Caraterização metrológica de contadores de micro caudal

Nas últimas décadas, as empresas têm sido sujeitas a uma maior concorrência, ao desenvolvimento tecnológico mais acelerado e a novos desafios no que respeita à qualidade. A Metrologia deverá assim acompanhar estas tendências do mercado. O Departamento de Metrologia (DMET) do Instituto Português da Qualidade, I.P. (IPQ) tem vindo a desenvolver esforços significativos que visam a melhoria contínua das técnicas e dos processos de medição e de calibração realizados nos laboratórios. A presente dissertação de mestrado foi realizada no Laboratório de Volume e Caudal (LVC) do DMET. Os objetivos iniciais do trabalho centraram-se na caraterização metrológica de contadores de fluidos, tendo como base a medição do caudal, utilizando como método de referência o método gravimétrico. De forma a validar o sistema de medição foram realizados ensaios entre 1 mL/h a 100 mL/h, em condições de reprodutibilidade, com dois sistemas padrão distintos de acordo com o caudal a ensaiar. Em todos os ensaios efetuados foi necessário monitorizar as condições ambientais, i.e. temperatura, pressão atmosférica, humidade relativa e a temperatura do líquido padrão, para a aplicação das correções necessárias. Outro feito importante foi a caraterização das fontes de incerteza, que permitiram caraterizar o resultado das medições. A metodologia utilizada para a avaliação e para a estimativa da incerteza de medição encontra-se descrita no Guide to the Expression of Uncertainty in Measurement (GUM). Neste projeto foram contempladas fontes de incerteza como as associadas à evaporação, à impulsão do tubo, à resolução da balança, entre outras. Com os resultados obtidos foi possível elaborar um procedimento técnico para a Calibração de Caudalímetros de Líquidos. Os resultados obtidos permitiram garantir a rastreabilidade das medições de caudal de líquidos ao SI, essencial para a calibração de equipamentos no Laboratório Nacional de Metrologia (LNM) do IPQ, nomeadamente para micro caudalímetros no intervalo de medição entre 0,12 mL/h e 600 mL/h.

O efeito de Coriolis: de pêndulos a moléculas

Coriolis force is an effect which arises in rotating reference frames such as the Earth. This force influences large oceanic motions, atmospheric inertial circles, horizontal and vertical deviations in moving bodies. The Foucault's pendulum is another special case about the Coriolis force influence on macroscopic processes. This pendulum is an example of how experimental sciences can be essential for philosophical and social changes, since it was crucial to prove the Earth's rotation. The Coriolis force has an important role also at microscopic level; it couples vibrational and rotational molecular motions and this fact has consequences in spectroscopic and energetic molecular processes. These points are discussed in this paper.

Coriolis effects in symmetric top spectra /

The "x-y Coriolis Coupling Theory" as presented by Dilauro and Mills (1966) is reformulated and extended to the determination of Raman intensities. Theoretical Raman and Infrared spectra are computed in order to understand the effects due to this coupling in both types of spectra. Both the Infrared and Raman spectra obtained indicate very real effects due to Coriolis coupling. In some of the cases chosen the computed spectra are grossly different from the normal spectra where coupling is absent. Such large effects can greatly impede the interpretation of experimental results. Theoretical spectra therefore aids in the interpretation of experimental results, as is clearly demonstrated in the results of this work.

El mito de la fuerza de Coriolis.

resumen ofrecido por la publicación

Coriolis interactions about x-y axes in symmetric tops

Selection rules and matrix elements are derived for Coriolis interactions between vibrational levels due to rotation about (x, y) axes in symmetric top molecules. The theory is developed in detail for the case of interaction between an A1 and an E species vibrational level in a C3v molecule; perturbations to both the positions and the intensities of the rovibration transitions in the spectrum are considered. A computer program has been written which calculates exactly the perturbed spectrum of two interacting rovibration bands according to this model, the results being presented directly by a graph plotter connected to the computer. This has been used to interpret perturbations observed in two pairs of interacting fundamentals in the spectrum of CH3F (ν2 - ν5 and ν3 - ν6) and one pair in CD3Cl (ν2 - ν5). The resulting analysis of the observed spectrum leads to new values for some vibration-rotation interaction constants and also leads to a unique determination of the sign relationship between the dipole moment derivatives in each pair of interacting normal vibrations. These sign relations are summarized in Figs. 8, 12, and 15.

Coriolis perturbations in the infrared spectrum of ethylene

Rotational structure has been resolved and analyzed in two of the infrared‐active perpendicular bands of C2H4 vapor: the Type b fundamental band, ν10, at 826 cm—1, and the Type c fundamental band, ν7, at 949 cm—1. Many of the individual PP and RR branch lines have been observed. The analysis has been confined to values of the quantum number K≥3, for which energy levels ethylene shows no detectable deviations from a symmetric‐top rotational structure. The analysis reveals a Coriolis interaction between ν7 and ν10, and between ν4 and ν10, and values of the Coriolis constants ζ7,10z and ζ4,10y are obtained; these are related to normal coordinate calculations for the appropriate symmetry species, and force constants are derived to fit the observed zeta constants. The band center of ν10 has been revised from the original figure of 810 cm—1 to the new value, 826 cm—1, and the inactive frequency ν4 is estimated to lie at 1023±3 cm—1, in good agreement with the previous estimate of 1027 cm—1. The change in the value of ν10 leads to a suggested change in the value of the Raman‐active fundamental ν6 from 1236 to 1222 cm—1. New combination bands have been observed at 2174 cm—1, assigned as ν3+ν10; and at 2252 cm—1, assigned as ν4+ν6; also rotational structure has been resolved and analyzed in the ν6+ν10 band at 2048 cm—1. The new data obtained for the C2H4 molecule are summarized in Table XII, with all of the other data presently available on the vibrational and rotational constants.

Coriolis perturbations in the infrared spectrum of allene

High resolution infrared spectra of the ν9 and ν10 perpendicular fundamentals of the allene molecule are reported, in which the J structure in the sub-bands has been partially resolved. Analysis of the latter shows that the vibrational origin ν9 = 999 cm−1, some 35 cm−1 below previous assignments. The pronounced asymmetry in the intensity distribution of the rotational structure which this assignment implies is shown to be expected theoretically, due to the Coriolis perturbations involved, and it is interpreted in terms of the sign and magnitude of the ratio of the dipole moment derivatives in the two fundamentals. The results of this analysis are shown to be in good agreement with observations on allene-1.1-d2, where similar intensity perturbations are observed, and with an independent analysis of the ν8 band of allene-h4. The A rotational constant of allene-h4 is found to have the value 4.82 ± 0.01 cm−1, and for the molecular geometry we obtain r(CH) = 1.084 A, r(CC) = 1.308 A, and HCH = 118.4°. A partial analysis of the rotational structure of the hot bands (ν9 + ν11 − ν11) and (ν10 + ν11 − ν11) is presented; these provide an example of a strong Coriolis interaction between nearly degenerate A1A2 and B1B2 pairs of vibrational levels. Some localized rotational perturbations in the ν9 and ν10 fundamentals are also noted, and their possible interpretations are discussed.

Second order Coriolis resonance in the v2, v5 Raman bands of CH3F

The vibration-rotation Raman spectrum of the ν2 and ν5 fundamentals of CH3F is reported, from 1320 to 1640 cm−1, with a resolution of about 0.3 cm−1. The Coriolis resonance between the two bands leads to many perturbation-allowed transitions. Where the resonance is still sufficiently weak that the quantum number K′ retains its meaning, perturbation-allowed transitions are observed for all values of ΔK from +4 to −4; in regions of strong resonance, however, we can only say that the observed transitions obey the selection rule Δ(k−l) = 0 or ±3. The spectrum has been analyzed by band contour simulation using a computer program based on exact diagonalization of the Hamiltonian within the ν2, ν5 vibrational levels, and improved vibration-rotation constants for these bands are reported. The relative magnitudes and relative sings of polarizability derivatives involved in these vibrations are also reported.

Coriolis perturbations in the infrared spectrum of diborane

High‐resolution infrared spectra of B2H6 vapor are reported. The sample was prepared from the naturally occurring 11B☒10B isotopic mixture. The rotational structure of the infrared bands has been analysed for Coriolis perturbations due to rotation about the axis of least moment of inertia (the B⋅⋅⋅B axis). The following results have been obtained: (a) interaction between the Type A fundamental ν18 and the inactive fundamental ν5 has been observed, thus confirming the assignment of ν5 at 833 cm—1, giving ∣ ζ5,18Z ∣=0.55±0.05; (b) interaction observed between the Type A combination band (ν10+ν12) at 1283 cm—1 and the inactive combination (ν10+ν7) gives an estimate of the unobserved fundamental ν7 as 850±30 cm—1, and an estimate of ∣ ζ7,12Z ∣=0.6±0.1; (c) the absence of any observed perturbation of the Type C fundamental ν14 at 973 cm—1, suggests, by negative arguments, that either the unobserved fundamental ν9 does not lie in the frequency range 900 to 1100 cm—1, or ∣ ζ9,14Z ∣<0.2. The assignment of the unobserved fundamental vibrations of diborane is discussed in the light of this evidence.

Determination of the vibrational transition moment ratio for the Coriolis interacting v9 and v10 fundamentals of allene

Comparison between observed and calculated infrared band contours has been made to determine the vibrational transition moment ratio |M10/M9| for the Coriolis interacting ν9 and ν10 perpendicular fundamentals of allene-h4. The ratio obtained is appreciably lower than that of a previous estimate and the result obtained by integrated band intensity measurements of Overend and Crawford. From the best estimate of the ratio, the dipole moment derivatives of the two bands are determined; the value for the weaker band ν9 is subject to a large uncertainty.

Intensity perturbations due to the v3, v4 Coriolis interaction in methane

Formulas are obtained for the intensity asymmetry (Herman-Wallis) factors in the ν3 and ν4 fundamentals of methane due to the ζ34 Coriolis interaction. The results are also applicable to the ν3 and ν4 bands of SF6.