Tanya L.
Myers
*,
Bruce E.
Bernacki
,
Michael J.
Wilhelm
,
Karissa L.
Jensen
,
Timothy J.
Johnson
,
Oliva M.
Primera-Pedrozo
,
Russell G.
Tonkyn
,
Steven C.
Smith
,
Sarah D.
Burton
and
Ashley M.
Bradley
Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352, USA. E-mail: tanya.myers@pnnl.gov
First published on 12th September 2022
This paper investigates the accuracy of deriving the composite optical constants of binary mixtures from only the complex indices of refraction of the neat materials. These optical constants enable the reflectance spectra of the binary mixtures to be modeled for multiple scenarios (e.g., different substrates, thicknesses, volume ratios), which is important for contact and standoff chemical detection. Using volume fractions, each mixture's complex index of refraction was approximated via three different mixing rules. To explore the impact of intermolecular interactions, these predictions are tested by experimental measurements for two representative sets of binary mixtures: (1) tributyl phosphate combined with n-dodecane, a non-polar medium, to represent mixtures which primarily interact via dispersion forces and (2) tributyl phosphate and 1-butanol to represent mixtures with polar functional groups that can also interact via dipole–dipole interactions, including hydrogen bonding. The residuals and the root-mean-square error between the experimental and calculated index values are computed and demonstrate that for miscible liquids in which the average geometry of the cross-interactions can be considered isotropic (e.g., dispersion), the refractive indices of the mixtures can be modeled using composite n and k values derived from volume fractions of the neat liquids. Conversely, in spectral regions where the geometry of the cross-interactions is more restricted and anisotropic (e.g., hydrogen bonding), the calculated n and k values vary from the measured values. The impact of these interactions on the reflectance spectra are then compared by modeling a thin film of the binary mixtures on an aluminum substrate using both the measured and the mathematically computed indices of refraction.
To this end, work has been undertaken in our laboratory to catalog the complex index of refraction for numerous liquids18 that can provide an alternative approach to identifying unknown liquid substances. In the event of chemical spills, for example, liquids are more likely encountered as thin films (submicron to 100's of microns) on metallic or dielectric substrates whereby both the substrate as well as the liquid contribute to the composite reflectance signature. By knowing the complex index of refraction of a liquid (as well as the substrate) the arrangement can thus be modeled (by varying liquid thickness, substrate type, angle of incidence, polarization) using methods such as ray tracing or thin film modeling along with the transfer matrix method (TMM)25 until a match is obtained for the previously unknown acquired signature. For the present purposes, the complex index of refraction is defined as below in eqn (1) where n(λ) governs the refraction and reflection of light, and k(λ) is concerned with attenuation and the reflectance of light, especially in metals.
ñ(λ) = n(λ) + ik(λ) | (1) |
Many prior studies have investigated the optical and thermodynamic properties of binary liquid mixtures due to their relevance for solvation and extraction chemistries.28–36 The earlier studies mostly focused on predicting the real part of the refractive index in non-absorbing spectral regions, e.g., in the visible region at select wavelengths such as 589 nm,28,29 546 nm and 436 nm.30,31 This study examines the complex refractive index in absorbing regions from 1 to 25 μm (10000 to 400 cm−1) as this spectral region is most important for chemical detection, containing both the fundamental absorption bands as well as weaker overtone and combination bands.
Different van der Waals forces, including London dispersion, dipole–induced dipole, and dipole–dipole interactions have the potential to influence the various functional groups within the mixtures and can therefore perturb the resulting spectra. Specifically, for dipole–dipole interactions, including hydrogen-bonding, the interaction is determined by the relative orientation of the two dipoles and therefore tends to be localized to specific functional groups within the pair of molecules. In the limit of two interacting molecules, the distribution of energetically favorable dipole–dipole interactions is not randomly distributed (i.e., there is a preferred orientation). Consequently, dipole–dipole interactions should have a greater tendency to influence the spectral responses of the functional groups involved in the interaction. Conversely, dispersion interactions simply involve transient perturbations to the electron clouds of the interacting molecules. Unlike dipole–dipole, the distribution of dispersion interactions is reasonably isotropic (i.e., there is not a preferred orientation since the geometry of the interaction is not limited to a specific functional group, and the two molecules can adopt any orientation relative to one another). As a result, dispersion interactions should have comparatively little influence on spectral properties, especially if both molecules exhibit comparable dispersion interactions. Thus, to gain a better quantitative understanding of the role of intermolecular interactions on the optical constants of mixtures, we examine two representative cases: (1) a binary mixture capable of interacting predominantly through dispersion interactions (and therefore exhibiting well-behaved spectral responses, characteristic of a linear combination of the neat spectra) and (2) a binary mixture that is also capable of hydrogen bonding (dipole–dipole) interactions which are more likely to impact the infrared spectral features. Specifically, the first case combines tributyl phosphate (TBP), [(CH3CH2CH2CH2O)3PO], a polar organophosphate compound, with n-dodecane, [CH3(CH2)10CH3], a long non-polar hydrocarbon chain. The P
O functional group in TBP leads to dipole–dipole interactions for neat TBP, whereas n-dodecane experiences stronger dispersion forces due to its long, linear hydrocarbon chain.37 These intermolecular interactions in the neat liquids are quite strong as evidenced by the high boiling points (i.e., TBP = 289 °C and n-dodecane = 216 °C).38 In addition to dispersion, dipole–induced dipole interactions can also occur between these two liquids. Prior studies have shown, however, that n-dodecane does not interact significantly with TBP;39 thus, it is expected that these binary mixtures should lead to more ideal spectral responses. The second case mixes TBP with 1-butanol, [CH3(CH2)3OH], a polar protic solvent with an OH moiety capable of hydrogen-bonding. Similar to the TBP:n-dodecane mixtures, TBP:1-butanol is capable of both dispersion and dipole–induced dipole interactions. However, due to the presence of the OH and PO moieties, the TBP:1-butanol mixtures are also capable of hydrogen bonding (dipole–dipole) interactions. Consequently, it is expected that these binary mixtures should lead to non-ideal spectral responses, particularly in regions associated with functional groups involved in the interaction.
A series of binary mixtures is prepared for both TBP:n-dodecane and TBP:1-butanol with different volume percentages to experimentally derive the composite index of refraction for both sample cases and investigate its impact on the resulting quality of the predicted spectra. The complex refractive indices of the binary mixtures are computed using three different mixing rules along with the measured optical constants of the neat liquids.30,40–42 The experimentally derived and computed optical constants of the mixtures are compared to assess the impact of the various intermolecular interactions. Finally, to investigate the efficacy of using the predicted optical constants for modeling reflectance spectra, thin liquid layers of the binary mixtures are modeled on an aluminum substrate using both sets of index values.
Commercially prepared optical cells (International Crystal Laboratories) with either potassium bromide (KBr) or potassium chloride (KCl) windows were used with path lengths of approximately 3000, 1000, 500, 200, 100, 50 or 25 micrometer (μm). In addition, cells of shorter path length, e.g., approximately 15, 10, 5, 2 and 1 μm, were prepared by compressing the 25 μm commercial cells with a hydraulic press. Prior to analyzing the liquid chemicals, a survey IR spectrum was recorded, and the path length of the empty cell was estimated from the fringe spacing using the equation d = (2 × n × Δv)−1 where n refers to the refractive index of air (n = 1) and Δv is the fringe spacing. The liquid sample was loaded into the optical cell using a syringe.
The optical cells were placed in sample holders in both Bruker Tensor 37 and Bruker Vertex 70 instruments for mid-infrared (MIR) and near-infrared (NIR) measurements, respectively. Cell path lengths of approximately 3000, 1000, 500, 200 and 100 μm were analyzed using the (NIR) Vertex 70 and cell path lengths of approximately 500, 200, 100, 50, 20, 10, 5, 2, and 1 μm were analyzed using the (MIR) Tensor 37. Typically, for the 500, 200 and 100 μm path lengths, the same cell with the same liquid fill was used for both systems. The spectrometer sample compartment was continuously purged with ultra-high purity N2 during data collection. The FTIR experimental parameters are provided in Table S1 of the ESI.†
A daily calibration was conducted for both the MIR and NIR systems to ensure consistent optimal performance. The x-axis (frequency) was calibrated by comparing an absorbance spectrum of air (obtained by opening the sample chamber) to reference CO2 and H2O lines from the PNNL gas-phase database.46 The y-axis (transmission) was calibrated with an MRC Infrared Linearity Standard (MRC-910-NG11 S/N 0108) where known transmission values were compared to measured values at various wavelengths across the spectrum. A signal-to-noise test was also performed to check for drift or reduction in the IR signal.
The real part of the complex index of refraction (n) was determined by first measuring the n-values for the binary mixtures at 480, 486, 546, 589, 644, 656 and 1550 nm using an ATAGO refractometer. A modified-Sellmeier equation was then used to interpolate n at 10000 cm−1.51 The final n vector for each point mixture was calculated using the composite k vector and the refractive index at 10
000 cm−1 per Bertie's “LZZKTB” program with the Kramers–Kronig relation. The real and imaginary parts of the complex index of refraction are provided for the neat substances in Fig. S1 and S2 of the ESI.†
TBPa mass (g) | Mole percent (%) | Volume percent (%) | n-dodecaneb mass (g) | Mole percent (%) | Volume percent (%) |
---|---|---|---|---|---|
a TBP properties: M = 266.32 g mol−1, ρ = 0.9727 g cm−3. b n-Dodecane properties: M = 170.33 g mol−1, ρ = 0.7495 g cm−3. c 1-Butanol properties: M = 74.121 g mol−1, ρ = 0.8095 g cm−3, Vm = 91.6 cm3 mol−1. d Mixture excluded from analysis since it is predominantly TBP. | |||||
13.1898 | 91 | 92 | 0.8750 | 9 | 8 |
11.7638 | 70 | 74 | 3.2448 | 30 | 26 |
9.1543 | 50 | 55 | 5.8678 | 50 | 45 |
6.0559 | 30 | 34 | 8.9859 | 70 | 66 |
2.2163 | 9 | 10 | 15.0088 | 91 | 90 |
The calculated volume percentages for the TBP:n-dodecane mixtures (Table 1) are almost equivalent to the mole percentages since the two species have similar molar volumes (Vm) whereas the calculated volume percentages for TBP:1-butanol mixtures (Table 1) are significantly different than the mole percentages. (The reported densities and molar masses can be used to calculate the molar volumes: Vm is equal to 273.8 cm3 mol−1 for TBP, 227.3 cm3 mol−1 for n-dodecane and 91.6 cm3 mol−1 for 1-butanol, respectively). To provide similar proportions for the volume percentages for the TBP–1-butanol mixtures, an additional mixture was prepared to include a 10:
90 volume percent ratio, and the 90
:
10 mole percent mixture was excluded from the analysis since it was mostly TBP, i.e. 96% TBP by volume.
ñmix(λ) = ϕaña(λ) + ϕbñb(λ) | (2) |
ñmix2(λ) = ϕaña2(λ) + ϕbñb2(λ) | (3) |
![]() | (4) |
1. The liquids are assumed to be non-reacting with each other.
2. The total volume or mass of the mixture is equal to the sum volume or mass of the two liquids being mixed.
3. All measurements and analyses are assumed at a fixed temperature, e.g., 27 °C.
For each of the TBP:n-dodecane mixtures, the composite n and k values were also calculated from the expressions in eqn (2) through eqn (4). These predicted n and k values were compared to the measured n and k values presented in Fig. 1, and the residuals determined by subtracting the calculated index of refraction from the values derived from the measurements of the binary mixtures. As an example, the results for the n and k spectra of the 55:
45 mixture of TBP:n-dodecane along with its residuals are shown in Fig. 2. Inspection of the residuals show that the differences are not randomly distributed but rather centered around spectral features. These residuals can also be referred to as the excess spectrum, similar to the excess molar volume and excess molar enthalpies described by other researchers.28,35,53 The differences for the n-values (Fig. 2a) range from −0.011 to 0.015 and show the model mostly overpredicts the n-values as indicated by the negative offset ca. −0.002. The root-mean square error (RMSE) between the modeled and measured refractive index of the mixtures is 0.002. For comparison, the standard measurement error (2σ) for the measured n-value at 1550 nm is 0.001. The measured and modeled n-values at 10
000 cm−1 for the five mixtures and the neat components are also provided in Fig. S4 of the ESI.† Similarly, as seen in Fig. 2b, the model mostly overpredicts the k-values, and the residuals vary from −0.16 to 0.008 in which the largest differences occur at 1280 and 2924 cm−1 corresponding to the P
O and C–H stretching regions, respectively. The RMSE between the calculated and measured k-values is 0.001. Note that the mixing rules require the use of volume fractions vs. mole fractions; using mole fractions with eqn (2) through eqn (4) leads to slightly higher errors in the calculated spectra since the mole fractions are slightly different than the volume fractions (see Table 1).
![]() | ||
Fig. 2 Plots showing (a) the real part (n) and (b) imaginary part (k) of the complex refractive index for both the experimentally measured and calculated values (using eqn (2)) for a 55![]() ![]() |
An expanded view of the measured (solid lines) and computed k-values (dashed lines) centered in spectral regions corresponding to the C–H and PO stretching regions is seen in Fig. 3 for all five binary mixtures of TBP:n-dodecane as well as neat TBP and n-dodecane. Fig. 3a is plotted from 1310–1220 cm−1 (7.6–8.2 μm) and highlights the P
O stretching region. Three peaks in the P
O stretching region are observed and have been previously attributed to different distributions of conformers.54 However, an ab initio calculation of the fundamental vibrational modes of TBP predicts three distinct P
O modes in this region: ν66 (1250 cm−1) and ν69 (1265 cm−1), both assignable to the P
O stretch plus different CH2 wags, as well as ν71 (1280 cm−1) which is assignable to the P
O stretch plus CH2 rocking motions (see S3 in ESI† for more detail). In this spectral region, the residuals for the k-values in the 55
:
45 mixture are primarily negative (Fig. 2b) indicating the mixtures of TBP and n-dodecane are interacting (if only slightly). The deviation from ideal behavior provides a measure of the degree of interaction between the two liquids. In addition, a slight blue-shift for the P
O peak for TBP at 1282 cm−1 is observed as the fraction of n-dodecane increases, e.g., the P
O peak is shifted to 1287 cm−1 for the 10
:
90 mixture. For TBP:n-dodecane, the mixture with the largest concentration of TBP (92
:
08) has the smallest errors. Fig. 3b is plotted from 3000–2817 cm−1 (3.3–3.55 μm) and highlights the C–H stretching region. In this spectral region, the residuals are also negative for most of the mixtures, particularly for the band located at 2924 cm−1, which is assigned to the CH2 antisymmetric stretch for n-dodecane.55 Note that the deviation between measured and computed k-values for this mode increases with the n-dodecane concentration and is largest for the 10
:
90 mixture. Slightly lower k-values at 2924 cm−1 are observed for the three mixtures with the highest concentration of n-dodecane (i.e., 55
:
45, 34
:
66 and 10
:
90) compared to the computed k-values. The alkyl chains in TBP and n-dodecane will interact via London dispersion forces and these are predicted to be the strongest cross-interactions (see Fig. S3 of the ESI†). However, dipole–induced dipole interactions between the P
O and CH2 moieties may also occur. These cross-interactions might explain the slight blue-shift of the P
O mode and the reduced amplitude of the CH2 stretch.
![]() | ||
Fig. 3 The k-spectra for the binary mixtures of TBP:n-dodecane in the region of the (a) P![]() |
For each of the mixtures, the n and k values were also computed using the expressions in eqn (2) through eqn (4) and compared to the measured n and k values presented in Fig. 4. Fig. 5 shows the measured and computed values for the 56:
44 mixture of TBP
:
1-butanol along with the residuals for both n and k values, respectively. The model mostly overpredicts the n-values and a negative offset of −0.01 is observed. The residuals for the n-values (Fig. 5a) vary from −0.077 to 0.042, and the RMSE between the measured and calculated n-values is 0.012, which is a factor of six larger than the RMSE of 0.002 observed for 55
:
45 mixture of TBP
:
n-dodecane and well outside of the measurement variability (2σ < 0.001). The measured and modeled n-values at 10
000 cm−1 for the five mixtures and the neat components are also provided in Fig. S4 of the ESI.†Fig. 5b shows the model both over and under-predicts the k-values, and the residuals range from −0.066 to 0.057 with an RMSE of 0.005, compared to an RMSE of 0.001 for the 55
:
45 mixture of TBP
:
n-dodecane. The largest differences in Fig. 5b occur at 1283 cm−1 (7.8 μm) and 1246 cm−1 (8.0 μm), i.e., the P
O stretching region. Similar to the TBP:n-dodecane mixtures, using molar fractions in eqn (2) through eqn (4) leads to higher errors in the calculated spectra due to the differences between molar and volume fractions (see Table 1).
![]() | ||
Fig. 5 Plots showing (a) the real part (n) and (b) imaginary part (k) of the complex refractive index for both the experimentally measured and calculated values (using eqn (2)) for a 56![]() ![]() |
While the TBP and 1-butanol are quite miscible, there is not a linear correlation between simply adding the k vectors of the two neat liquids in ratios corresponding to the volume fractions for all spectral regions in the infrared. The OH moiety in 1-butanol enables H-bonding with the phosphoryl oxygen in TBP28 causing non-ideal behavior that is not captured by the mixing rules. This behavior can be better understood by inspection of Fig. 6 which plots the experimentally derived k values (solid lines) and calculated k values (dashed lines) using eqn (2). Fig. 6a highlights the PO stretching region from 1310–1220 cm−1 (7.6–8.2 μm). With increasing fraction of 1-butanol, the P
O (phosphoryl) peak for TBP at 1282 cm−1 (7.8 μm) shows a reduction in predicted amplitude whereas an increase in amplitude and broadening is observed around the two peaks at 1262 cm−1 (7.9 μm) and 1236 cm−1 (8.1 μm). The change in the measured spectra indicates an increase in the number of chemical environments for the P
O moiety, suggesting some of the TBP molecules continue to interact with itself, but some also interact with the 1-butanol molecules via hydrogen bonding between the phosphoryl oxygen and the hydroxyl group (see Section III.D). To further assess if hydrogen-bonding is indeed occurring, Fig. 6b is expanded from 3600–3030 cm−1 (2.8–3.3 μm) and includes the broad band for the O–H stretching frequency at 3333 cm−1 for 1-butanol. As the volume percentage of TBP increases, the broad OH peak changes to a doublet and shifts to higher wavenumber (e.g., shifts to 3446 cm−1 for the 88
:
12 mixture), with the O–H band vanishing entirely as the volume fraction moves to that of 100% TBP. The doublet nature of the peak is seen most clearly in the spectrum for the 56% by volume TBP mixture (light green trace in Fig. 6b). The peak shift to higher wavenumber is attributed to hydrogen bonding of the P
O oxygen atom with the OH moiety in 1-butanol.58 It is blue-shifted from the OH peak in neat 1-butanol indicating that some of the OH groups begin to associate with the P
O group of TBP versus other OH groups in 1-butanol. The blue-shift may indicate the strength of the interaction is weaker as steric effects from the bulky butyl groups are forcing the interactions between the OH and P
O groups over larger distances. Both proton-NMR (Fig. S5 in the ESI†) and phosphorus-31 NMR (Fig. S6 in the ESI†) data support the notion that the OH and P
O groups are interacting and causing electron density perturbations as the 1H NMR data indicate an upfield chemical shift for the OH proton58 with increasing TBP concentration, and, in contrast, the 31P NMR data show a downfield chemical shift for the 31P with increasing TBP concentration.59,60
![]() | ||
Fig. 6 The k-spectra for the binary mixtures of TPB:1-butanol in the region of the (a) P![]() |
For both binary mixtures, all three approaches show similar agreement although Fig. 7b shows a slight edge in accuracy for the k-values using the L–L method for TBP:1-butanol and the Arago–Biot method for TBP:n-dodecane (except for the 92:
8 mixture). As seen in Fig. 7, the RMSEs for n and k are lower for TBP:n-dodecane with RMSE values below 0.003 and 0.002, respectively, for all mixtures except for the mixture with the highest percentage of n-dodecane. The RMSE generally increases as the volume percentage of dodecane increases. On the other hand, for TBP:1-butanol mixtures, the RMSE for both n and k is highest for the 56
:
44 mixture peaking at 0.012 and 0.005 for n and k, respectively.
A binary mixture of liquids, composed of components x1 and x2, can be modeled by a simple equilibrium expression, x1 + x2 x1::x2. This modest description suggests that there exist discrete populations of each component that can be assigned as being effectively isolated (i.e., x1 and x2, which behave like the neat liquid samples), as well as a population for which the two components are interacting with one another (i.e., x1::x2). Note that this simple model ignores self-interactions (i.e., consisting of two or more of the same molecules interacting with each other), as the primary interest here is in distinguishing binary mixtures from neat samples. This is not to suggest that self-interactions are not occurring in these mixtures. Rather, for the interacting population, we are solely concerned with cross-component interactions as these lead to spectral perturbations relative to the neat samples. Self-interactions, on the other hand, are already contained within the neat spectra and are hence already accounted for in each of the three models. We first consider the hydrogen bonding interaction in the P
O stretch of TBP for binary mixtures with 1-butanol. Based upon the above equilibrium model, the k-spectra depicted in Fig. 6a can be described as a convolution of two distinct vibrational bands: (1) a band resembling the P
O stretch of neat TBP and (2) a frequency and intensity perturbed band that is characteristic of the intermolecular interactions between TBP and 1-butanol. Note that neat 1-butanol (Fig. 6a, purple trace) does not exhibit measurable vibrational transitions over this wavelength range. Consequently, the TBP::1-butanol intermolecular interaction band can be deduced as a perturbation to the P
O spectrum of neat TBP.
Specifically, it is feasible to deconvolute the measured k-spectra and isolate the individual components by subtracting out an intensity scaled copy of the neat TBP PO stretch band. This analysis was done iteratively with the constraints that the scaled TBP fraction is maximized, and the intensity profile of the resulting difference spectrum remains positive over the entire wavelength range. The rationale for maximizing the TBP fraction is two-fold: (1) the spectral band predominantly originates from TBP (i.e., it is not present in the neat 1-butanol spectrum) and (2) without some constraint, there exists an infinite combination of band shapes which could sum together to produce the measured signal. The remaining spectral features can then be assigned as the vibrational band of the TBP::1-butanol intermolecular interaction complex. Fig. 8a depicts a representative deconvolution of the measured k-spectrum for the 75
:
25 mixture of TBP
:
1-butanol (solid orange line) into an isolated TBP band (dashed black line) and a TBP::1-butanol complex band (dashed green line).
![]() | ||
Fig. 8 Spectral deconvolution of measured k-spectra into separate populations assignable to either isolated or interacting liquids. The insets depict the relative fraction of the deconvoluted populations plotted as a function of the volume fraction of the reference component. (a) P![]() ![]() ![]() ![]() ![]() ![]() ![]() ![]() ![]() ![]() ![]() ![]() ![]() ![]() |
The deconvoluted spectral bands (Fig. 8a) are useful in that they permit an assessment of the concentration dependence (volume fraction) for which the deduced populations transition between isolated (neat) liquids and interacting liquids. Specifically, deconvolution analysis was performed for each of the binary mixtures in Fig. 6a (Fig. S3a in ESI†) and the relative fractions of the isolated (black dots) and interacting populations (green dots) were plotted as a function of the TBP volume fraction (Fig. 8a, inset). These trends were then fit to power functions in order to estimate continuous trends. As a basis for comparison, we then defined the quantity Γ50 as the volume fraction of the reference component for which the intensity of the measured absorption band is composed of equal parts of the isolated and interacting populations. For mixture ratios above Γ50, the absorption band is dominated by the isolated population and should be reasonably well described by the three mixing rules. Conversely, for mixture ratios below Γ50, the absorption band will be dominated by the interacting population and will have a greater propensity to deviate from model predictions. As depicted in the inset of Fig. 8a, for the binary mixture of TBP:1-butanol, the PO stretch of TBP can be characterized with a Γ50 of 78%. This suggests that, except for high volume ratios of TBP (≥78%), the measured TBP P
O stretch absorption will be dominated by the hydrogen bonding interaction and will therefore tend to deviate from model predictions.
Similar analysis was performed on the O–H stretch of 1-butanol for the TBP:1-butanol mixtures depicted in Fig. 6b. Whereas the PO stretch acts as a reporter for TBP, the O–H stretch provides a complementary measure of the hydrogen bonding interaction from the perspective of 1-butanol. As stipulated above, neat TBP (Fig. 6b, black line) does not exhibit measurable vibrational transitions over this wavelength range. Consequently, the TBP::1-butanol intermolecular interaction band can likewise be deduced as a perturbation to the O–H band of neat 1-butanol. Fig. 8b depicts a representative deconvolution of the O–H stretch of 1-butanol in the 56
:
44 mixture of TBP:1-butanol (solid green line) into an isolated 1-butanol band (dashed black line) and a TBP::1-butanol complex band (dashed blue line). Similar deconvolution analysis was performed for each of the binary mixtures in Fig. 6b (see Fig. S3b in ESI†). The relative fractions of the isolated (black dots) and interacting populations (blue dots) were then plotted as a function of the 1-butanol volume fraction (Fig. 8b, inset). The trends were fit to power functions and Γ50 for the O–H stretch of 1-butanol (in a TBP:1-butanol binary mixture) was deduced as 47%. As noted above, this suggests that, except for high volume ratios of 1-butanol (≥47%), the O–H stretch absorption is dominated by the hydrogen bonding interaction with the P
O group in TBP. Given the complementary nature of these interactions (i.e., both TBP and 1-butanol contribute to the intermolecular interaction), it is initially surprising that the Γ50 values are not more similar. This disparity could stem from several possibilities, including differences in hydrogen bonding-induced changes in absorption cross sections (which may well differ for phosphates and hydroxyl groups) or even different stoichiometric ratios of the components involved in the interaction. Thermodynamically, this could result from the fact that unlike TBP, 1-butanol is capable of self-hydrogen bonding. Consequently, while mixing of TBP and 1-butanol is certainly going to be entropically favorable, the process of breaking 1-butanol hydrogen bonds and forming TBP:1-butanol hydrogen bonds may be enthalpically hindered. We plan to further explore this possibility in future temperature dependent studies. In general, this observation suggests that the influence of hydrogen bonding on an absorption feature is likely dependent upon the specifics of the intermolecular interaction, including the strength of the interaction and the fraction of molecules involved in the interaction complex. Further, it is worth emphasizing that both TBP and 1-butanol exhibit reasonably high Γ50 values (≥47%), indicating that hydrogen bonding significantly alters absorption bands that are susceptible to these types of interactions.
Finally, in addition to hydrogen bonding, other van der Waals based interactions in binary mixtures of TBP and n-dodecane were also analyzed. Due to the concurrent presence of C–H bonds in both TBP and n-dodecane, we chose not to analyze the C–H stretch bands (Fig. 3b) and instead focused on the PO stretch of TBP (Fig. 3a). Similar to the hydrogen bonding interaction discussed above, the k-spectra depicted in Fig. 3a can be described as a convolution of vibrational bands: (1) a band resembling the P
O stretch of neat TBP and (2) a perturbed band that is characteristic of the various van der Waals interactions between TBP and n-dodecane. Similar to 1-butanol, n-dodecane (Fig. 3a, purple line) does not exhibit measurable vibrational transitions over this wavelength range. Consequently, the TBP::n-dodecane intermolecular interaction band can be deduced as a perturbation to the P
O spectrum of neat TBP. Fig. 8c depicts a representative deconvolution of the P
O stretch of TBP in the 55
:
45 mixture of TBP
:
n-dodecane (solid green line) into an isolated TBP band (dashed black line) and a TBP::n-dodecane complex band (dashed blue line). Deconvolution analysis was performed for each of the binary mixtures in Fig. 3a (see Fig. S3c in ESI†). The relative fractions of the isolated (black dots) and interacting populations (blue dots) were then plotted as a function of the TBP volume fraction (Fig. 8c, inset). The trends were fit to power functions and Γ50 for the P
O stretch of TBP (in the TBP:n-dodecane binary mixture) was deduced as 1.5%. As detailed above, this suggests that the P
O stretch of TBP will almost always resemble the neat liquid. It is only for extremely low volume ratios of TBP (≤1.5%) that van der Waals interactions between the binary components dominate the absorption band. This is in stark contrast to the influence of the hydrogen bonding interactions (Fig. 8a and b), for which the intermolecular interaction complex dominates the measured spectra for TBP (1-butanol) volume fractions below ca. 50%. These observations nicely account for the fact that the three mixing rules (eqn (2)–(4)) do an excellent job of predicting the k-spectra of binary mixtures exhibiting only isotropic interactions (e.g., dispersion), but a less satisfactory job for binary mixtures capable of anisotropic interactions (e.g., hydrogen bonding) as they have a greater propensity to perturb the spectra.
To examine how the differences in the computed optical constants will impact the synthetic reflectance spectra, ray tracing models of both binary mixtures were constructed and reflectance versus wavelength (wavenumber) computed using the simplest model, i.e., eqn (2) (Arago–Biot). These computed results were compared to reflectance spectra generated using the experimentally measured n and k values for the binary mixture, and the RMSE was calculated to determine the predictive capability for the computed spectra using just the optical constants for the neat liquids. For this work, TracePro63 was used to model the mixture(s) on a substrate of aluminum. A profile view of a 1 μm layer of a binary liquid mixture is given below in Fig. 9 to illustrate the cumulative effect of absorption in the thin film as well as reflective losses at each film interface.
The reflectance spectra were modeled for both (a) a 55:
45 mixture of TBP
:
n-dodecane and (b) a 56
:
44 mixture of TBP
:
1-butanol applied to an aluminum substrate with a 1 μm layer thickness. Fig. 10 shows the results of the modeled reflectance spectra using the complex index of refraction values that were either measured (black trace) or mathematically computed using the Arago–Biot method of eqn (2) (red trace). As illustrated by the residuals in the bottom panels of Fig. 10a, excellent agreement is observed for the thin film of TBP:n-dodecane using calculated n and k values when compared to measured index of refraction values (RMSE is 0.004). On the other hand, Fig. 10b shows higher residuals for the modeled reflectance for the thin film of TBP:1-butanol on aluminum. The RMSE increases by a factor of six to 0.024 due to the cross-interactions between TBP and 1-butanol, which impact the optical constants as seen in Fig. 5. As expected, the largest errors for TBP:1-butanol appear in the OH stretching region at 3449 and 3264 cm−1 and the P
O stretching region at 1283 and 1246 cm−1 due to frequency shifts induced by the interaction between the TBP and 1-butanol molecules.
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Fig. 10 Results of modeling a 1 μm layer on an aluminum substrate of a (a) 55![]() ![]() ![]() ![]() ![]() ![]() ![]() ![]() |
Indeed, as evidenced by lower residuals (Fig. 2 and 5) and lower RMSE values (Fig. 7), overall better agreement with the three models was achieved with TBP:n-dodecane compared to TBP:1-butanol. For example, the RMSE of the k-values for all TBP:n-dodecane mixtures and methods was consistently below 0.002 (Fig. 7b). This low RMSE was only achieved for the TBP:1-butanol mixture with the highest percentage of TBP (i.e., 88:
12, Fig. 7b), indicating that TBP and 1-butanol have intermolecular interactions that lead to larger deviations, including frequency shifts. Further, it is worth noting that all three models (eqn (2)–(4)) produced remarkably similar results (Fig. 7), with only slight differences, indicating that any of the three expressions could be used, as long as intermolecular interactions do not lead to significant perturbations.
It is also of interest to note the characteristic trends of the deduced errors at higher TBP concentrations. For the TBP:n-dodecane mixtures (no cross dipole–dipole interactions), the RMSE values were shown to increase almost monotonically as the percentage of TBP decreased (Fig. 7). In general, this appears to suggest that each of the three methods is better at simulating TBP spectra compared to n-dodecane (i.e., the errors increased as the spectra became more characteristic of n-dodecane). Lower RMSE values were also observed for the TBP:1-butanol mixtures preferentially enriched with TBP. If we consider the specific self-intermolecular interactions at play in these systems, n-dodecane which is a non-polar molecule, exhibits dispersion interactions (i.e., no dipole–dipole) whereas 1-butanol is polar and capable of hydrogen bonding (dipole–dipole). Tributyl phosphate is capable of both dipole–dipole and dispersion interactions and has the highest boiling point of the three liquids, indicating it has the strongest intermolecular forces. Since higher concentrations of both n-dodecane and 1-butanol lead to larger errors from the models, the addition of TBP appears to have a bigger impact on the mixture properties (and hence the cross-intermolecular interactions) than either the addition of n-dodecane or 1-butanol. Due to the strong intermolecular interactions in neat TBP, a larger concentration of 1-butanol is required before most of these interactions are disrupted. Perhaps more interesting, however, is the behavior of the 56:
44 mixture of TBP:1-butanol. For this mixture, which corresponds to when the sample is roughly equal parts (by volume) TBP and 1-butanol (Fig. 7), the maximum RMSE between the measured and computed n and k spectra is observed. Importantly, for this specific mixture ratio, hydrogen bonding should significantly influence both components in the sample (i.e., the P
O stretch of TBP and the O–H stretch of 1-butanol). Conceptually, as the mixture ratio is decreased in either direction, there should be an increased propensity for the remaining dominant component to behave as an isolated (rather than interacting) liquid. Given that none of the three models explicitly considers intermolecular interactions between the two components, it is therefore reasonable that the approximately 50
:
50 mixture (i.e., for which cross-component H-bonding should be maximally occurring) should exhibit the greatest RMSE.
As depicted in Fig. 2 and 5, intermolecular interactions are shown to measurably influence the spectra of binary mixtures. Dispersion forces were shown to have minimal impact on the spectra of binary mixtures (Fig. 3), whereas dipole–dipole interactions (e.g., hydrogen-bonding) resulted in significant perturbations in the spectral regions that are impacted by these forces (Fig. 6). For example, in TBP, the phosphoryl oxygen (PO) is a H-acceptor, so the addition of 1-butanol can lead to H-bonding between the phosphoryl oxygen and the hydroxyl group. Since the OH moiety in 1-butanol can be either a H-donor or H-acceptor, self-association via H-bonding also occurs in neat 1-butanol. Due to disruption of the H-bonding between 1-butanol molecules from the addition of TBP, a blue-shift is observed for the O–H band at 3300 cm−1 (Fig. 6b). This blue-shift may also indicate the interactions between the O–H and P
O bond occur over larger distances due to steric hindrance from the bulky butyl chains. Investigating smaller alcohols with TBP would help determine if steric hindrance is a contributing factor. In the same way, the introduction of H-bonding between the OH and P
O groups leads to a broad peak that is red-shifted for the P
O band at 1282 cm−1 (Fig. 6a). The change in intermolecular interactions upon mixing causes much more significant spectral alteration for the binary mixtures of TBP and 1-butanol (Fig. 5) compared to mixtures of TBP and n-dodecane (Fig. 3). For binary mixtures of TBP and n-dodecane, only a small blue-shift (up to 5 cm−1 for the 10
:
90 mixture) is observed for the P
O band (Fig. 3a), likely due to dispersion (and possibly dipole–induced dipole) interactions between TBP and dodecane molecules disrupting some of the self-interactions in the neat liquids. These results were supported by the spectral deconvolution analysis presented in Section III.C, which quantified the influence of cross-component intermolecular interactions on the resulting spectra. Specifically, as depicted in Fig. 8, hydrogen bonding between TBP and 1-butanol was shown to dominate the measured spectra for all volume ratios consisting of less than 78% TBP. This is in stark contrast to the binary mixtures of TBP and dodecane which only began to show the influence of cross-component van der Waals interactions (e.g., dispersion or dipole–induced dipole) for extremely dilute volume ratios of TBP (i.e., below 1.5%).
Finally, Section III.D showed that spectral modeling using the three mixing rules is a viable approach for materials that are dominated by dispersion (and weak dipole–induced dipole) forces as these interactions only induce minimal perturbations in the spectra of liquid mixtures. For example, spectral modeling of a thin layer of a 55:
45 TBP
:
n-dodecane mixture yielded excellent agreement between the reflectance spectrum calculated using either measured or computed n and k values (Fig. 10a). Larger perturbations were observed for mixtures of TBP:1-butanol, particularly in spectral regions where hydrogen-bonding occurs (Fig. 10b). These results demonstrate the need for improved mixing models which implicitly incorporate intermolecular interactions between the binary components. In the meantime, one potentially viable approach is to simply exclude spectral regions which are strongly influenced by such interactions from modeled spectra. For example, for stand-off chemical detection, excluding the OH bands is reasonable as this spectral region is notoriously problematic due to the presence of atmospheric water which hinders detection efforts. As a result, this spectral region is routinely ignored in such analysis. However, such an approach is largely impractical for other spectral regions that are characteristic of the distinct functional groups present in the mixture components and are therefore necessary to help with material identification, such as the P
O bands. For these samples, the only viable path forward is improved models which consider intermolecular interactions between the mixture components.
The largest differences between the calculated and measured spectra were seen in regions where cross-intermolecular interactions, particularly H-bonding, occur. Good agreement is achieved for both mixtures in regions with ideal mixing behavior, but regions that are affected by dipole–dipole interactions, particularly H-bonding, need to be accounted for in the modeling. Modeling these interactions using e.g., effective medium models,64 will be a future area of study.
Footnote |
† Electronic supplementary information (ESI) available: FTIR data collection parameters, the n(λ) and k(λ) spectra for neat TBP, n-dodecane and 1-butanol, the calculated intermolecular interactions, the measured and modeled n-values for mixtures of TBP with n-dodecane and 1-butanol at 10![]() |
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