C Yellow #5 has two charged
sulfonate groups, two azo nitrogens, and a phenol with good
potential to form hydrogen bonds with water due to minimal
steric hindrance. FD&C Blue #1 shows increased hydrocarbon
character with five benzene rings instead of only three. Although
FD&C Blue #1 has four charged groups, the resonance structure
with the positive charge on the central carbon atom is considerably stabilized as a tight ion pair with the neighboring ortho
sulfonate group (supported by molecular modeling). Finally, the
nitrogen atoms in FD&C Blue #1 are expected to have reduced
hydrogen bonding potential due to steric hindrance and the
resonance structures involving their lone pairs of electrons.
Acknowledgment
The authors would like to thank Angie Person for assistance
with the photography and digital photo processing. Catherine
Banks (Department of Chemistry, Peace College, Raleigh, NC)
is thanked for checking this demonstration.
Literature Cited
1. Shakhashiri, B. Z. Chemical Demonstrations;A Handbook for
Teachers of Chemistry; The University of Wisconsin Press: Madison,
WI, 1989; Vol. 3, p 313-316.

pubs.acs.org/jchemeduc

r 2010 American Chemical Society and Division of Chemical Education, Inc.

In the Classroom
2. Shakhashiri, B. Z. Chemical Demonstrations;A Handbook for
Teachers of Chemistry; The University of Wisconsin Press: Madison,
WI, 1989; Vol. 3, p 301-304.
3. Shakhashiri, B. Z. Chemical Demonstrations;A Handbook for
Teachers of Chemistry; The University of Wisconsin Press: Madison,
WI, 1989; Vol. 3, p 242-248.
4. Shakhashiri, B. Z. Chemical Demonstrations;A Handbook for
Teachers of Chemistry; The University of Wisconsin Press: Madison,
WI, 1989; Vol. 3, p 266-268.

r 2010 American Chemical Society and Division of Chemical Education, Inc.

5. Smith, E. T. Chem. Educator 1996, 1; http://chemeducator.org/


sbibs/samples/spapers/11smi897.htm (accessed May 2009).
6. McCormick Product Detail - Green Food Color. http://www.
mccormickgourmet.com/ productdetail.cfm?id=6036 (accessed May
2009).

Supporting Information Available


Video of the demonstration using green food coloring and ammonium
sulfate. This material is available via the Internet at http://pubs.acs.org.

pubs.acs.org/jchemeduc

Vol. 87 No. 12 December 2010

Journal of Chemical Education

1335

You might also like