Spectroscopic Measurements of Methane Solid-Gas Equilibrium

Mar 28, 2019 - appropriate spectroscopic method. 47. Despite the interest in ..... the list of selected transitions for analysis is presented in Tab.1...
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A: Spectroscopy, Molecular Structure, and Quantum Chemistry

Spectroscopic Measurements of Methane Solid-Gas Equilibrium Clapeyron Curve between 40 and 77 K Patrice Cacciani, Peter Cermak, Cedric Pardanaud, Gabriela Valentova, Jean Cosleou, Céline Martin, Stephane Coussan, Jennifer Anna Noble, Younes Addab, Corinne Boursier, Pascal Jeseck, Mathieu Bertin, Jean-Hugues Fillion, and Xavier Michaut J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.9b01278 • Publication Date (Web): 28 Mar 2019 Downloaded from http://pubs.acs.org on March 29, 2019

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Spectroscopic Measurements of Methane Solid-Gas Equilibrium Clapeyron Curve between 40 and 77 K ˇ Patrice Cacciani,† Peter Cerm´ ak,∗,‡ C´edric Pardanaud,¶ Gabriela Valentov´a,‡ Jean Cosl´eou,† C´eline Martin,¶ St´ephane Coussan,¶ Jennifer A. Noble,†,¶ Younes Addab,¶ Corinne Boursier,§ Pascal Jeseck,§ Mathieu Bertin,§ Jean-Hugues Fillion,§ and Xavier Michaut§ †Laboratoire de Physique des Lasers, Atomes et Mol´ecules, Universit´e Lille, CNRS, UMR 8523, 59655 Villeneuve d’Ascq, France ‡Department of Experimental Physics, Faculty of Mathematics, Physics and Informatics, Comenius University, Bratislava, Slovakia ¶Aix Marseille Universit´e, CNRS, PIIM, Marseille, France §Sorbonne Universit´e, Observatoire de Paris, Universit´e PSL, CNRS, LERMA, F-75005, Paris, France E-mail: [email protected]

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March 28, 2019 Abstract

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The infrared gas phase absorption spectrum of methane was used to determine its

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Clapeyron solid-gas equilibrium curve in the 40-77 K temperature range. For com-

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parative purposes, and to obtain more reliable results, two different optical experi-

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mental setups were used. At higher temperatures (53-77 K), a single pass cryogeni-

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cally cooled cell was coupled to a standard low-resolution FTIR spectrometer. The

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second system was a state-of-the-art VECSEL tunable source operating at around

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2.3 µm, combined with a 7 m path Herriott cell, to record methane absorption fea-

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tures down to 40 K. From the measurements, the vapor pressure curve ln(p/Pa) =

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−(1191.92 ± 8.92)/(T /K) + (22.49 ± 0.16) was derived in the range 40-77 K. This cor-

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responds to a value of (9910 ± 75) J/mol for the sublimation enthalpy. The relation

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was validated down to 40 K, increasing our knowledge of the saturation pressure by

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two orders of magnitude. Data were compared with available pressure measurements

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from the literature, obtained by manometric or mass spectrometry techniques, and the

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sublimation enthalpy was compared with a thermodynamic approach based on heat

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capacity measurements in the solid and gas phases.

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Introduction

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Methane (CH4 ) is a particularly interesting molecule of significant influence in many scien-

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tific fields, including atmospheric sciences, astrophysics, geoscience, combustion science, the

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chemical technology of hydrogen generation, and biotechnology. It is the main constituent

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of natural gas that power stations and industrial and residential users consume. 1 Addition-

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ally, there is a trend towards the increased use of methane as a fuel for appliances, vehicles,

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industrial applications, and power generation. 2 CH4 plays an important role in the chem-

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istry of the upper atmosphere, as it is the third most abundant greenhouse gas (after water

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and carbon dioxide), and thus responsible for significant global warming. 3 Methane is also 2

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present in the atmospheres of giant planets like Jupiter, Saturn, Uranus, and Neptune, 4 as

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well as their satellites, such as Titan. 5 More recently, its presence in small but significant

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quantities has been reported in the Martian atmosphere. 6 In all of these cases, the basic

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thermodynamic properties of methane are of crucial importance.

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In this study, we present a determination of the Clapeyron solid-gas equilibrium curve

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for methane in the 40-77 K range. Commonly, the vapor pressure is measured using contact

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pressure probes. However, at low temperatures, where the density of molecules in the gas

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phase is so low that the collisions with the walls become non-negligible in comparison with

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the inter-sample collisions, the so-called “thermal transpiration effect” prohibits manometric

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measurements. 7 The motivation for this work was to investigate the performance of optical

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measurements compared to these “conventional” contact methods, as applied to the case

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of methane. The main advantage is that the use of light as a probe allows for vacuum

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isolation of the studied sample in thermal and phase equilibrium at a given temperature.

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Secondly, both the temperature and pressure of the sample can be retrieved from a single

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optical spectrum, significantly simplifying the experimental scheme. A similar approach has

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previously been applied to water, where the saturation pressure was measured below its triple

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point using highly accurate measurements from Cavity Ring Down Spectroscopy. 8 Although,

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in the CRDS experiment, the low pressure sample was not measured at low temperature,

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but rather flushed by nitrogen from a humidity generation system at room temperature,

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the commonality with our setup is the measurement of a low molecular density with an

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appropriate spectroscopic method.

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Despite the interest in methane in terms of its nuclear spin dynamics (e.g. Ref. 9 ), and

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the fact that several extensive reviews on methane vapor pressure have been published, few

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experimental vapor pressure measurements have been made below its triple point, TT P =

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(90.6941 ± 0.0025) K and pT P = (116.96 ± 0.02) × 10−2 Pa. 10 In these studies, pressure was

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determined using manometers in the case of Eucken et al. 11 and Armstrong et al., 12 or using

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mass spectrometers by Tickner et al. 13 The temperature range of the sublimation was limited

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to [76.89-90.6 K], [53-90.6 K] and [47.5-90.6 K], respectively. These references can be found

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in the database of the National Institute of Standards and Technology Chemistry WebBook

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(NIST), 14 which provides the methane vapor pressure temperature curves for sublimation

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down to 50 K and for vaporization up to the critical point, TCP = (190.564 ± 0.012) K

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and pCP = (4.5922 ± 0.002) MPa. 10 Indirectly, the sublimation vapor pressure can also be

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retrieved from the calorimetric capacities, which can be measured with good precision and

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accuracy even at very low temperatures. This was done by Colwell et al. 15 for methane and its

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deuterated isotopologue CD4 in the 4-90 K range. Comparison of pressure and sublimation

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enthalpy with our data will be discussed.

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Our experimental work was aimed at establishing reliable vapor pressure data for methane

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below 77 K and extending the lower temperature boundary to 40 K (from the previous 47.5 K

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obtained by Tickner et al. 13 ). To perform this task, we have combined data from two separate

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experiments. The “High-Resolution Setup” (HRS) laser source was a prototype frequency

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tunable Vertical-External-Cavity Surface-Emitting Laser (VECSEL) operating in the 2.3 µm

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region coupled to a 7 m path length cryogenically cooled Herriott cell, 16,17 and probed the

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lowest rotational levels of the ν1 + ν2 , ν1 + ν4 , ν3 + ν4 , and 2ν2 + ν4 combination bands of

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the ν1 (A), ν2 (E), ν3 (F), and ν4 (F) vibrational bands. 18 The second experiment, referred to

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hereafter as the “Low-Resolution Setup” (LRS) was based upon a standard “low resolution”

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Bruker IFS66 Fourier Transform Infra-Red (FTIR) spectrometer with a simple path cell

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approximately 2 cm in length to cover the CH4 absorption from the strongest ν3 band, around

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3 µm, to the components of the ν1 + ν4 and ν2 + ν3 combination bands, around 2.3 µm and

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2.2 µm, respectively. 18 There were a number of reasons to combine these two experiments.

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In terms of sensitivity, due to the longer path length, the HRS offered a better signal-to-

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noise ratio down to low temperature but the accuracy was limited by the interferences in

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the signal, characteristic of Herriott cells. 17 On the other hand, although the LRS allowed

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the registration of the absorption signal only down to 55 K, its readings in the 60-77 K

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range were more accurate and served as absolute calibration for the HRS data. Secondly,

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as the “low resolution” FTIR spectrometer (∼0.1-10 cm−1 ) is a common tool found in many

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research laboratories studying molecules in the solid or liquid phases, its ability to measure

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gas pressure (limits and error sources) could be considered as an interesting alternative to

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manometric measurements.

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This paper is organized as follows: the first part is an overview of the methodology used

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to determine pressure and temperature from the optical absorption measurements. Part two

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details the two cryogenic experimental setups used to record the methane infrared absorption

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spectra. Part three gives the experimental results and their analysis in terms of pressure and

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sublimation enthalpy. This latter value is then compared to sublimation enthalpy derived

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from a thermodynamic approach using heat capacities measurements of the solid and gas

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phases, and finally, the vapor pressure curve including previous references 11–13 is addressed.

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Some technical details regarding the LRS experiment are presented in the appendix (i.e. the

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treatment of the interferogram and the determination of optical path length).

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Methodology

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The principle of the experiment is to retrieve both the pressure p and the temperature T

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from the absorption pattern imprinted onto the light beam passing through a gas sample

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at thermal and phase equilibrium. Therefore, by definition, the pressure retrieved is equal

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to the sample vapor pressure at the corresponding temperature. The following text briefly

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reviews the process of the extraction of p and T from the absorption spectra following

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the methodology used by the High-resolution transmission molecular absorption database

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(HITRAN). 18

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To quantitatively characterize the absorption of a given substance we can use the di-

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mensionless Napierian absorbance Aηη0 (˜ ν ). It describes the rate of light attenuation on the

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interaction path of a length L at a given wavenumber (˜ ν ) due to the absorption by the

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transition between the lower state η and upper state η 0 , separated by the energy difference

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ν˜ηη0 . The total absorbance for a substance of concentration n is then a composition of

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contributions Aηη0 , active in the targeted spectral range:

A(˜ ν) =

X

Aηη0 (˜ ν) =

∀(η 0 ←η)

X

n · L · Sηη0 · φηη0 (˜ ν − ν˜ηη0 ),

(1)

∀(η 0 ←η)

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where the product Sηη0 · φ(˜ ν − ν˜ηη0 ) represents the rate of absorption by the molecule, with

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Sηη0 the strength of the transition and φ(˜ ν − ν˜ηη0 ) its normalized line shape.

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In the equation 1, the simplest variable to calculate is the concentration, from which the

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pressure dependence is obtained from the ideal gas law: n = p/kB T , with kB the Boltzmann

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constant. The line shape φηη0 (˜ ν − ν˜ηη0 ) is, to a first order approximation, described by a Voigt

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function, in which the Lorentz component represents the pressure broadening and the Gauss

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component accounts for the Doppler broadening of the transition. For a sample composed

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of a single substance of molar mass M , the HITRAN database uses the following formulae

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to calculate the corresponding Half-Widths at Half Maximum (given in cm−1 ): Tref nT · p · γself (Tref , pref ) T s ν˜0 RT = 2ln2 c M 



wLor = wGauss

(2) (3)

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where γself is the self-broadening coefficient for reference values of Tref = 296 K and pref =

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1 atm (as defined by the HITRAN database), nT the coefficient of temperature dependence,

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ν˜0 the transition wavenumber, c the speed of light, and R the molar gas constant. Finally,

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for a given molecule and transition, Sηη0 depends only on the temperature, as:

Sηη0 (T ) = Sηη0 (Tref ) ·

Q(Tref ) exp[−Eη /kT ] 1 − exp[−c2 × ν˜ηη0 /T ] · · , Q(T ) exp[−Eη /kTref ] 1 − exp[−c2 × ν˜ηη0 /Tref ]

(4)

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where Sηη0 (Tref ) is the tabulated line strength at the reference temperature (296 K), and Eη

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is the energy of the initial state (given in cm−1 ). The total internal partition function Q

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runs through all allowed rovibrational states i, including the vibrationally fundamental and 6

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excited states: Q(T ) =

X

gi exp[−Ei /kT ]

(5)

i 125

with gi the degeneracy of the level i. Due to its internal structure – having four half-integer

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spin hydrogen atoms at equivalent positions – the main isotopologue of CH4 exists in three

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possible nuclear spin (NS) configurations differing in the value of the total nuclear spin

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(0/1/2 for para/ortho/meta isomers with spin symmetries E/F2 /A1 respectively). 9

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Assuming there is no NS conversion, the para, ortho, and meta isomers constitute three

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independent species and have their own partition functions Qp (T ), Qo (T ), and Qm (T ). Their

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relative populations remain constant and are defined by the initial conditions in which the

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gas is stored before being processed. In our experiments, gas was stored at 300 K, and

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the statistical weight between the nuclear spin isomers at this temperature is 2/9/5, for

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para/ortho/meta, respectively. This is an important phenomenon to consider, especially

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at low temperatures. As some of the lowest rotational levels are forbidden for some NS

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isomers (e.g. J = 0 of the vibrational ground state is allowed only for the meta isomer) 9

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this will impact the dependence of Sηη0 (T ) differently for each NS isomer, especially at low

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temperatures where the lowest J levels dominate the rotational distribution.

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In the opposite case, assuming NS conversion, all three NS species can be considered as

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a single ensemble with a single Q(T ) = Qp (T ) + Qo (T ) + Qm (T ). The principle and details

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of the calculation on the relative line absorbance of the different nuclear spin species in the

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two cases (NS Conversion or NS Conservation) for CH4 can be found in Ref. 17 Considering

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the temperature range addressed by this study (down to 40 K), we find a maximum relative

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difference of the partition functions between the two cases of around 2 %. This value is

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beyond the accuracy of our model based on the HITRAN2016 line intensities S (with best

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precision Serr in the 2-5 % range, see Tab. 1), therefore throughout the text, the effect of NS

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dynamics is omitted. For more details on the values of different terms in the equations or

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their relations to the internal molecular structure (e.g. dipole moments), see the appendix

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of Ref. 19 or the HITRAN online database. 20 7

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Finally, by applying the aforementioned relations, the p and T values can be retrieved,

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by optimizing the Eq. 1 to obtain the best possible match with Aexp (˜ ν ). In the experiments

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described here, however, we do not measure A(˜ ν ) directly. The transmitted signal is detected

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as a power per unit area – intensity I(˜ ν ). The Napierian absorbance is then retrieved by

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applying the Beer-Lambert law: A(˜ ν ) = ln(I0 /I), where I0 (˜ ν ) is the light intensity before

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the interaction.

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A standard approach to find the optimal model, composed of individual components

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corresponding to observed transitions ν˜ηη0 (Eq. 1), is to minimize the χ2 function on the

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digitized data points ν˜i :

χ2 =

X i

 

X



∀(η 0 ←η)

w(˜ νi ) A(˜ νi ) −

2 

[Φηη0 · φV oigt (˜ νi − ν˜ηη0 )]

,

(6)



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where w(˜ νi ) is the weight for given spectral point i, usually equal to the inverse of the square

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of its standard deviation. Also for practical reasons, the integrated transition intensity Φηη0 =

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n · Sηη0 is fitted rather than the pressure of the substance. Applying the relations Eq. 2 and

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Eq. 3 to define the surface normalized Voigt line-shape φV oigt (˜ νi − ν˜ηη0 ) only three quantities

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remain indetermined and are varied in the fit: the baseline function I0 , the temperature

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T and the aforementioned transition intensity Φηη0 . After the convergence is achieved, the

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pressure corresponding to the intensity of transition (η 0 ← η) is calculated using the gas law

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and Eq. 4: "

pηη0

Φηη0 Q(T ) 1 1 kT · · exp −Eη − = L Sηη0 (Tref ) Q(Tref ) kTref kT

!#

.

(7)

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In an ideal case, the shape of the detected intensity would be driven only by the absorption

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of the substance under study. However, in many cases the detection scheme itself could

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also influence the result. When this happens, the recorded Iexp is a convolution of the

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apparatus function Fapp and the original transmitted signal I (Iexp = I ∗ Fapp ). This poses

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an additional problem because, in a general case, Fapp does not commute with the Beer-

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Lambert transformation. Thus, additional processing of the signal must be applied before 8

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treating the spectra. This was also the case in our work where each of the experiments

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suffered from a different type of instrumental function distortion. As they are both different

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and closely related to the experiment, the details of the treatments are provided in the

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corresponding sections where the retrieval of p and T from the spectra is discussed.

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Experiment

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The spectral regions targeted by the two experimental setups are shown in Fig. 1, while

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the list of selected transitions for analysis is presented in Tab.1. In both setups, whose

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schematic outlines are given in Fig. 2, CH4 with a natural abundance of isotopologues and

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99.9995 % purity was used (N55, Air Liquide). The target for the LRS was to focus on

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the optimum accuracy and absolute precision in the higher temperature range, in order to

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provide reference measurements. To this end, a relatively simple optical layout was used to

184

minimize the measurement uncertainties which can arise when using a more complex layout,

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like the Herriott cell in the HRS case. Here, the aim was to exploit a long path length

186

system, and the high spectral resolution and fast mode-hop-free scanning properties of the

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VECSEL to push the sensitivity limits to the lowest temperature limit. Combining the two

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datasets, we were able to provide a coherent and accurate pressure analysis of methane at

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its solid and gas phase equilibrium across the whole temperature range studied, 40-77 K.

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Low resolution setup description

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In the LRS, absorption spectra were recorded in the 1600-4500 cm−1 spectral range using a

192

Bruker IFS66 FTIR spectrometer. We used two wide range spectral sources: a halogen lamp

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for near IR or a SiC globar lamp for mid IR, coupled to an infrared Mercury-Cadmium-

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Telluride (MCT) detector cooled with liquid nitrogen. To avoid residual signal from remain-

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ing atmospheric methane, the spectrometer and the volumes located on the line of sight were

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purged with pure N2 (Alphagaz 2, Air Liquide).

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The Journal of Physical Chemistry

1 E -1 8

H IT R A N 2 0 1 6 - C H 4

V E C S E L - H R S

ν3

1 E -2 0

F T IR

- L R S

ν1+ν2

1 E -2 1

ν1+ν4

 

'

( c m /m o le c u le )

1 E -1 9

L in e s tr e n g th S

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ν2+ν3

1 E -2 2

2ν2+ν4

1 E -2 3

1 E -2 4

1 E -2 5 2 5 0 0

3 0 0 0

3 5 0 0

4 0 0 0

W a v e n u m b e r (c m

-1

4 5 0 0

5 0 0 0

)

Figure 1: Methane line transitions strengths Sηη0 according to the HITRAN2016 database. 18 The arrows point to the lowest J transitions of the bands used in this work.

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Table 1: Selection of the targeted CH4 lines with their parameters according to the HITRAN2016 database. 18 Transition Band Br.(J, Sym.)1

ν3

ν1 + ν4

ν3 + ν4 2ν2 + ν4 ν1 + ν2 ν2 + ν3

R(0, A1 ) R(1, F1 ) R(2, F2 ) R(2, E) R(3, A2 ) R(3, F2 ) R(3, F1 ) Ra (0, A1 ) Ra (1, F1 ) Ra (2, F2 ) Ra (2, E) Ra (3, A2 ) Ra (3, F2 ) Ra (3, F1 ) Qb (1, F1 ) Rb (1, F1 ) Qb (3, F2 ) Rb (0, A1 ) Rb (3, F1 ) Q(2, F2 ) Q(4, F2 ) Q(4, F1 ) R(1, F1 ) R(0, A1 ) R(1, F1 ) R(2, F2 ) R(2, E) R(3, A2 ) R(3, F2 ) R(3, F1 )

ν˜0 2 (cm−1 )

Sηη0 3 (cm/mol)

3028.7523 3038.4985 3048.1533 3048.1691 3057.6874 3057.7265 3057.7607 4223.9053 4229.1940 4234.3498 4234.4173 4239.2506 4239.4278 4239.5765 4324.9331∗ 4328.4319∗ 4330.6300∗ 4333.6690∗ 4334.4357∗ 4330.1079∗ 4332.2360∗ 4333.3108∗ 4337.5489∗ 4555.5645 4566.9963 4578.6120 4578.6808 4590.2357 4590.4613 4590.6085

9.210 × 10−20 8.853 × 10−20 1.132 × 10−19 7.543 × 10−20 2.106 × 10−19 1.260 × 10−19 1.260 × 10−19 2.353 × 10−21 2.236 × 10−21 2.935 × 10−21 1.891 × 10−21 5.160 × 10−21 3.115 × 10−21 3.179 × 10−21 1.307 × 10−21 7.519 × 10−23 1.024 × 10−22 4.087 × 10−21 6.777 × 10−23 1.067 × 10−21 6.978 × 10−23 1.000 × 10−22 1.082 × 10−21 5.226 × 10−22 4.362 × 10−22 4.723 × 10−22 3.137 × 10−22 7.456 × 10−22 4.362 × 10−22 4.338 × 10−22

Serr

1

6 6 6 6 6 6 6 6 6 6 6 6 6 5 6 3 6 6 3 6 3 6 6 4 4 4 4 4 4 4

4

Ei 5 (cm−1 ) 0 10.4816 31.4424 31.4421 62.8781 62.8768 62.8757 0 10.4816 31.4424 31.4421 62.8781 62.8768 62.8757 10.4816 10.4816 62.8768 0 62.8757 31.4424 104.7799 104.7746 10.4816 0 10.4816 31.4424 31.4421 62.8781 62.8768 62.8757

γself 6 (cm−1 / atm) 0.081 0.081 0.083 0.083 0.079 0.079 0.079 0.076 0.087 0.087 0.076 0.080 0.093 0.082 0.078 0.081 0.083 0.091 0.079 0.081 0.078 0.079 0.77 0.080 0.081 0.083 0.075 0.076 0.083 0.081

γerr

4

3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 4 4 4 4 4 4 4

Rotational Branch (Br.), J and symmetry (E, A1,2 or F1,2 ) of the lower state, the index letters ”a” and ”b” allow for distinguishing between lines with the same indicated quantum numbers. 2 Line center. 3 Line strength (Tref = 296 K). 4 HITRAN code for relative uncertainty: 3 (≥ 20 %); 4 (≥ 10 % and ≤ 20 %); 5 (≥ 5 % and ≤ 10 %); 6 (≥ 2 % and ≤ 5 %). 5 Energy of the lower state. 6 Self broadening coefficient. ∗ Transitions used in HRS.

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(a)

Page 12 of 51

PD

Laser: VECSEL

He

T= 12-300 K

PD PD

Cooled Herriott cell

Reference cell

Fabry-Perot étalon

(b)

T = 4-300 K He

InSb detector

FTS Glowbar

10-7 mbar Cooled direct pass cell

N2 purged volume

Figure 2: Experimental setups: (a) the High Resolution Setup (HRS) and (b) the Low Resolution Setup (LRS). PD=Photodiode.

12

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The Journal of Physical Chemistry

197

The direct path optical cell was initially designed for adsorption isotherm measure-

198

ments. 21 The copper cell was equipped with two sapphire windows forming an optical path

199

of length LLRS = 1.746 ± 0.035 cm through the gas sample at thermal equilibrium (the de-

200

scription of the precise path length determination is presented in the Appendix ). The cell

201

was placed inside a cryostat equipped with KBr windows, continuously maintained under

202

a vacuum of 10−7 mbar and cooled by a CTI CRYOGENICS model 22 closed-cycle helium

203

cryocooler. The cell temperature was regulated using a heater and a Lakeshore controller

204

connected to a silicon diode (Lake Shore Cryogenics Model DT-500) fixed on the cell. The

205

cell temperature was adjusted between 40 and 300 K with a precision of 0.1 K. The cell was

206

connected to a stainless steel vessel at ambient temperature where the equilibrium pres-

207

sures were measured in the range 10−4 –10 mbar using two MKS baratron pressure gauges

208

(0–1 mbar and 0–10 mbar capacitive gauges with an accuracy of 0.25% ± 0.0001 mbar and of

209

0.25% ± 0.001 mbar, respectively).

210

To prepare the solid-gas mixture for the Clapeyron curve measurements, roughly 3 mmol

211

of methane were introduced at 100 K (corresponding to 100 Torr in the cryogenic cell and

212

ambient vessel). The cell was then cooled down to 45 K. At each fixed temperature between

213

45-80 K, the (p, T ) and the corresponding IR spectra were collected at thermodynamic

214

equilibrium. For each spectrum, 250 to 500 scans were recorded and averaged. In between

215

measurements, the vessel maintained at ambient temperature was pumped to 10−7 mbar to

216

avoid the contribution of molecules outgassing from the stainless steel walls.

217

After the measurement, the spectra were extracted from the recorded interferograms. To

218

concentrate spectral information around the central lobe of the transition line, a common

219

and standard procedure, named apodization, was applied. It consists of multiplying the

220

interferogram by a selected mathematical function. The effect is to obtain a cleaner spectrum,

221

useful when the density of lines is high but at the expense of the resolution RS . In our

222

case, the apodization function was set to the standard three-term Blackman-Harris function

223

(BH3). 22 The resulting value of RS = 0.13 cm−1 was then determined experimentally by

13

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The Journal of Physical Chemistry

T = 5 5 K ra w 3 1 2 8

3 1 2 4

3 1 2 0

I ( ν~ ) ( a . u . )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 51

P Q

R

c o rre c te d

R (0 ) R (3 )

3 1 5 0

R (2 )

3 1 0 0

3 0 5 0

W a v e n u m b e r (c m

n

R (1 ) -1

3

3 0 0 0

)

Figure 3: Effect of the interferogram correction on spectra recorded with the low resolution setup, in the ν3 asymmetric stretching vibrational band. The interferences due to the use of non wedged windows create a spike in the interferogram and give rise to oscillations on the raw spectrum. Replacing this spike by a straight line suppresses oscillations and gives the corrected spectrum with smooth baseline after Fourier transform (shifted in intensity on the figure, for clarity). 224

measuring the width of isolated R(0, A1 ) and R(1, F1 ) transitions. Also, before extracting

225

spectra from the interferogram, the spike associated with the reflections on the non-wedged

226

windows of the sample cell was replaced by a flat line (see the blue curve in Fig. 3). A

227

detailed description of the numerical process applied to our FTIR spectra is described in

228

Ref. 23

229

The resulting transmittance spectra, together with the absorptance signal αP,exp =

230

1 − Iexp /I0 , for the lowest components of the rovibrational P , Q and R branches are shown

231

in Fig. 4. The absorptance αP (˜ ν ) was preferred before the absorbance A(˜ ν ) for two reasons.

232

First, it is a recommended quantity to account for the effects inherent to the Fourier trans-

233

form spectra, 24,25 and second, it allows a better graphical comparison of the spectra. Note,

234

that in case of small absorption I ≈ I0 , the αP converges towards A/L.

235

The main target for the FTIR analysis was to record the rovibrational lines in the ν3

236

asymmetric stretching vibrational CH4 band around 3048 cm−1 (Fig. 4b). Lines from the

237

ν1 +ν4 band were used to obtain better signal at higher temperatures (Fig. 4c), while the lines 14

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Page 15 of 51

(a ) 5 0 K 5 2 K 5 4 K 5 6 K 6 0 K 6 5 K 7 0 K 7 7 K

0 .2 5

0 .1 5

Ie

x p

( ν~ )

0 .2 0

ν2 + ν3

0 .1 0

ν1 + ν4 0 .0 5

ν3

0 .0 0 2 7 5 0

(b )

3 0 0 0

3 0 2 8

3 0 2 9

3 0 3 8

4 2 0 0

4 4 0 0

4 6 0 0

(c )

3 0 3 9

0 .0 4 1

R (1 ,F )

1

)

0 .1 5

ν3

0 .0 2

,e x p

R

ν1 + ν4 R

= 1 - I

e x p

/I0

R (0 ,A

A b s o r p t a n c e αP

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

a

(0 ,A

0 .1 0

1

) R

a

(1 ,F 1

a

(2 )

R )

a

(3 )

0 .0 0

R (2 )

R (3 ) 0 .0 5

0 .0 2

0 .0 0

0 .0 0 3 0 4 8

3 0 4 9

3 0 5 8

3 0 5 9

4 2 2 5

W a v e n u m b e r (c m

-1

4 2 3 0

4 2 3 5

4 2 4 0

)

Figure 4: Absorption spectra of methane in the spectral region of the ν3 and ν1 +ν4 vibrational bands recorded at different temperatures using the LRS. (a) Evolution of recorded light intensity, I(˜ ν ), with temperature. Spectra have been shifted vertically from each other for clarity. The transitions used in the analysis are indicated by red and pink arrows for the lowest and higher temperature range, respectively. The evolution of the absorptance αP = 1 − I/I0 , for selected rovibrational transitions in the ν3 band (b), and in the ν1 + ν4 band (c), is shown in detail on the lower plots. 15

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238

from the ν2 +ν3 band were used for the precise measurement of the LLRS (see Appendix). The

239

baseline noise, estimated from the RMS of the fully transmitted signal, was approximately

240

0.002, comparable to that of the HRS. However, due to the much smaller optical path, the

241

minimum detectable absorption coefficient (Aexp (˜ ν )/L)min was only around 1 × 10−3 cm−1 .

242

High resolution setup description

243

The VECSEL source, used in the HRS, was a custom developed device based on the unit

244

described in detail in Ref. 26 The optically-pumped semiconductor core containing the active

245

medium on top of a Bragg mirror provided by IES Montpellier. 27 The 0.33 mm long external

246

cavity was formed by a highly reflective spherical mirror of 2 mm radius placed on a tubular

247

piezo transducer. It produced a single mode continuous emission with a narrow linewidth

248

below 3 MHz on a 1 ms time-scale. Variation of substrate temperature allowed VECSEL to

249

cover the spectral range between 4270 and 4340 cm−1 . The continuous and mode-hop-free

250

tuning of up to 15 cm−1 was performed by the external cavity piezo-driven scans.

251

The light from the VECSEL was coupled into the LHRS = 692 ± 5 cm path length Herriot

252

Cell (HC) and then analyzed by a photodiode (type G8423 from Hamamatsu coupled with a

253

home-made transimpedance amplifier with a bandwidth of 0.6 MHz). The details of the HC

254

design can be found in Ref. 16 and the precise LHRS determination in Ref. 17 A part of the

255

main beam was also diverted to a Fabry-Perot (FP) ´etalon (with Free Spectral Range, FSR

256

∼ 0.0242 cm−1 ) and to a reference cell filled with methane at low pressure (40 cm long and

257

about 10 mbar of CH4 ) to provide signal for precise frequency calibration (with a precision

258

better than 0.001 cm−1 ).

259

The HC temperature was stabilized to absolute variations below 0.1 K using the Lake

260

Shore Cryogenics Model 331 temperature controller. Cryogenic cooling was supplied by the

261

CTI-Cryogenics Model 22C Cryodyne cooler and two 25 Ω resistors were used for the heating.

262

The temperature was measured with two calibrated silicon diodes, Lake Shore Cryogenics

263

Model DT-670 with calibration accuracy ±0.25 K between 30 and 60 K, and ±0.15 K between 16

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The Journal of Physical Chemistry

264

60 and 300 K. 16 One of the probes, TA , was placed close to the ”cold finger” cooler and was

265

used as a reference for the temperature-locking circuit. The second, TB , was located on the

266

cell far from the heating resistors, to provide an independent measurement of the actual

267

temperature. The difference between TA and TB varied from 0.12 to 0.20 K for the series

268

of measurements performed, in which the temperature was decreased slowly from 70 K to

269

40 K. The importance of this temperature measurement will be discussed later. For sample

270

manipulation and the pressure measurements (performed by the 0-10 mbar Pfeiffer CMR

271

capacitive gauge with a precision of 0.001 mbar) the HC was connected to a vacuum system

272

(at room temperature) through a 6 mm inner diameter steel pipe. Detailed descriptions of

273

the VECSEL, the Herriott cell, and the calibration process can be also found in a previous

274

study performed with the HRS. 28

275

To probe the entire rotational population of the lowest levels (J = 0 to 4) of combina-

276

tion bands of different vibrational modes (Tab. 1), we performed scans about 12 cm−1 wide

277

centered around 4330 cm−1 . The repetition rate of the scans was limited by the rapidity of

278

the amplified photo-diode detector. On the other hand, high recording speed was beneficial

279

in reducing the effects of mechanical noise in the system (caused by both the cryogenic cool-

280

ing system and the vacuum pumps). As a compromise, we set the tuning speed to around

281

18 THz.s−1 , corresponding to a 50 Hz spectral acquisition repetition rate.

282

At the beginning of the Clapeyron curve measurements, the HC was pumped down to

283

10−5 mbar and was then filled with around 9 mbar of methane at 77 K. Filling was stopped

284

once the absorption signal stabilized, i.e. once the saturated vapor pressure was reached.

285

The gaseous sample was then cooled progressively (∼ 4 hours) down to 40 K (when the

286

absorption signal disappeared in the baseline noise) with intermediate temperature plateaus

287

of a few minutes duration to record corresponding IR spectra. For each temperature, 32

288

scans were recorded, calibrated, and averaged (Fig. 5a). Fig. 5b and Fig. 5c show part of

289

the absorptance corresponding to a couple of the transitions used in the analysis. The

290

baseline noise, estimated from the root mean square of the fully transmitted signal was

17

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The Journal of Physical Chemistry

(a ) 4 0 K 8

4 3 K 4 5 K 5 0 K 6

( ν~ )

5 5 K Ie

x p

6 0 K 6 3 K 4

6 5 K 7 0 K 2

0 4 3 2 5 .2

(b )

4 3 3 3 .6 3

,e x p

= 1 - I

e x p

/I0

0 .9

A b s o r p t a n c e αP

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 51

R

b

4 3 2 7 .4

4 3 3 3 .6 8

4 3 2 4 .9 2

Q

(0 ,A 1)

4 3 2 9 .6

b

4 3 3 1 .8

4 3 3 4 .0

(c )

4 3 2 4 .9 7

4 3 2 8 .3 6 0 .9

(1 ,F 1)

0 .6

0 .6

0 .3

0 .3

0 .0

0 .0 0 .0 9

Y -z o o m x 2 0

0 .0 4

b

R

4 3 2 8 .4 6

4 3 3 8 .4

4 3 3 4 .3 8

R

(1 ,F 1)

b

4 3 3 4 .4 8

(3 ,F 1)

Y -z o o m x 1 0

0 .0 6 0 .0 2

4 3 3 6 .2

0 .0 3

0 .0 0

0 .0 0 4 3 3 3 .6 3

4 3 3 3 .6 8

4 3 2 4 .9 2

4 3 2 4 .9 7

4 3 2 8 .3 6

W a v e n u m b e r (c m

-1

4 3 2 8 .4 6

4 3 3 4 .3 8

4 3 3 4 .4 8

)

Figure 5: Absorption spectra of methane in the spectral range around 4330 cm−1 recorded with the HRS. The intensity of light, I(˜ ν ), recorded at different temperatures, is shifted vertically for clarity(a). Red and black arrows correspond to the rovibrational transitions used at lower and higher temperatures, respectively. The panels (b) and (c) show the absorptance signal for an example of two transitions from each group.

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The Journal of Physical Chemistry

291

approximately 0.001, leading to a minimum detectable absorption coefficient (Aexp (˜ ν )/L)min

292

of about 1.4 × 10−6 cm−1 .

293

Analysis of the vapor pressure curve

294

In the first part of this section we discuss the procedure used to retrieve the p and T

295

values from the LRS and HRS experimental spectra. In the second part, we deal with

296

the thermodynamics interpretations of the results and their comparison with previously

297

published data.

298

Retrieval of p&T from the spectra

299

An important point to discuss before dealing with the treatment of the absorption spectra at

300

temperatures below the freezing point is the influence of solid phase absorption. In the case

301

of methane, this is a well-known phenomenon. For example, a detailed spectroscopic study

302

covering both the temperature and spectral ranges of our work was performed by Grundy

303

et al. 29 Above 20 K, methane is in its crystalline phase I, in which the absorption peaks are

304

tens of nanometers broad. 30 In our case (Fig. 5a and Fig. 4a), this effect was observable only

305

by a small decrease of the baseline level, with no impact on the retrieval process.

306

Due to differences in the apparatus function, two different approaches were used to treat

307

the signals from the LRS and HRS experiments. The common point of the analysis was

308

the application of the aforementioned methodology. This included the approximation of the

309

absorption profile by the Voigt function. Although it is well known that it does not exactly

310

reproduce the molecular transition profiles, neither the Hartmann-Tran profile (HTP), which

311

is currently suggested by the IUPAC task group to model the molecular transition line

312

shape, 31 nor any other “beyond Voigt” line shape models were used here, due to the fact that

313

(i) our measurements were performed at low temperatures, where the Doppler broadening

314

dominates the collisional one, and (ii) the uncertainty of Sηη0 (Tab. 1) in the range 2 to 5 %

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Page 20 of 51

315

was greater than the possible error of using the Voigt line shape model within the p and T

316

values of this work. 32

317

LRS

318

The first fact we had to consider before fitting the spectra was the role of the apparatus

319

function FLRS . Note, that at 60 K, neglecting the collisional broadening, transitions in the

320

3000 cm−1 range have wGauss around 120 MHz or 0.004 cm−1 (Eq. 3). This is almost a hundred

321

times less than the width of the instrument apparatus function (around 0.1 cm−1 – see the

322

section Low resolution setup description). It means that the retrieved signal ILRS (˜ ν ) is the

323

convolution of the absorption I0 exp[−A(˜ ν )] with the apparatus function FLRS (˜ ν ). Trying

324

to extract A(˜ ν ) using first Beer Lambert transformation ln(I0 /I(˜ ν )) and then deconvoluting

325

this by FLRS (˜ ν ) is not strictly correct as the two operations do not commute.

326

In case of Fourier transform spectra a boxcar function was used to represent the FLRS :

FLRS (˜ ν ) = 2/R · sinc(2˜ ν /R),

(8)

327

with R the LRS resolution. As in FTIRs the entrance intensity I0 (˜ ν ) is generated by a

328

light source which is spectrally broad compared to the width of the apparatus function, the

329

convolution I0 (˜ ν ) ∗ FLRS (˜ ν ) leaves I0 intact. Contrary to A(˜ ν ) the resulting absorptance

330

αP,exp is then directly proportional to the sample absorptance αP (˜ ν ): "

#

(I0 ∗ FLRS ) − (I ∗ FLRS ) I0 − ILRS ≈ αP (˜ ν ) ∗ FLRS . = 1− αP,LRS (˜ ν) = 1 − I0 (I0 ∗ FLRS ) 



331

(9)

In this case, the modified convergence criteria would be:

χ2αP =

X

w(˜ νi ) [αP,exp (˜ νi ) − αP,model (˜ νi )]2 .

(10)

∀˜ νi

332

There were two main reasons why we did not apply this procedure, but instead, a modified

20

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333

The Journal of Physical Chemistry

criterion based solely on the amplitudes of the observed transitions αP,exp (˜ νηη0 ) was used: ( 2

κ (p, T ) = log10

[αP,exp (˜ νηη0 ) − αP,model (˜ νηη0 )]2 . αP,model (˜ νηη0 )2 )

(11)

334

First, we had to take into account the low resolution of our LRS system hindering the

335

physical line shape of the transitions. As a consequence, the only reliable information we

336

can get from the spectra is the intensity of absorption peaks. Even more, this only stands

337

for individual transitions like R(0, A1 ). In cases like the R(2) line at 3048.2 cm−1 , the two

338

ortho and para transitions are separated only by 0.016 cm−1 (Tab. 1), and further information

339

about their relative intensities is necessary to retrieve their individual intensities from the

340

LRS spectra. Second point to be considered was the intensity noise. Although the filtering

341

of the interferogram removed the largest oscillation, the remaining interference patterns had

342

a greater influence on the surface than the height of the absorption lines. Considering both,

343

the low signal to noise ratio and the low resolution of the system, the choice of the amplitude

344

based convergence criteria (Eq. 11) over the integrated absorptance one (Eq. 10) was justified.

345

To further simplify the situation, the transitions for analysis were selected in such a way

346

that they could be treated individually in a narrow spectral region surrounding the line.

347

For T 65 K no transpiration effect occurs, and the value is equal to one. For

391

T < 50 K, the p/ph ratio roughly evolves as (T /Th )1/2 (Knudsen domain). For T between

392

50 and 65 K, the ratio evolves in an intermediate way, following an empirical law proposed

393

by Ref. 33 Trying to determine new values for coefficients of a more recent refined empirical

394

law proposed in Ref. 7 was not possible in this work because the outgassing from the walls

395

limits the methane pressure measurements.

396

HRS

397

Unlike in the FTS case, the combination of narrow VECSEL linewidth with its fast frequency

398

tuning rate ensures that the spectra recorded by the HSR contain negligible broadening by

399

the apparatus function. In that case the absorbance AHRS (˜ ν ) = A(˜ ν ) and the corresponding

400

p and T values can be found by minimizing Eq. 6 and then using Eq. 7.

401

However, as seen in Fig. 5, in our case a small asymmetry was observed in the line profiles,

402

which could affect the retrieval of the integrated area. Indeed, for strong lines this effect is

403

clearly visible, as can be observed in the example shown in Fig. 9. The reason was determined

404

to be that, compared with previous experiments, the recorded spectral range was enlarged (to

405

12 cm−1 to record in the same scan the lines Qb (1, F1 ) and R(1, F1 ) located at 4324.9331 and

406

4337.5489 cm−1 , respectively) while maintaining the same repetition rate. Consequently, the

407

scanning speed was increased and the response time of the detector became visible. In this

408

case, the convolution of the absorption spectrum with the apparatus function, which could

409

be represented by an exponential decay (defined by the time constant τ ), does not commute

26

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The Journal of Physical Chemistry

410

with the logarithm in the Beer-Lambert law. This leads to a systematic underestimation of

411

the retrieved line intensities, in the case of strong peaks, when they are obtained by simply

412

fitting the absorbance (Eq. 10). To correctly account for this effect, the recorded signal must

413

be fitted by the numerical representation of this convolution:

χ2HRS =

X

w(˜ νi ) {IHRS (˜ ν (ti )) − I0 · exp [−A(˜ ν (ti ))] ∗ exp [−∆t/τ ]}2 ,

(12)

∀˜ νi

414

note, that in this case, the convolution is in the temporal space, rather than in the spectral

415

space like for the LRS, due to the nature of the instrument effect. To this end, we have

416

developed a dedicated fitting program which was used to treat all HRS signals with the

417

time-decay constant deduced from the HRS detector bandwidth (1.7 µs). An example is

418

given in Fig. 9 where the fitting curve is drawn for the Rb (0, A1 ) transition recorded at 40

419

and 55 K. The residual curves confirm the correctness of the fit, for both “small” symmetric

420

and “strong” asymmetric lines. A small excess of noise is visible at 55 K due to the fact

421

that, in this region where the signal nearly drops to zero level (complete absorption), a lesser

422

weight is used in the fit.

423

Considering the aforementioned issues, the selection of the transitions used for analysis

424

was limited to those with a reasonable level of transmittance signal (approximately A < 3) in

425

order to have the best possible estimation of surface. Due to the large temperature range ad-

426

dressed in the study, there was no transition which would fit this criterion across all measured

427

spectra. Therefore we had to create different selections for temperatures. Q(1, F1 ), Q(2, F2 ),

428

Rb (0, A1 ), and R(1, F1 ) lines (see Table 1 for attribution) with Sηη0 > 10−21 cm/mol were

429

used between 40 and 50 K (Fig. 5b), while less intense Rb (1, F1 ), Q(3, F2 ), Q(4, F2 ), Q(4, F1 ),

430

and Rb (3, F1 ) lines were preferred at higher temperatures (Fig. 5c) up to 70 K. Unfortunately,

431

for three of them (Rb (1, F1 ), Q(4, F2 ), and Rb (3, F1 ) ), the accuracy of S is claimed to be

432

above 20 % (Tab. 1). In the treatment, their weights were reduced accordingly. For each

433

temperature, up to four values of pressure were obtained and had to be averaged correctly.

27

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The Journal of Physical Chemistry

2 .2 5

Z o o m

2 5 x

2 .2 0

2 .1 5

2 .0

ν1+ν4 b

R

(0 , A 1

)

R S

( ~ )

1 .5

IH

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 51

1 .0

0 .5

F it 5 5 K 4 0 K

0 .0

0 .0 0 5 0 .0 0 0 -0 .0 0 5

4 3 3 3 .6 5 6

4 3 3 3 .6 6 8

W a v e n u m b e r (c m

4 3 3 3 .6 8 0 -1

)

Figure 9: Example of HRS signal fit. The graph shows the fit and residuals for the Rb (0, A1 ) transition of ν1 + ν4 recorded at 40 and 55 K.

28

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The Journal of Physical Chemistry

434

In such measurements, error analysis is crucial, and in our case, was done considering the

435

factors present in Eq. 7. The relative error δp/p was obtained by summing the contribution

436

to L (0.8%), Aηη0 (given by the fit process from 1 to 10 %), S (given by the error code in HI-

437

TRAN Table 1), and temperature T . For the evaluation of the temperature contribution, an

438

absolute accuracy of 0.25 K (as mentioned in the experimental part) yields a relative error of

439

0.6 % for the lowest temperature of 40 K, this propagates in Eq. 7 to less than 1 %, including

440

the three T -dependent terms present. The value of 0.25 K is discussed below because of the

441

exponential dependence of the pressure with the temperature.

442

Fig. 10a presents the data points corresponding to the nine transitions in a (ln(Π), 1/θ−1)

443

plot as defined above compared to Armstrong’s formula 12 converted to dimensionless Π and

444

θ. In this case, the dynamical range of the variation of the saturated pressure does not allow

445

us to clearly visualize the differences between the different data. Thus, two residuals are

446

plotted on the lower panels: the difference with the pressure given by Armstrong’s formula

447

(Fig. 10b) and the difference with a linear fit ln(Π) function of (1/θ − 1) (Fig. 10c).

448

Although the error bars are wide compared to the dispersion of the data, it is clear that

449

one data set is shifted. This corresponds to the Q(4, F2 ) transition located at 4333.2360 cm−1 .

450

The value of SHIT RAN 2016 = 6.978×10−23 cm/mol appears to be too low, leading to an overes-

451

timation of the pressure. For this reason, different methane databases (experimental or the-

452

oretical) have been considered and compared to HITRAN2016: GEISA2016, 34 Theo296K, 35

453

EXOMOL, 36 Mecasda, 37 and ESA-Birk. 38 The more experimental ones (GEISA, ESA-Birk)

454

give a value around 8.1 × 10−23 cm/mol. The relative difference of 16 % remains within the

455

accuracy of >20 % assumed in HITRAN2016 but could be corrected.

456

The ESA-Birk database was developed for the atmospheric instrument TROPOMI and

457

gives positions, intensities and also air-broadening of molecular lines including HTP pro-

458

file and line-mixing effects. The given uncertainty on the linestrength is less than 0.5 %.

459

Fortunately, their range studied (4200 to 4340 cm−1 ) covers that of our HRS data, so it is

460

straightforward to use this database rather than HITRAN2016. Confirmation was given

29

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The Journal of Physical Chemistry

T (K ) 6 9 .7 5

5 6 .6 7

2ν +ν

(a )

2

T P

ln ( p ) - ln ( p

ν +ν

-8

3

Q -1 2

) m s tr.

Q

4 2

(4 , F (4 , F

ν +ν 1

4

1

2

b

Q )

b

R )

b

)

Q R R

b b

2

(1 (1 (3 (0 (3

4

, F 1 ) , F 1 ) , F 2 ) , A 1 ) , F 1 )

R (1 , F 1)

-1 6

(b )

0 .0 -0 .3

l n ( ΠE

x p

) - l n ( ΠA

Q

(2 , F

ν +ν 1

0 .3

4 1 .2 1

4 7 .7 2

)

-4

-0 .6

H IT R A N

2 0 1 6

0 .3

l n ( ΠE

x p

) - F it

(c )

0 .0

-0 .3

E S A - B ir k

0 .3

x p

) - F it

(d )

l n ( ΠE

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 51

0 .0

-0 .3 0 .3

0 .6

1/θ−1

0 .9

1 .2

Figure 10: Upper panel (a): saturated pressure data points. The relative differences of saturated pressure, measured by the spectroscopy using the HITRAN2016 database, between Armstrong formula from Ref. , 12 and fitted linear curve are plotted in panel (b) and (c), respectively. The last panel (d) shows the relative differences between p retrieved using the ESA-Birk database and a fitted linear curve. 30

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The Journal of Physical Chemistry

461

within our experiment, where a reference spectrum of methane at room temperature was

462

simultaneously recorded to calibrate each cold spectrum. It was possible to compare the two

463

simulated spectra from the HITRAN2016 and ESA-Birk databases to our reference spectrum,

464

and although minor discrepancies were observed with the first, the second spectrum almost

465

perfectly matched the experimental data. Tab. 3 presents the comparison between the two

466

databases for the nine transitions used in this study. The corrected data sets are shown as

467

residuals in the lower panel of Fig. 10d, where it can be observed that the major discrepancy

468

has disappeared and the error bars have been reduced by one order of magnitude. Tab. 4

469

compares the pressures derived from the two databases including their uncertainties. Table 3: Comparison between HITRAN 2016 and ESA-Birk databases. Energy (cm−1 ) 4324.9331 4328.4319 4330.1079 4330.6300 4332.2360 4333.3108 4333.6690 4334.4357 4337.5489

Label Qb (1, F1 ) Rb (1, F1 ) Q(2, F2 ) Qb (3, F2 ) Q(4, F2 ) Q(4, F1 ) Rb (0, A1 ) Rb (3, F1 ) R(1, F1 )

Eη (cm−1 ) 10.4816 10.4816 31.4424 62.8768 104.7800 104.7747 0 62.8768 10.4816

SHIT RAN 2016 (cm.mol−1 ) 1.307E-21 7.519E-23 1.097E-21 1.024E-22 6.978E-23 1.000E-22 4.087E-21 6.777E-23 1.041E-21

SESA−Birk (cm.mol−1 ) 1.375E-21 7.803E-23 1.113E-21 1.040E-22 8.155E-23 1.058E-22 4.295E-21 6.727E-23 1.137E-21

∆ (%) 4.9 3.6 1.4 1.5 14.4 5.5 4.8 -0.7 8.4

Eη is the energy of the lower state of the transition and the last column ∆ is the relative difference in % for the two databases.

470

The Clapeyron curve

471

The measurement of the saturated pressure at temperatures below the triple point allowed

472

us to consider the thermodynamics of sublimation and to determine its enthalpy for the

473

methane molecule. The following paragraph recalls the basic aspects and tries to compare

474

the results obtained by spectroscopy to previous determinations.

475

The boundary between two phases of a single (pure) substance is described by the Clapey-

31

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Page 32 of 51

Table 4: Analysis of pressure values in HRS from the two databases.

Database T δT 40.189 0.25 41.109 0.25 42.123 0.25 43.115 0.25 45.138 0.25 50.107 0.25 55.046 0.25 60.098 0.25 65.036 0.25 70.079 0.25

476

HRS ESA-Birk p δp δp/p 0.000727 1.3E-05 0.019 0.001496 4.0E-05 0.027 0.00300 7E-05 0.023 0.00598 6E-05 0.009 0.0202 0.0002 0.010 0.278 0.004 0.014 2.375 0.041 0.017 14.60 0.17 0.012 65.2 0.8 0.012 238.5 4.4 0.019

HITRAN2016 p δp 0.000764 3.4E-05 0.001575 7.8E-05 0.00320 0.00017 0.00630 0.00031 0.0212 0.0010 0.294 0.017 2.44 0.15 15.10 0.89 67.6 4.0 249.0 14.7

δp/p 0.044 0.049 0.052 0.050 0.045 0.058 0.062 0.059 0.060 0.059

ron equation: dp ∆s = , dT ∆v

(13)

477

with ∆s the difference of molar entropies and ∆v the difference of molar volumes of the solid

478

and gas phase.

479

Considering that our case is obviously far below the critical temperature, ∆v can be ap-

480

proximated by the molar volume of the gas phase vg for which the ideal gas law applies :

481

vg = RT /p, with R = 8.3144598 J.mol−1 .K−1 the molar gas constant. Accordingly, ∆s can

482

be characterized by the molar enthalpy of sublimation ∆sub H as follows: ∆s = ∆sub H/T as,

483

during phase change, temperature and pressure remain constant. Therefore: ∆sub H dT dp = p R T2

(14)

484

and, if the molar enthalpy of sublimation is considered as constant in the temperature range,

485

the integration gives:

ln(p) = − 486

∆sub H 1 + const., R T

(15)

which is the classical form of Clapeyron’s law. If ∆Hsub is constant up to the triple point, its 32

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The Journal of Physical Chemistry

487

value is directly related to the slope of the straigth line written with dimensionless parameters

488

θ and Π: ln(Π) = −

∆Hsub RTP T



1 −1 θ



(16)

Table 5: Experimental data used for the final fit, including both LRS and HRS data. T (K) 40.18 41.10 42.12 43.11 45.14 50.10 55.05 60.10 65.03 70.08 53.13 54.14 55.14 59.13 64.14 69.14 76.14 90.69

θ = T /TT P 0.443 0.453 0.464 0.475 0.498 0.552 0.607 0.663 0.717 0.773 0.586 0.597 0.608 0.652 0.707 0.762 0.839 1

Π = p/pT P 6.22E-08 1.28E-07 2.56E-07 5.11E-07 1.72E-06 2.37E-05 2.03E-04 1.24E-03 5.58E-03 2.04E-02 6.95E-05 1.11E-04 1.93E-04 8.54E-04 3.99E-03 1.71E-02 7.98E-02 1

Type HRS HRS HRS HRS HRS HRS HRS HRS HRS HRS LRS LRS LRS LRS LRS LRS LRS TP

x = (1/θ − 1) 1.256 1.205 1.152 1.103 1.009 0.809 0.647 0.509 0.394 0.294 0.706 0.675 0.644 0.533 0.414 0.311 0.191 0

δx 1.40E-02 1.34E-02 1.28E-02 1.22E-02 1.11E-02 9.02E-03 7.48E-03 6.27E-03 5.36E-03 4.61E-03 1.61E-02 1.55E-02 1.49E-02 1.30E-02 1.10E-02 9.48E-03 7.82E-03 3.30E-04

y = lnΠ -16.592 -15.871 -15.177 -14.487 -13.272 -10.648 -8.500 -6.686 -5.187 -3.892 -9.573 -9.099 -8.548 -7.064 -5.524 -4.068 -2.528 0.000

δy = δp/p 1.80E-02 2.60E-02 1.80E-02 5.00E-03 7.00E-03 1.00E-02 1.50E-02 1.00E-02 1.00E-02 1.70E-02 8.20E-02 1.02E-01 5.90E-02 6.70E-02 5.80E-02 7.00E-02 5.80E-02 5.00E-03

σ 0.19 0.18 0.17 0.16 0.15 0.12 0.10 0.08 0.07 0.06 0.23 0.23 0.20 0.18 0.16 0.14 0.12 0.01

The last column σ is the error including the linear fit uncertainties δy on y and δx on x, calculated by σ 2 = δy 2 +a2 δx2 , where a = −13.15 ± 0.1 is the slope of the straight line, y = ax + b. The values of T P : TT P = (90.6941 ± 0.0025) K and pT P = (116.96 ± 0.02) × 10−2 Pa, were taken from Ref. 10 489

Indeed, as shown in Fig. 7 for LRS and Fig. 10a for HRS, the data points are nearly aligned

490

on a straight line, and a preliminary value of the sublimation enthalpy can be estimated using

491

Eq. 16. In fact, our data sets are limited to the range 40-77 K and Eq. 15 is preferred for

492

a weighted fit on this limited temperature range y = ax + b with y = ln(Π), x = 1/θ and

493

a the slope ∆Hsub /RTT P . To carefully evaluate uncertainties, it is important to consider

494

the absolute accuracy of T in each set-up and to propagate it on the pressure. So, the

495

uncertainty σy to be regarded on includes δy = δΠ/Π, and that of the measurement of 33

ACS Paragon Plus Environment

The Journal of Physical Chemistry

496

x = 1/θ, aδx = aδθ/θ2 . The expression to be minimized is thus:

χ2 =

X (y − ax − b)2

(17)

δy 2 + (aδx)2

q

δy 2 + (aδx)2 . The data points are presented in Tab. 5 and

497

considering an error σy equal to

498

the residuals are plotted in Fig. 11. The result of the fit is a slope of a = −13.15 ± 0.10 and

499

an intercept of b = 13.13 ± 0.160. With the value of RTP T = 753.872 J, the molar enthalpy

500

of sublimation is (9910 ± 75) J.mol−1 .

T (K ) 9 0 .6 7 0 .3

6 9 .7 5

5 6 .6 7

4 7 .7 2

4 1 .2 1

0 .3

0 .6

0 .9

1 .2

H R S L R S T P

0 .2 0 .1

l n ( Π) - F i t

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 34 of 51

0 .0 -0 .1 -0 .2 -0 .3 0 .0

1/θ − 1

Figure 11: Residuals from the fit ln(Π) function of (1/θ − 1) on the whole range 40-90 K. The Triple point is included in the fit with its uncertainties.

501

Looking at Fig. 11 we can conclude that the data points from the two independent exper-

502

iments overlap well on the common temperature interval confirming correct calibrations of

503

the two experiments (mainly the optical path measurements). Secondly, considering the un34

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The Journal of Physical Chemistry

504

certainties of our measurements, it would be tempting to extrapolate the curve to the triple

505

point. Putting θ = 1 gives a pressure of p = 11518(710) Pa which is compatible with the

506

value pT P = 11696(2) Pa. This extrapolation could suggest to take ∆sub H constant on the

507

whole 40-90.6941 K range and to include the triple point in the data. However, this happens

508

because of too large experimental uncertainties on the pressure and we will see in the next

509

paragraph that a thermodynamical approach based on the measurement of heat capacity Cp

510

for both gas and solid phases yields a small dependence of ∆sub H with the temperature.

511

512

The following equation expresses the enthalpy of sublimation at a temperature T below the triple point by:

∆sub H(T ) = ∆sub H(TT P ) +

Z

T

TT P

g s (CpM (T ) − CpM (T ))dT

(18)

513

g s (T ) and CpM (T ) are the isobaric molar heat capacities in the gas and solid phases, where CpM

514

respectively, and ∆sub H(TT P ) is the molar enthalpy of sublimation at the triple point tem-

515

perature TT P . Its value is equal to the sum of the easily derived enthalpies of vaporization

516

and fusion: ∆sub H(TT P ) = ∆vap H(TT P ) + ∆f us H(TT P )

(19)

517

The former value was calculated from a polynomial equation ∆vap H(T ) = f (T /TT P )

518

containing four fitted parameters and is suitable for temperatures from the triple point to

519

the critical point. 39 This value ∆vap H(TT P ) = 8721 J.mol−1 is not far from ∆vap H(TT P ) =

520

8731.29 J.mol−1 obtained by Setzman and Wagner 10 using a more complete analysis of ex-

521

perimental data obtained between 60 and 3000 K. The enthalpy of fusion at the triple point

522

is ∆f us H(TT P ) = 928.4 J.mol−1 , determined by Colwell et al. 15 in the range 90.659-92.325 K.

523

Here, ∆sub H(TT P ) will be taken to be (9659 ± 12) J.mol−1 . Below the triple point, the value

524

g of CpM (T ) was calculated from the molecular properties. 40 A very small change is observed

525

from 60 K (4.0014×R) to 90.6941 K (4.0021×R) very near to the value of 4R deduced from

526

g the kinetic theory. CpM (T ) is taken at 4.0021 × 8.3144598 = 33.275 J.K−1 .mol−1 . Solid

35

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Page 36 of 51

527

heat capacities were measured by Colwell et al. between 5 and 90.37 K. Taking into account

528

that solid methane exists in two differents solid phases, we considered only data in the

529

temperature range of the present work, between 30 and 88.4 K, corresponding to the so-

530

called Phase I solid methane. To perform the integration of Eq. 18, it was useful to express

531

g s CpM (T ) − CpM (T ) as a polynomial formula. Hence:

g s CpM (T ) − CpM (T ) = 34.2 − 1.20 T + 1.40 10−2 T 2 − 6.9 10−5 T 3

(20)

532

The model reproduces the experimental data better than the experimental uncertainty

533

estimated at 1 %. 15 The measurement at 90.4 K was not regarded in the fit, since it is

534

s too close to the triple point, for which a divergence of CpM is produced because of the

535

s discontinuity of the entropy. In order to estimate how the 1 % errors on CpM are propagated

536

to the enthalpy in the integration, two third order polynomial formulae similar to Eq. 20

537

have been calculated with Cps increased or decreased by this amount. The uncertainty of

538

12 J.mol−1 on ∆sub H(TT P ) in Eq. 18 was also included. Finally, the result is represented

539

on Fig. 12 by an uncertainty zone around the calculated enthalpy of sublimation ∆sub H(T ).

540

The maximum of the curve is obtained at about 53 K (∆sub H(T ) = 9870 J.mol−1 ) and the

541

variation of ∆sub H(T ) is less than 2 % within the range of temperature 30-90.6941 K. Due

542

to integration from the triple point Eq. 18, the uncertainty increases as the temperature

543

decreases reaching a value of about 20 J.mol−1 at 40 K. For comparison, on Fig. 12 we plot

544

a rectangle corresponding to our experimental determination ∆sub H = (9910 ± 75) J.mol−1

545

within our experimental range 40-77 K.

546

It can be observed that the difference between the experimental and calculated 15 ∆sub H(T ),

547

both determined independently, is not significant. This becomes all the more evident if we

548

consider that the uncertainties presented in the figure are one standard deviation. The physi-

549

cal meaning of the experimental enthalpy of sublimation is thus confirmed, and consequently,

550

the quality of experimental pressures and temperatures. However, their accuracy, and in par-

551

ticular that of the absolute value of T , is not yet high enough to observe a T -dependence of 36

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Page 37 of 51

552

∆sub H(T ) as proposed by the model given in (Eqs. 18 and 20), the dependence being very

553

small as mentioned above. The required accuracy should be better than 1 %. On the other

554

hand, from the calculated curve it is clear that the average of molar enthalpy in the 40-77 K

555

range differs from the value at the triple point (9659 ± 12) J.mol−1 by more than 1%. This

556

confirms our reservations to include the triple point TT P , pT P in the data and to analyse

557

them restricted to our studied temperature range.

m o d e l a c c o r d in g to R e f.[1 4 ] + - σ1%

1 0 2 0 0

∆H

-1

S u b lim a tio n e n th a lp y ( J m o l )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

( L in e b y lin e ) { T m in . , T m a x . }

1 0 1 0 0

∆H

( L R S + H R S fit) { + - σ ;T m in . , T m a x . }

4 3 3 7 .5 5 1 0 0 0 0

4 3 3 3 .6 7

4 3 3 0 .1 1

4 3 3 4 .4 4

4 3 2 4 .9 3

9 9 0 0

4 3 3 3 .3 1 4 3 2 8 .4 3

9 8 0 0

4 3 3 0 .6 3

4 3 3 2 .2 4

T P

9 7 0 0 3 0

4 0

5 0

6 0

7 0

8 0

9 0

T e m p e ra tu re (K ) Figure 12: Variation of the sublimation enthalpy with temperature from 30 K to the triple point calculated from measured solid and gas heat capacities Eq. 18 (blue curve) with 1 % uncertainty (greyed zone). Our experimental values are represented by the red squares corresponding to the nine individual transitions, by the green rectangle derived from both LRS and HRS pressures. The vertical error bars are the 1-σ uncertainty and the horizontal extension concerned the temperature range.

558

Following this remark, considering the HRS set-up, the relative uncertainty of the tem37

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559

perature measurement is clearly better than its absolute accuracy of 0.25 K. Then, Eq. 14

560

tells us that the enthalpy, slowly temperature dependent, can be considered as the derivative

561

of the logarithm of the saturated pressure curve as a function of the inverse of the tempera-

562

ture. Thus, our measurements can be analysed in a different way, focusing on the variation

563

of the saturated pressure for a definite elevation of temperature (1 or 5 K in our case). In

564

addition, each transition can be separately treated over a limited temperature range where

565

its measurement is regarded confident. For our sets of transitions, we consider that enthalpy

566

remains constant within each range, such a value being attributed to the middle of the range.

567

In this process, the relative uncertainty on T is reduced to 0.03 K and the value of S does

568

not interfere as it only goes in the intercept value of the linear fit of ln(p) as a function of

569

1/T (see Eq. 7). The results are reported in Fig. 12 and show a small but not significant in-

570

crease of enthalpy with decreasing temperature. Considering a constant value over the range

571

40-70 K, an average value including the nine transitions leads to the value 9885 ± 75 J.mol−1 ,

572

practically identical value to the one obtained from the linear fit of the average pressures

573

(9910 ± 75 J.mol−1 ).

574

Finally, in Fig. 13 we compare the saturated pressures derived from the thermodynamics

575

(Colwell et al. 15 ) with the experimental measurements of Tickner et al. , 13 the derived curve

576

from Armstrong et al. 12 , and the present work. Let us note here that the pressure varies

577

over six orders of magnitude within the temperature range (and even seven orders if the

578

triple point is included). For clarity, the relative difference from the thermodynamic model

579

is plotted. An uncertainty of 1 % on the heat capacity measurement has been propagated in

580

the pressure curve (grey zone) and gives an error of 3 % at 40 K. Armstrong’s curve shows a

581

discrepancy of 18 % at 54 K, Tickner’s lowest points are 100 % off around 50 K but this was

582

already mentioned in his paper, our data points lie from 18 to 5 % lower in the range from

583

40 to 77 K.

38

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Page 38 of 51

Page 39 of 51

1 .2

m o d e l b a s e d o n R e f. [1 4 ] ( + - σ1 % ) R e f. [1 2 ] R e f. [1 3 ] T h is w o r k

0 .8 0 .6

s o u rc e

- p

R e f.[1 4 ]

)/p

R e f.[1 4 ]

1 .0

(p

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

0 .4 0 .2 0 .0 -0 .2 -0 .4 4 0

5 0

6 0

7 0

8 0

9 0

T e m p e ra tu re (K )

Figure 13: Comparison between the thermodynamic model derived from Colwell et al. 15 and experimental data for the saturated vapor pressure below the triple point. For clarity, the relative difference is plotted. Green curve: Armstrong’s formula, 12 Red squares: Tickner et al. data, 13 Blue dots: our work.

39

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584

Discussion

585

In our experiment the uncertainty, dominated by the absolute accuracy of the temperature

586

(Fig. 11), did not allow for the detection of a significant variation of the molar enthalpy of

587

sublimation nor for a more refined computed curve, 41 as was done for water. 8 However, the

588

retrieved value of ∆sub H = (9910 ± 75) J.mol−1 for the temperature range of 40-77 K was in

589

agreement with the variation of ∆Hsub calculated for the 30-90 K range from Eq. 18 (Fig. 12).

590

To go further, it is important to improve the pressure measurement below 10−2 P a as well

591

as the absolute value of temperature. As demonstrated, spectroscopic measurement of the

592

absorption of the gas is a good candidate for the first challenge. In principle, this can be done

593

considering only one transition. As an example, the absorption of the Rb (0, A1 ) transition

594

can be considered. Measurements in the 41-50 K range has an uncertainty better than 1 %,

595

which yields saturated pressure values given in Tab. 6 with a focus on the temperature

596

TB and TA (temperature of the second sensor used for the servo-locking process). The

597

choice of TB was guided by the argument of an independent measurement with no coupling

598

with electronics. However, here, TA is also a temperature measurement at another point

599

of the cell, and less than TB . Considering that saturated pressure is determined by the

600

lowest temperature in the cell, it seems to be more appropriate to choose TA instead of TB .

601

Do TA or TB really represents the real temperature of the gas? The difference TB − TA

602

varies from 0.081 K at 70 K to 0.19 K at 40 K and influences by less than 1 % the pressure

603

derived from Eq. 7. However, for enthalpy determination, these pressure values have to be

604

connected to a precise temperature. Using TA instead of TB in the treatment above including

605

the nine transitions has been tested, and led to a decrease in the enthalpy value of 1 % ,

606

∆sub H = 9807(57) J.mol−1 instead of 9885(75) J.mol−1 . Let us recall that around 40 K a

607

variation of 7 % on the pressure is observed for a temperature difference of 0.1 K, and 90 %

608

for a gap of 1 K.

609

Therefore, the question of the temperature measurement must be posed. Instead of the

610

contact sensors, there are two possible ways on our HRS set-up to derive the temperature 40

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The Journal of Physical Chemistry

Table 6: Pressure derived from Eq. 7 for the transition Rb (0, A1 ) considering the two available temperatures of the cell in HRS, TB and TA . TB (K) 40.189 41.109 42.123 43.115 45.138 50.107

TA (K) 39.996 40.947 41.963 42.969 44.992 49.984

p(TB ) (Pa) 7.32E-04 1.47E-03 2.98E-03 5.99E-03 2.02E-02 2.75E-01

p(TA ) (Pa) 7.24E-04 1.46E-03 2.96E-03 5.95E-03 2.00E-02 2.73E-01

δp (Pa) 1.33E-05 1.23E-05 1.61E-05 1.79E-05 7.86E-05 9.07E-04

δp/p

(p(TB ) − p(TA ))/p

0.018 0.008 0.005 0.003 0.004 0.003

-0.011 -0.009 -0.009 -0.008 -0.007 -0.006

611

from the spectra. The first one is to consider the shape of each transition and to measure

612

their Gaussian width driven by the Doppler effect. The result is quite good but not enough to

613

reach even a 1 K precision, especially at low temperature where the signal to noise decreases.

614

The second method is well known to spectroscopists looking at the shape of R or P branches

615

which results from the Maxwell distribution of the fundamental state. This method can be

616

simplified in our case, by measuring the ratio of the integrated absorbances σ1 and σ2 of two

617

transitions with different lower state energies. An example is given with the R(0, A1 ) and

618

Qb (1, F1 ) transitions at 4333.669 and 4324.9331 cm−1 , respectively. T can be derived from

619

the following equation: σ1 ln σ2 



S1 (T ) = ln S2 (T )

!

!

S1 (T0 ) 1 1 = ln − (E1 − E2 ) × − S2 (T0 ) kT kT0 



(21)

620

where E1 and E2 are the energies of the lower level (fundamental state) of transitions 1 and

621

2 (accurately measured by rotational spectroscopy), and S1 (T0 ) and S2 (T0 ) the oscillator

622

strength at T0 = 296K. Unfortunately, the uncertainties on σ1 and σ2 and those on S1 (T0 )

623

and S2 (T0 ) were not low enough to reach uncertainties in the range of 1 K for the temperature.

624

Accurate values of the transition strengths Sηη0 are required to derive temperature but

625

also to obtain reliable pressure. Only nine transitions were used in the study, more lines

626

could be used in the relevant temperature range if their transition strengths are confident.

627

On the other hand, one can imagine reversing the problem and using the low-temperature

41

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The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

628

saturated vapor pressure spectra recorded at high resolution to increase the accuracy of

629

some transitions strengths. In particular, transitions corresponding to low J values are often

630

better measured at low temperature, taking advantage of larger absorption, better resolution

631

(Doppler effect), and less dense spectra (less blended transitions). Indeed, the work is

632

continuing in this direction as such an improvement would be useful in the perspective of

633

new space missions . 42

634

Also, as mentioned in the text, the temperature of 40 K is a limit where the population

635

ratio of the three nuclear spin isomers of methane starts to differ from its value at room

636

temperature. Data analysis at lower temperatures would allow consideration of the nuclear

637

spin conversion dynamics. 9

638

Conclusion

639

In this paper, we have applied absorption spectroscopy techniques to probe gas phase

640

methane at temperatures below 91 K to deduce its Clapeyron solid-gas equilibrium curve.

641

To this end, we used two distinct experimental setups.

642

The first one is a standard commercial “low resolution” spectrometer which allowed us

643

to measure the Clapeyron curve in the range 53-77 K and demonstrate that it is possible to

644

derive this type of data at low pressures (down to ∼ 10−1 Pa for methane) and temperatures

645

using a spectrometer that is not generally used to characterize the gas phase. This limit cor-

646

responds to the limit of detection raised by standard manometric measurements according

647

to Fray et al. 43 In that study, it is claimed that several molecules have no or poor measure-

648

ments of the p(T ) law in that pressure domain (C2 H2 , CH2 =C=CH2 , C6 H6 , HCN,. . .) and

649

that the empirical relations deduced at higher pressures cannot be extrapolated to lower

650

temperatures. With a low resolution set-up it becomes possible to extend our knowledge of

651

the saturation pressure curve for many molecules of astrophysical interest.

652

A second setup used a home-made high resolution laser source at 2.3 µm performing

42

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The Journal of Physical Chemistry

653

high sensitivity absorption measurements which yielded novel data in the thermal range 40-

654

50 K (with p down to ∼ 10−3 Pa) increasing by two orders of magnitude the validity of the

655

Clapeyron law. On the other side, it is possible to measure pressure up to 70 K, by choosing

656

transitions with low line strength S as soon as this value is known with enough precision.

657

With the two techniques, we were able to provide reliable and precise information about

658

the methane vapor pressure in the 40-91 K range corresponding to a pressure variation of

659

seven orders of magnitude. We have shown that this in situ method is more convenient than

660

standard manometric measurements. Reasons include the absence of the transpiration effect,

661

which typically occurs when using gauges, and also that the measurement of the targeted

662

molecular density is not sensitive to any impurity.

663

Acknowledgments

664

This work was supported by the Programme National “Physique et Chimie du Milieu Inter-

665

stellaire” (PCMI) of CNRS/INSU with INC/INP co-funded by CEA and CNES. This work

666

was also supported by the French National Research Agency (Project ANR GASOSPIN

667

number 09-BLAN-0066-01). This project has received funding from the European Union’s

668

Horizon 2020 research and innovation programme under grant agreement No 692335. G.V.

669

thanks NSP of SR for financial support of her internship in Laboratoire PhLAM Lille.

670

References

671

672

673

674

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(3) Wuebbles, D. J.; Hayhoe, K. Atmospheric Methane and Global Change. Earth Sci. Rev. 2002, 57, 177–210.

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(4) Lutz, B. L.; Owen, T.; Cess, R. D. Laboratory Band Strengths of Methane and their

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Application to the Atmospheres of Jupiter, Saturn, Uranus, Neptune, and Titan. As-

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spiration and a Critical Appraisal of Correction Methods for Capacitive Diaphragm

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Accuracy Measurements of the Vapor Pressure of Ice Referenced to the Triple Point.

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version in CH4 : A Multichannel Relaxation Mechanism. J. Phys. Chem. A 2016, 326,

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Properties for Methane Covering the Range from the Melting Line to 625 K at Pressures

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(16) Mondelain, D.; Camy-Peyret, C.; Mantz, A. W.; Tang, E.; Valentin, A. Performance

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of a Herriott Cell, Designed for Variable Temperatures between 296 and 20 K. J. Mol.

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Spectrosc. 2007, 241, 18–25.

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Michaut, X.; Moudens, A.; Fillion, J.-H.; Bertin, M. et al. Observation of Methane

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(18) Gordon, I.; Rothman, L.; Hill, C.; Kochanov, R.; Tan, Y.; Bernath, P.; Birk, M.;

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Spectroscopic Database and HAWKS (HITRAN Atmospheric Workstation): 1996 Edi-

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Huet, T.; Roy, P.; Fournier, M. et al. Nuclear Spin Symmetry Conservation in 1 H2 16 O

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Tourni´e, E.; Genty, F. GaSb-based VCSELs Emitting in the Mid-Infrared Wavelength

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Spectroscopy of

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Laser Source. J. Quant. Spectrosc. Radiat. Transfer 2014, 137, 13–22.

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NH3 and

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NH3 in the 2.3 µm Spectral Range with a New VECSEL

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(39) Somayajulu, G. R. New Equations for Enthalpy of Vaporization from the Triple Point to the Critical Point. Int. J. Thermophys. 1988, 9, 567–575. (40) McDowell, R. S.; Kruse, F. H. Thermodynamic Functions of Methane. J. Chem. Eng. Data 1963, 8, 547–548.

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783

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785

Appendix

786

Determination of the path length in the LRS

787

The precise optical path length, LLRS , was needed to model the spectra recorded with the

788

low resolution setup. For the high resolution setup, this length has been determined in a

789

previous work: LHRS = 692 ± 5 cm. 17 For the LRS, we introduced methane progressively 48

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The Journal of Physical Chemistry

790

into the cell from 0.755 up to 6.938 Torr at a temperature of 76.19 K, recording spectra

791

corresponding to each pressure. The spectra of the ν2 + ν3 band are displayed in Fig. 14a,

792

where only the R(0) and R(1) lines correspond to an isolated transition. Fig. 14c displays for

793

each of the six pressures the difference between experimental and modeled spectra, defined

794

above, and varying the path length LLRS . Each curve has a minimum situated between

795

1.711 and 1.781 cm. From that, we have determined that LLRS = 1.746 ± 0.035 cm. Fig. 14b

796

displays the simulated spectra corresponding to the minima of Fig. 14c. We see that the

797

agreement is satisfactory.

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The Journal of Physical Chemistry

-1

W a v e n u m b e r (c m

A

o b s

= 1 - I ( ~ ) / I 0 ( ~ )

4 5 5 5

4 5 5 6

4 5 6 7

4 5 7 8

0 .0 4

C H 0 .0 3

)

4 5 8 0

4 5 9 0

4 5 9 1

( ν2 + ν3 ) 4

(a )

0 .0 2 0 .0 1 0 .0 0

R (1 )

R (0 )

R (3 ) (b )

R (2 )

A

c a lc

0 .0 3 0 .0 2 0 .0 1 -0 .5

(c ) -1 .0

L

L R S

= 1 .7 4 6 + /-0 .0 3 5 c m

)

-1 .5

χ2 ( L

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 50 of 51

-2 .0 -2 .5 -3 .0

p (to 0 .7 1 .3 1 .9 2 .4 4 .1 6 .9

rr) 5 5 9 0 1 6 2 7 6 8 3 8

T = 7 6 .1 9 K

-3 .5 1 .5

1 .6

L

1 .7 c e ll

1 .8

1 .9

(c m )

Figure 14: Determination of the optical path length of the absorption cell used with the LRS. Plot (a) shows experimental absorption while plot (b) shows the best simulated absorption obtained for six pressures between 0.755 and 6.938 Torr at 76.19 K. Plot (c) shows the χ2 difference between experimental and modeled spectra.

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TOC Graphic:

2.3 mm R(0)

p (Pa)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

T=40-77K

T (K)

798

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