Properties Estimation: Estimation of Refractive Index
2011.6.26
Lecture note of Dr. Hiroshi Yamamoto
The program that Pirika provide.
Pirika neural network method (JAVA version 2004.11.14)
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Please refer to Refractive Index part2
Definition:
The index of refraction (n) and molar refraction (RD) are indications of the manner in which a molecule interacts with light. The index of refraction is the ratio of the speed of light in a vacuum (c) to the speed of light in the medium (v):
n = c/v
This is a dimensionless parameter which ranges between 1.3 and 1.5 for organic liquids. The refractive index is measured using a beam of monochromatic light - typically, the yellow light of the sodium D line (wavelength l = 589.3 nm). Thus, n20D indicates the wavelength used, D, and the temperature, 20'C. Other wavelengths used are the C and F lines of hydrogen l = 656.3 nm and 486.1 nm, respectively) and the G line of mercury ( l = 435.8 nm). Molar refraction, RD, is a function of the density, r, of the medium. The Lorentz-Lorenz equation expresses the relationship between RD, r, and n, based upon electromagnetic theory:
RD =(n^2-1/n^2+2)M/ r
where M is molecular weight and RD has units of volume. (A term related to RD is the specific refraction, which equals RD divided by M.) Rearrangement of this scheme allows evaluation of n:
n = sqrt((M+2 r RD)/(M- r RD))
Molar refraction and refractive indices have many uses. They are often required in confirming the identity and purity of a compound Determination of molecular structure and weight is often aided by these parameters. RD is also used in other estimation schemes, such as in critical properties , surface tension , and the solubility parameter, which is a measure of intermolecular forces . The refractive index, n, is affected by changes in temperature, pressure, and wavelength of radiation. (RD remains nearly constant with changes of temperature and pressure by virtue of the density factor, which is a function of temperature and pressure and. thus offsets these effects.)
The refractive index increases as pressure increases, due to the resulting increase in density. This effect is not as significant with liquids as with gases. Lastly, the refractive index decreases as the wave length increases. For this reason, one cannot compare indices measured at different wavelengths of light.
Estimation Method
As the refractive index estimation scheme, following scheme is very popular. I already expand this scheme for Halogen-containing functional groups.
I validated this scheme for data base compounds.
If the boiling point is smaller than 25℃, the estimation result come out of the line. Maybe the measurement was done with high pressure. For other compounds, the accuracy is high enough with group contribution method. The temperature dependency of refractive index is not so high and too little experimental data are available for temperature dependency.
This type of estimation scheme is similar with density, so if the molecular size become larger that does not mean larger refractive index. But some of the estimation schemes use plain group contribution method to predict Refractive Index. Such scheme answer very bad result for larger molecule.
For YMB-simulator, I build (RI * Mol volume) estimation QSPR model and get RI.
Estimation result is very bad for high melting point compounds. So please use this result only for liquids compounds at room temperature.
