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Chemical Education Today

edited by
Susan H. Hixson

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National Science Foundation


Arlington, VA 22230

Projects Supported by the NSF Division of Undergraduate Education

Richard F. Jones

Spectroscopic Determination of Ternary


Phase Diagrams

Sinclair Community College


Dayton, OH 45402-1460

by Kerry K. Karukstis,* Sara K. Avrantinis, Stephanie L. Boegeman, Jeanie N. Conner,


Blaine M. Hackman, Jennifer M. Lindsay, Alexander L. Mandel, and Elizabeth J. Miller

Chemists employ phase diagrams as convenient tools to


convey information about the thermodynamically stable
phases of a system under a given set of conditions. Ternary
phase diagrams describe phase equilibria among three
components as a function of composition at constant
temperature and pressure. For a system of three components,
a two-dimensional phase diagram is constructed at fixed
temperature and pressure by using an equilateral triangle for
graphic representation. Chemists often use such diagrams to
characterize the phase behavior in systems of alloys,
surfactants, polymers, and lipids.
Among the simplest examples of the behavior of threecomponent systems is a system of three liquids (A, B, C) in
which two liquids (A, B) are partially miscible with each other
and completely miscible with the third (C). The ternary phase
diagram for partially miscible liquid systems is generally determined in an undergraduate laboratory experiment by solely
visual methods. This phase diagram consists of two well-demarcated regions, as illustrated in Figure 1. There is a onephase liquid region, I, in which all three liquids mix to form
a miscible solution. A second region, II, indicates compositions where two immiscible liquid phases exist. This region

I
II

is separated from the one-phase region by a boundary curve.


Within the two-phase region are tie lines (not necessarily parallel) with endpoints representing the compositions of the two
immiscible liquid phases in equilibrium. One liquid is rich
in A, while the other liquid is characterized as B-rich. Here,
the slope of the tie lines indicates that component C preferentially distributes in the A-rich liquids.
As a novel approach to characterizing three-component
phase diagrams, we have demonstrated that the ternary phase
diagram of n-propanoln-heptanewater can be accurately
and conveniently constructed using either absorbance or fluorescence spectroscopic measurements. This experiment is
readily incorporated into a physical chemistry laboratory curriculum as a modern acquisition of a classic phase diagram.
In this ternary system, the apolar hydrocarbon n-heptane and
the polar solvent water are completely immiscible, while the
alcohol n-propanol is soluble with both liquids. Thus, the
ternary system of n-propanoln-heptanewater exhibits a region of liquid miscibility at high proportions of n-propanol.
Two immiscible liquid phases coexist when n-propanol is reduced in concentration. Our spectroscopic approach can be
used to determine both the phase boundaries and the tie lines
of the two-phase regions for mixtures of these three
components.
With the use of a conventional UVvisible spectrophotometer, the composition of the ternary mixtures can be characterized with the absorption probe methyl orange (4-[4(dimethylamino)phenylazo]benzene sulfonic acid, sodium
salt; MO; Fig. 2a). Similar determinations are possible with
the use of a steady-state fluorescence spectrophotometer and
A
Na+ O3S

Figure 1. A ternary phase diagram for three liquids in which liquids A and B are partially miscible with each other and completely
miscible with the third liquid, C. The apices of the triangle represent 100% of each liquid. Imaginary lines drawn parallel to the
AB side represent the various percentages of C; similar lines drawn
parallel to the BC and AC sides represent the percentage contributions from components A and B, respectively. The one-phase liquid region, I, is delineated from the region of two immiscible liquid phases, II. The endpoints of the tie lines in region II indicate
the compositions of the two immiscible liquid phases that are in
equilibrium when an overall solution composition is given by any
point on the tie line.

B
(CH3)2N
C

CH2CH3

O
Figure 2. The chemical structures of (a) the absorption probe methyl orange (4-[4-(dimethylamino)phenylazo]benzene sulfonic acid,
sodium salt; MO) and (b) the fluorescence probe Prodan (6propionyl-2-(dimethylamino)-naphthalene).

JChemEd.chem.wisc.edu Vol. 77 No. 6 June 2000 Journal of Chemical Education

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the fluorescence probe Prodan (6-propionyl-2-(dimethylamino)-naphthalene; Fig. 2b). These probes are selected for
their powerful spectral sensitivity to the polarity of their environment. For example, the absorption wavelength maximum of methyl orange shifts from 462 nm in an aqueous
solution to 394 nm in the nonpolar medium of cyclohexane
(1). Prodan exhibits a similar spectral shift of its emission
wavelength maximum as solvent polarity is reduced, from 520
nm in an aqueous environment to 388 nm in heptane (2).
As the immiscible liquids in the two-phase region of the npropanoln-heptanewater ternary diagram are essentially
water-rich and heptane-rich layers, the spectral signatures of
the probes in these two liquids are distinctive and identifiable. As the compositions of the liquids vary with solution
composition, wavelength shifts in the absorption or emission
maxima will result.

The ternary phase diagram is constructed by monitoring the wavelengths of methyl orange absorbance or Prodan
emission in solutions with varying weight percentages of npropanol, n-heptane, and water. To prepare the mixtures,
solvents are dispensed from burets, and then samples are

weighed after the addition of each liquid. Two features of


the phase diagram are specifically determined: (1) the boundary curve separating the homogeneous liquid-phase region
from the two-phase liquid region, and (2) the tie lines of the
two-phase region of liquidliquid immiscibility. To determine
the boundary curve between the one-phase liquid region and
the two-phase region of liquid-liquid immiscibility, various
mixtures of propanol and heptane are prepared and titrated
with water until the saturation point is reached (judged by
the appearance of a small amount of a second liquid phase).
The compositions of these saturated solutions are located on
ternary graph paper, and the boundary curve is drawn. An
aliquot of each saturated sample is then placed in a quartz
cuvette with the requisite amount of methyl orange or Prodan
probe. The appropriate absorption or emission spectrum is
collected, and the wavelength of maximum absorbance or
emission is noted. These spectral wavelengths are then recorded next to the composition points on the one-phase
liquid boundary curve. Solutions with an overall composition in the two-phase liquid region are prepared next, and
the two immiscible phases are then separated. Aliquots of the
separated liquid phases are then mixed with each probe. Absorption or emission spectra are then recorded for the two
coexisting liquid phases, and the wavelengths of maximum

n-heptane

n-heptane

The Experiments

402

400
461

442
454
476

412

474
476

413 413
415

477

415

479

484
417
418

417

488

419

493

420
465

water

449 436

426 425
430

423

415
419.5

n-propanol

Figure 3. The ternary phase diagram for the system n-heptanenpropanolwater as determined using the absorption probe methyl
orange. The numbers (unboxed) indicate the maximum MO absorption wavelength (max) in nm observed for solutions whose compositions are given by the filled circles ( ). These solutions correspond to the pure solvents and to solutions on the boundary curve
between the one-liquid and two-liquid phase regions. The filled
boxes ( ) indicate solutions with an overall composition in the
two-phase liquid region. These solutions separate into two liquid
phases whose compositions are indicated by the open boxes at
the endpoints of the dashed tie lines (
). The boxed numbers
indicate the max observed for MO in these coexisting liquid phases.

702

496

522

water

514 506
510 504

501

499 498

480

n-propanol

Figure 4. The ternary phase diagram for the system n-heptanenpropanolwater as determined using the fluorescence probe
Prodan. The numbers (unboxed) indicate the maximum Prodan
emission wavelength ( max) in nm observed for solutions whose
compositions are given by the filled circles ( ). These solutions
correspond to the pure solvents and to solutions on the boundary
curve between the one-liquid and two-liquid phase regions. The
filled boxes ( ) indicate solutions with an overall composition in
the two-phase liquid region. These solutions separate into two liquid phases whose compositions are indicated by the open boxes
at the endpoints of the dashed tie lines (
). The boxed numbers
indicate the max observed for Prodan in these coexisting liquid
phases.

Journal of Chemical Education Vol. 77 No. 6 June 2000 JChemEd.chem.wisc.edu

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absorption or emission are determined. Tie lines are then
drawn between the two compositions on the one-phase liquid boundary curve that exhibited absorption or emission
wavelengths most consistent with those observed for the immiscible phases.
Figures 3 and 4 present the ternary diagram obtained
by assessing the dependence of the absorption maximum of
methyl orange and the emission maximum of Prodan on system composition, respectively. The max values observed in
pure n-heptane, n-propanol, and water, respectively, are included and illustrate the increase in max with increasing solvent polarity.

difficult concepts depicted in the ternary diagramthat of


partial miscibility. By observing spectral wavelengths intermediate between those measured for the pure components,
students have direct evidence for the coexistence of two separate liquid phases with compositions distinct from the pure
components.

Advantages of This Experimental Approach

Literature Cited

This spectroscopic determination of the ternary phase


diagram of n-propanoln-heptanewater illustrates a novel
approach to the characterization of phase equilibria. Such a
visual tool provides students with a more modern analytical
method to examine this classic ternary system. With a conventional UVvisible spectrometer and a common acidbase
indicator or with a steady-state fluorescence instrument and
a readily available probe, an accurate ternary phase diagram
can be constructed in one or two laboratory periods. Furthermore, with a spectroscopic signal to characterize solution
composition, students more readily grasp one of the more

Acknowledgments
Instrumentation for this effort has been acquired through
the National Science Foundation Instrumentation and Laboratory Improvement Program and is gratefully acknowledged.

1. Karukstis, K. K.; Savin, D. A.; Loftus, C. T.; DAngelo, N.


D. J. Colloid Interface. Sci. 1998, 203, 157163.
2. Karukstis, K. K.; Frazier, A. A.; Martula, D. S.; Whiles, J. A.
J. Phys. Chem. 1996, 100, 1113311138.

Kerry K. Karukstis is a member of the Department of Chemistry, Harvey Mudd College, Claremont, CA 91711; email:
Kerry_Karukstis@hmc.edu. Sara K. Avrantinis, Stephanie L.
Boegeman, Jeanie N. Conner, Blaine M. Hackman, Jennifer M.
Lindsay, Alexander L. Mandel, and Elizabeth J. Miller are undergraduates in the department.

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