Escolar Documentos
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edited by
Susan H. Hixson
NSF Highlights
Richard F. Jones
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II
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).
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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
n-heptane
n-heptane
The Experiments
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water
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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.
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water
514 506
510 504
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499 498
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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.
NSF Highlights
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.
Literature Cited
Acknowledgments
Instrumentation for this effort has been acquired through
the National Science Foundation Instrumentation and Laboratory Improvement Program and is gratefully acknowledged.
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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