Electronic polarization is also called molar (or molar) refraction and denoted by the letter R.

So, at high enough frequencies for non-polar substances molar refraction can be determined by the formula:

The change in the speed of light when moving from one medium to another is associated with the interaction of light with the electrons of molecules. Therefore, the refractive index n associated with electronic polarization R.

Based on the electromagnetic theory of light, Maxwell proved that for transparent non-polar substances there is a relationship:

where n ¥ is the refractive index of a substance at an infinite wavelength, l ® ¥.

Let's substitute Maxwell's relation into formula (4.21). We get the following equation

R= (4.23)

Since R = P el = ,

That (4.24)

Relationship (4.24) is called the Lorentz–Lorentz formula. It relates the refractive index of a substance n with electronic polarizability a its constituent particles. Formula (4.24) was obtained in 1880 by the Dutch physicist H.A. Lorentz and, independently of him, the Danish physicist L. Lorentz. Formula (4.23) is convenient to use for pure substances.

Refractive index n depends on the wavelength according to the Cauchy formula:

n l = n ¥ + a/l 2 ,

where a is some empirical constant.

Consequently, refraction is also a function of wavelength, i.e. R = f(l).

Usually, to determine refraction, it is enough to use the refractive index corresponding to the visible region of the spectrum. The yellow line in the sodium spectrum was chosen as the standard (for a more accurate determination of the refractive index, a sodium lamp is used as a light source). The wavelength corresponding to the yellow line Na, l D = 5893 A 0 = 589.3 nm. Refractive index accordingly n D.

For nonpolar substances, n weakly depends on frequency (or wavelength).

For example, for benzene A

For polar substances, Maxwell's relation does not hold. Yes, for water A .

If the molecule is approximately considered as a sphere of radius r, then a » r 3,

and R = , (4.25)

those. molar refraction R is equal to the volume of all molecules, contained in one mole of a substance, and characterizes the polarizability of all electrons contained in 1 mole of a substance. This is physical meaning of refraction.

Dimension [R] = m 3 (in the SI system), [R] = cm 3 (in the GHS system).

Molar refraction R has a number of properties, thanks to which it is widely used in solving issues related to the structure of matter.

Let's consider the properties of refraction.

1. Refraction practically does not depend on the state of aggregation, temperature, pressure. Therefore, it can be considered as some constant characteristic of a given substance.

2. Molar refraction is the quantity additive . This property is manifested in the fact that the refraction of a molecule will consist of the refractions of ions, atoms, atomic groups, and individual bonds.

Thus, the molar refraction of a substance can be calculated using the formula:

R= , (4.26)

where R i (at) – atomic refraction;

R i (inc) – refraction of increments, i.e. additional terms for double, triple bonds, cycles, etc.;

n i – number of atoms, bonds, cycles.

The latter method is physically more justified, because the polarizable electron cloud belongs to the bond, not to individual atoms. However, both methods usually lead to almost the same results.

The refraction values ​​of individual atoms and bonds were obtained by comparing the experimental values ​​of molar refractions determined from the refractive indices for different molecules containing these atoms and bonds.

3. Refraction is a quantity constitutive , i.e. the value of R can be used to judge the structure of molecules.

Application of refraction. Using refraction values, you can solve many problems:

1. Calculation of electronic polarizability a el and effective radius of the particle (atom, molecule). Using the Lorentz–Lorentz formula (4.24) and the relation a el » r 3 we can write:

,

(4.27)

However, the value for r, calculated using formula (4.28) is correct only to a first approximation.

2. Refraction can be used for an approximate estimate of the dipole moment of polar molecules .

It is known that P = P el + P at + P or

Because P at<< П эл, то П » П эл + П ор или П = R + П ор,

hence P or = P – R

On the other hand P or =

From the last two expressions we get:

(4.29)

This method of determination m makes sense only for weakly polar substances, because polar molecules interact with each other. It is much more effective to use the method of dilute solutions of polar substances in non-polar solvents to determine polarization.

3. The equation R 1.2 = x 1 R 1 + x 2 R 2 can be used to determine the composition of the mixture And refractive components . Based on the value of refraction, the concentration of solutions can be determined with a very high degree of accuracy.

x 2 = , (4.30)

where R 1 is the refraction of the solvent;

R 2 - refraction of the dissolved substance;

R 1.2 - refraction of the mixture.

4. Constitutivity of refraction used as a simple a way to check the correctness of the expected structure of molecules .

When determining the structural formula of a substance, proceed as follows:

A) determine r, n at one temperature;

b) according to the Lorentz–Lorentz formula, they calculate R– experimental value;

V) Having written several structural formulas that correspond to the empirical formula of the substance, calculate the refraction value for each structure, using tabular data for this R at And R St;

G) compare the experimental value of refraction R op and calculated R calc. The correct structural formula is the one with R op closest to R calc .

REFRACTOMETRIC ANALYSIS METHOD IN CHEMISTRY

Introduction

1.1 Propagation of light

1.3 Light dispersion

1.4 Total internal reflection

2. Dipole moments and refraction

2.1 Polarizability and dipole moment

2.1.1 Molar polarizability

2.2 Molar refraction

3. Refraction and molecular structure

3.1 Additivity of refraction

3.2 Optical exaltation

3.3 Dispersion of molecular refraction

3.4 Refraction and molecular sizes

4. Refractometry of solutions

4.1 Analysis of two-component solutions

4.2 Analysis of three-component solutions

5. Refractometry of polymers

Conclusion

Bibliography

Introduction

The refractometric method has a long history of use in chemistry.

Refractometry (from the Latin refraktus - refracted and Greek metréō - measure, measure) is a branch of applied optics that deals with methods for measuring the refractive index of light (n) during the transition from one phase to another, or, in other words, the refractive index n is ratio of the speed of light in the surrounding media.

In relation to chemistry, refraction has a broader semantic meaning. Refraction R (from the Latin refractio - refraction) is a measure of the electronic polarizability of atoms, molecules, ions.

The polarization of electron clouds in molecules is clearly manifested in the infrared (IR) and ultraviolet (UV) absorption of substances, but to an even greater extent it is responsible for the phenomenon that is quantitatively characterized by molecular refraction.

When light as electromagnetic radiation passes through matter, even in the absence of direct absorption, it can interact with electron clouds of molecules or ions, causing their polarization. The interaction of the electromagnetic fields of the light beam and the electron field of the atom leads to a change in the polarization of the molecule and the speed of the light flow. As the polarizability of the medium increases, so does n, an indicator whose value is related to molecular refraction. This phenomenon is used along with the method of dipole moments to study the structure and properties of inorganic, organic and organoelement compounds.

Refractometry is also widely used to determine the structure of coordination compounds (molecular and chelate-type complexes), study hydrogen bonds, identify chemical compounds, quantitative and structural analysis, and determine the physicochemical parameters of substances.

In industrial practice, the refractive index n is used to control the degree of purity and quality of substances; for analytical purposes - for the identification of chemical compounds and their quantitative determination. Thus, refractometry is a method for studying substances based on determining the refractive index (refractive index) and some of its functions. Of the n functions used in chemistry, the most important are: the Lorentz–Lenz function, the derivative of n with respect to the concentration of dissolved substances (increment n) and dispersion formulas that include differences in refractive indices for two wavelengths. Increments n are used in liquid chromatography and in determining the molecular weight of polymers by light scattering. For refractometric analysis of solutions in wide concentration ranges, tables or empirical formulas are used, the most important of which (for solutions of sucrose, ethyl alcohol, etc.) are approved by international agreements and form the basis for the construction of scales of specialized refractometers for the analysis of industrial and agricultural products. Methods have been developed for the analysis of three-component solutions based on the simultaneous determination of n and density or viscosity, or on the implementation of chemical transformations with the measurement of n of the initial and final solutions; these methods are used in the control of petroleum products, pharmaceuticals, etc. Identification of organic compounds, minerals, and medicinal substances is carried out according to tables n given in reference publications. The advantages of the refractometric method are its simplicity and the relatively low cost of instruments for determining the refractive index of light.

1. Some concepts of physical optics

1.1 Propagation of light

refraction polarizability refraction chemical

The first hypothesis - emission or corpuscular, stated that light is a stream of tiny particles - corpuscles, emitted by a heated luminous body. Reaching the eye, these particles reflect visual sensations. When hitting an obstacle, particles are reflected from its surface or penetrate inside, depending on the properties of the material of the body.

While easily explaining the laws of light reflection, this hypothesis could not explain some features of the refraction of light and did not explain the interference of light at all.

The second hypothesis, the wave hypothesis, argued that particles emitted by a luminous body are in a state of extremely rapid vibrations, generating waves that spread in all directions and, reaching the eye, cause visual sensations. The wave theory did a good job of explaining the interference of light and other phenomena that were inaccessible to the corpuscular hypothesis, but it was unable to explain how waves propagate in a vacuum. Subsequently, this ambiguity was eliminated by the recognition that light waves were of an electromagnetic nature. Thus, according to this hypothesis, light is a rapidly changing electromagnetic field.

Subsequently, with the accumulation of experimental data and their theoretical interpretation, it was possible to establish the special, dual nature of light phenomena and combine both seemingly mutually exclusive hypotheses into one coherent theory, free from internal contradictions. In accordance with this theory, light can equally be considered both as a wave movement of an electromagnetic nature, and as a flow of particles emitted by a light source in the form of individual portions of light - quanta or photons.

At the same time, light phenomena can also be considered from the position of geometric or ray optics, which is the application of geometric constructions and theorems.

The foundation for the rapprochement of geometry with the doctrine of light and the development of ray optics was the idea of ​​​​the straightness of the propagation of light. Beam optics still retains a leading role in all optical and lighting calculations due to its simplicity and clarity, and usually shows complete agreement between calculated and experimental data.

Beam optics is based on three main applications:

Straightness of light propagation in a homogeneous medium;

The behavior of light at the interface between two media, provided that such a boundary is an ideally smooth surface;

Independence of light propagation.

These provisions are established empirically, that is, experimentally by comparing geometric relationships without taking into account the features associated with the complex nature of light.

In order to operate only with visual geometric elements, two conventional concepts have been introduced in ray optics: a ray and a luminous point.

A ray refers to the direction in which light travels. It has been experimentally established that in a vacuum and in a homogeneous (gas, liquid or solid) transparent medium (for example, in air at constant pressure, in water or glass), light propagates rectilinearly, and the beam is a straight line, the beginning of which is the light source.

A luminous point is a light source whose small dimensions can be neglected. Physically, any light source has certain dimensions, however, if you compare these dimensions with the distances over which the action of light extends, then conditionally (without a significant error) the light source is taken as a point.

From a luminous point of light, an infinite number of rays diverge in all directions in the form of a beam, filling the entire surrounding space. Such a sheaf is called unbounded. However, if a diaphragm - an opaque screen with a hole - is placed in the path of such a beam, then behind the diaphragm the light will propagate as a limited beam.

By reducing the diaphragm opening, finer and finer beams can be isolated. It would seem that this should lead to such a thin beam that it can be considered a “separate beam”. However, experience does not confirm this assumption. As the diameter of the hole decreases, the rays lose their straightness and begin to bend around its edges, and the smaller the hole becomes, the larger the rays become.

The phenomenon of light (sound, etc.) waves bending around obstacles encountered along the way is called diffraction of light and is due to its wave nature. For this reason, it is impossible to isolate a single ray and in reality only bundles of rays exist.

1.2 Index of refraction of light (index of refraction)

If on the path of a light beam propagating in a transparent homogeneous medium (for example, in air), it encounters another transparent homogeneous medium (for example, glass), then at the interface between the media, the light beam is divided into two rays, of which one ray enters the new medium, changing its direction (refracts), and the other, reflecting from the interface and changing its direction, continues to propagate in the first medium. When a beam propagates in homogeneous media, changing its unidirectionality, it maintains the straightness of propagation both before and after the interface (Fig. 1).

Thus, refraction and reflection do not contradict the rectilinearity of light propagation in homogeneous media.

Rice. 1. Beam behavior at the interface

Line MM in Fig. 1 depicts the interface (border) between air and glass. An incident beam of monochromatic light (light, conventionally of one wavelength) makes an angle ABO = α with the normal O\O ' to the interface between the media. This angle is called the angle of incidence of the beam. In another medium, the ray makes an angle of refraction with the normal O ’ BC = β.

DETERMINATION OF MELTING TEMPERATURE

Goal of the work: determine the melting point of naphthalene and, based on its temperature range, evaluate the degree of its purity.

2.1.1. Materials, reagents, equipment:

Glass capillary (diameter 1 mm, length 40-50 mm) sealed at one end, glass tube (diameter 10 mm, length 40-50 mm), a device for determining the melting point, naphthalene, electric stove.

General provisions.

Melting point determination

Melting point of the substance is the temperature at which its solid phase is in equilibrium with its own melt.

Melting point is the most important characteristic of a compound. By the value of the melting temperature, it is possible to identify a compound, since this constant is always given in reference books on the properties of compounds, for example, /2, 4/.

To identify substances, the so-called is also often used. "mixed melting sample". To do this, carefully mix equal quantities of the substance being identified and the known substance. If the melting point of the mixture remains unchanged, then a conclusion is made about the identity of both substances. If the melting point of the sample is lower than the melting point of the starting substances, then, consequently, these substances are different. This method is based on the established fact that pure substances have a clearly defined (“sharp”) melting point (with an accuracy of 0.01 C). The presence of impurities tends to lower the melting point. In addition, substances containing any impurities melt in temperature range, i.e., they do not have a clearly defined melting point. Thus, determining the melting point can provide qualitative information about the purity of a substance.

Determining the melting point also allows one to draw indirect conclusions about the possible molecular structure of the substance. For example, it has been established that isomers with symmetrical molecules melt at a higher temperature than substances with a less symmetrical structure. The melting point also increases with increasing degree of association of molecules (for example, due to intermolecular hydrogen bonds).

Approximately estimate The melting point of a substance can be determined using a regular laboratory thermometer. Several crystals of the compound being tested are carefully placed directly onto the mercury bulb of the thermometer. Next, the thermometer with crystals is carefully placed over the surface of a preheated hotplate with a closed spiral. By adjusting the height of the thermometer above the heated surface, the rate of temperature rise is roughly set. Carefully observing alternately the state of the crystals and the temperature value, note Start melting of the substance (appearance of the first droplets of the liquid phase). This process can be repeated several times, achieving the most accurate determination of the beginning of the melting process. Of course, this method gives only an approximate idea of ​​the melting temperature, but it makes it possible to significantly simplify further experiments to accurately determine this constant.

General process methodology

To accurately determine the melting point, there are several structurally different devices of varying degrees of complexity and ease of use, but the principle of their operation is the same. The compound to be tested is placed in a glass capillary (diameter 1 mm, length 40–50 mm), sealed at one end. First, the substance is ground in a mortar into a fine powder. To fill the capillary, its open end is immersed in powder, with some of the substance entering the upper part of the capillary. Next (to move the substance to the lower part of the capillary and compact the layer), the capillary is thrown, sealed end down, into a long, narrow, vertically placed glass tube (diameter 10 mm, length 40 - 50 cm). By repeating this technique several times, one achieves a dense layer of the substance in a capillary 3-5 mm high.

Direct determination of the melting point is carried out in a special glass device (Figure 5), consisting of a round-bottomed flask (1) with a high-boiling coolant, a test tube (2) and a thermometer (3). The capillary (4) with the test substance is attached to the thermometer with a ring of rubber tube (5) so that the column of the substance is at the level of the middle of the mercury ball. The device is heated in an air bath (heating mantle, electric stove) quickly at first, and the last 15-20 below the expected melting temperature, the temperature is increased at a rate of no more than 2 degrees min –1. The melting point is the temperature at the moment of complete melting of a substance.

Typically, a substance melts within a temperature range, and the purer the substance, the smaller the range. The beginning of melting is considered to be the moment the first drop appears in the capillary, and the end is the disappearance of the last crystals of the substance.

Processing the results

In the course of the work done, the melting point of naphthalene was determined, it was found that the temperature range exceeds the permissible values, so we can say that technical naphthalene is not pure enough. It can also be added that mixtures of different substances, as a rule, melt at a lower temperature than the individual substances themselves. To establish whether substances with similar melting points are the same or different, determine the melting point of a mixture of these substances (mixed sample); if the melting point of the sample is lower than the melting point of the substances taken for preparation, then, therefore, we are dealing with different substances. On the contrary, the absence of a depression in the melting point of a mixed sample is considered evidence of the identity of the substances taken.

Lab 2.2

DETERMINATION OF MOLECULAR REFRACTION

ORGANIC COMPOUNDS

Goal of the work: determine the refractive index and identify an unknown organic compound.

2.2.1. Materials, reagents, equipment:

Abbe refractometer, conical flask with an unknown compound, pipette, cotton wool (moistened with ether).

General provisions

The refractive index relative to vacuum is called the absolute refractive index. When measuring refractive indices liquids and solids are usually determined by the relative refractive indices relative to the air in the laboratory room.

The refractive index of a substance is determined by its nature, but also depends on external conditions - temperature and wavelength of light. For organic liquids, with an increase in temperature by 1, it drops by 4·10 –4 -5 · 10 –4.

The refractive index characterizes the polarizability of a molecule, which is understood as its ability to polarize, that is, to change the state of the electron cloud under the influence of an external electric field. As the polarizability of the molecule increases, n increases, and this value is related to the molecular refraction MR according to the Lorentz-Lorentz equation:

,

where n is the refractive index of the substance or solution;

M is the molecular weight of the substance;

d is the specific gravity of the substance (density).

Unlike the refractive index, molecular refraction does not depend on temperature.

In the electromagnetic field of visible light, the polarizability of molecules is almost entirely due to the displacement of electrons and is equal to the sum of the effects of the displacements of individual electrons. The latter circumstance gives the MR of chemical compounds the character of an additive constant. It can be defined theoretically as the sum of the refractions of individual atoms that make up the molecule, taking into account additives (incrementals) that take into account the presence and number of multiple bonds:

MR theor. = Σ AR at. + Σ ink. ,

where AR at. – atomic refraction of one atom;

ink– increment of one connection.

The AR values ​​for individual atoms and the increments of multiple bonds are known and are given in most relevant manuals and reference books
/5, p. 17/ (Table 1). Knowing the hypothetical structural formula of a compound, one can calculate its MR theorem. as the sum of AR at.

For example, for isopropylbenzene (cumene) MR theor. is equal to:

MR theor. = AR C 9 + AR H 12 + ink dv. St. · 3

Substituting the corresponding values ​​of AR and ink (Table 1), we obtain:

MR theor. = 2.418 ∙ 9 + 1.100 ∙ 12 + 1.733 ∙ 3 = 40.161

Table 1 – Atomic refractions of individual atoms and increments

To determine the value of the refractive index, a special device is used - a refractometer. The standard instrument for organic chemistry laboratories is the Abbe refractometer. It is designed in such a way that, when using polychromatic (solar or artificial) light, it gives the refractive index value for the sodium D-line. The measurement requires only a few drops of liquid, and the measurement accuracy is 0.0001 refractive index units. To achieve such accuracy, a constant temperature must be maintained during measurement with an accuracy of 0.2 C (which is achieved using a thermostat). It is advisable to measure the refractive index at 20C, and for low-melting solids - slightly above the melting point.

Since each substance is characterized by its own refractive index value, refractometry, together with other methods, can be used to identify (recognize) substances. Identification is carried out on the basis of the coincidence of the measured and reference values ​​of the refractive index of pure substances found under the same conditions. Due to the fact that different substances may have similar refractive index values, refractometry is usually complemented by other methods of identifying substances (spectral measurements, determination of melting or boiling points, etc.). The refractive index can also be used to judge the purity of a substance. The discrepancy in the measured and reference (for a pure substance) values ​​of the refractive indices of substances found under the same conditions indicates the presence of impurities in it. In cases where there is no information in the literature about the physical constants of a substance (including the refractive index), it can be considered pure only when the physical constants do not change during repeated purification processes. Refractometric structural analysis provides the greatest accuracy for liquid substances. In this case, it is necessary to have data on the composition and molecular weight (gross formula) or grounds for assuming the structural formula of the substance. A conclusion about the structure of a substance is made based on a comparison of MR exp, found using the Lorentz-Lorentz formula, and MR theor. The coincidence of the values ​​of MR exp and MR theor with an accuracy of 0.3-0.4 confirms the probability of the proposed gross formula and structure. Discrepancy Mr theor Mr exp. more than 0.3-0.4 units indicates that the MR theory made when calculating was incorrect. assumptions about the structure and composition of matter. In this case, it is necessary to consider other possible molecular structures of the substance for a given gross formula.

Since the refractive index depends on the concentration of solutions, refractometry is also used to determine their concentration, to check the purity of substances and to monitor separation processes, for example, distillation can be monitored (for analytical purposes). The refractive index of a binary mixture depends linearly on the concentration of the components (in percent by volume), unless there is a change in volume during mixing. If deviations from the linear relationship occur, it is necessary to construct a calibration curve.

Refraction of light– change in the direction of light rays in a medium with a variable refractive index. Refraction of light is a special case of a sharp change in the direction of rays at the interface between two media with different refractive indices.

The cause of these phenomena from the point of view of classical physics is the interaction of the electric field of a light wave with elementary charges. The electric field of the wave acting on the atom displaces the outer electron from the equilibrium position, and the atom acquires an induced dipole moment

p=α E ,

where α is the polarizability of the atom (or molecule), E is the electric field strength of the incident wave. The dipole moment of the atom oscillates with the frequency of the incident light, and the atom becomes a source of secondary coherent waves. The electron's oscillations are delayed in phase relative to the oscillations of the original light wave, so the secondary waves are also emitted with a delay. The field of secondary waves is added to the field of the original light wave, which causes the resulting electromagnetic wave to slow down.

Classical electronic theory allows us to relate the refractive index of a substance with the microscopic characteristics of the medium - density and electronic polarizability, depending on the nature of atoms or molecules and the frequency of light.

It is usually not the refractive index itself that is expressed through microscopic characteristics, but the associated molecular refraction:

Where R – molecular refraction [cm 3 /mol],

M – molecular weight [g/mol],

ρ – density [g/cm 3 ],

N A = 6.023∙10 23 – Avogadro number [mol -1 ],

– specific refraction [cm 3 /g].

Molecular refraction is a physical quantity that characterizes the polarizability of a molecule, or more precisely, 1/3 of a mole of a substance. Its measurement is based on measuring the refractive index and density of the substance.

Different models of the structure of matter lead to slightly different expressions for the function f(n); Most often, the Lorentz-Lorentz formula is used, according to which. It is not the SI system that is used here, but the old GHS system, according to which data are presented in most chemical reference books. As can be seen from the last part of formula (6), molecular refraction does not depend on temperature and density, and, consequently, pressure and state of aggregation and is a measure only of the polarizability α of molecules:

that is, it is a characteristic of a chemical compound.

Values R in the visible region of the spectrum characterize the polarizability of the electron shells of the molecules of a substance. If the polarizability of the components does not change during dissolution, then the refraction of solutions is composed of R i refraction components:

Where x i– concentration i th component in mole fractions.

The rule of additivity of molecular refractions of solutions allows us to calculate R dissolved solids. Moreover, the additivity of molecular refraction is approximately observed for pure compounds. For ionic compounds it is equal to the sum of ionic refractions (see Table 1 in the Appendix).

Example 1. Potassium chloride

Calculated R theor (KCl) = R(K +) + R(CI –) = 2.2 + 8.7 = 10.90;

Molar mass M(KCl) = 74.56 g/mol;

Density ρ(KCl)=1.985 g/cm 3 ;

Refractive index for the yellow D line of sodium at 20 degrees Celsius n D20 (KCl) = 1.490; then calculated from experiment

We get the error Δ R= 0.04 and relative error or 0.4%.

The molecular refraction of compounds with valence bonds can be presented as the sum of atomic refractions (see Table 2 in the Appendix).

Example 2. n-Pentane CH 3 –(CH 2) 3 –CH 3

R theor (C 5 H 12) = 5R(C) + 12R(H) = 5∙2.418 + 12∙1.100 = 25.290;

M(C 5 H 12) = 72.15 g/mol;

ρ(C 5 H 12) = 0.62619 g/cm 3 ;

n D 20 (C 5 H 12) = 1.35769;

We get the error Δ R= 0.008 and relative error or 0.03%.

The atomic refractions that appear in such calculations partially include the effects of the mutual influence of atoms and are not equal to the atomic refractions of the corresponding simple substances. The influence of the structure of the molecule on molecular refraction is taken into account by introducing different values ​​of atomic refractions for the same element in different groups (for example, different atomic refractions for oxygen in ethers, alcohols and carboxyl compounds (see Table 2 in the Appendix)) or by using group refractions (for example, group refractions of groups NO, N0 2, CN, etc.), as well as by using special increments (i.e. increments) for multiple bonds (double bond C=C, triple bond C≡C) .

Instead of atomic and group refractions, bond refractions are often used, and molecular refraction is decomposed into terms according to the number and types of bonds, to which the polarizability of electrons not involved in the formation of bonds is conventionally attributed (see Table 3 in the Appendix).

Example 3. 1-Bromopropane CH 3 –CH 2 –CH 2 –Br

R theor (C 3 H 7 Br) = 7R(C–H) + 2R(C–C) + R(C–Br) = 7∙1.70 + 2∙1.21 + 9.47 = 23.79 ;

ρ(C 3 H 7 Br) = 1.353 g/cm 3 ;

n D 20 (C 3 H 7 Br) = 1.4344;

We get the error Δ R= 0.10 and relative error or 0.4%.

Example 4. 2-Bromopropane CH 3 – CHBr – CH 3

R theor (C 3 H 7 Br) = 23.79 (since the number and quality of bonds are the same as in 1-bromopropane);

M(C 3 H 7 Br) = 123.00 g/mol;

ρ(C 3 H 7 Br)=1.310 g/cm 3 ;

n D 20 (C 3 H 7 Br) = 1.4256;

We get the error Δ R= 0.3 and relative error or 1.0%.

It cannot be said that in some scheme (by atoms or by bonds) additivity is performed better. Both of them are approximately equivalent within the limits of applicability of the additive scheme for molecular refraction.

Example 5. Bromoform CHBr 3

For atoms R theor (CHBr 3) = R(C) + R(H) + 3R(Br) = 2.418 + 1.100 + 3 ∙ 8.865 = 30.113 (see Table 2 in the Appendix);

For bonds R theor (CHBr 3) = R(C–H) + 3R(C–Br) = 1.70 + 3 ∙ 9.47 = 30.11 (see Table 3 in the Appendix);

Δ R≈ 0.3 and or 1.0%.

Sometimes summation of molecular refraction over bonds gives slightly better results than summation over atoms.

Example 6. Ethyl alcohol CH 3 –CH 2 –OH

R theor (C 2 H 5 OH) = 2R(C) + 6R(H) + R(O in the alcohol group) = 12.961 (see Table 2 in the Appendix);

R theor (C 2 H 5 OH) = 5R(C–H) + R(C–C) + R(C–O) + R(O–H) = 13.05 (see Table 3 in the Appendix) ;

Accordingly, and and 2∙10 -3 (0.2%).

Comparison of the experimental value of molecular refraction with that calculated using additive schemes is one of the simplest physical methods for determining the structure of chemical compounds. This method can confirm the gross formula of a substance and the presence of certain functional groups (for example, information can be obtained on the number of rings in the molecule, the number, nature and location of multiple bonds, etc.). In some cases, conclusions about the cis or trans configuration of the molecule are also possible.

A el substance (see. Polarizability atoms, ions and molecules) with its refraction Within the limits of applicability of expressions for M. r. she, characterizing as P, the ability of a substance to refract differs from n in that it practically does not depend on density, temperature and aggregate matter.

Basic f-la M. r. looks like

Where M- molecular weight of the substance, r - its, N A - Avogadro's constant. F-la (*) is the equivalent Lorentz - Lorentz formula(with the same restrictions on applicability), but in plural. cases is more convenient for practical purposes. applications. Often M. r. can be represented as the sum of the “refractions” of atoms or groups of atoms that make up a molecule of a complex substance, or their bonds in such a molecule. For example, M. r. saturated hydrocarbon CkH 2 k+2 is equal kR C+ + (2 k + 2)R N ( k= 1, 2,...). This is an important property of M. r. - additivity - allows you to successfully use refractometric. methods for studying the structure of compounds, determining the dipole moments of molecules, studying hydrogen bonds, determining the composition of mixtures, and for other physical-chemical. tasks.

Lit.: Volkenshtein M.V., Molecules and their structure, M.-L., 1955; Ioffe B.V., Refractometric methods of chemistry, 3rd ed., Leningrad, 1983; see also lit. at Art. Lorentz - Lorentz formula.

Physical encyclopedia. In 5 volumes. - M.: Soviet Encyclopedia. Editor-in-chief A. M. Prokhorov. 1988 .

See what "MOLECULAR REFRACTION" is in other dictionaries:

Molecular refraction is a measure of the electronic polarization of a substance; it has the dimension of volume, which in order of magnitude coincides with the volume of all molecules in a gram molecule. It follows from this that the order of magnitude of R must coincide with the correction for... ... Wikipedia

molecular refraction

molecular refraction- molekulinė refrakcija statusas T sritis chemija apibrėžtis Dydis, apibūdinantis molekulės elektroninį poliarizuojamumą. atitikmenys: engl. molar refraction; molecular refraction rus. molecular refraction; molar refraction ryšiai: sinonimas –… … Chemijos terminų aiškinamasis žodynas

molecular refraction- molekulinė refrakcija statusas T sritis fizika atitikmenys: engl. molecular refraction; molecular refractivity vok. Molekularrefraction, f rus. molecular refraction, f pranc. réfraction moléculaire, f … Fizikos terminų žodynas

See Molecular refraction...

- (R), connects the electronic polarizability ael in va (see POLARIZABILITY OF ATOMS, IONS AND MOLECULES) with its refractive index n. Within the limits of applicability of expressions for R. m., it characterizes, like n, the ability in va to refract light, is different… … Physical encyclopedia

- (R connects the electronic polarizability αel of a substance (see Polarizability of atoms, ions and molecules) with its refractive index (See Refractive index) n. Within the limits of applicability of expressions for R. m., it, characterizing, like n, ... ... Great Soviet Encyclopedia

AND; and. [from lat. refractio] 1. In optics: a range of phenomena associated with the refraction of light. R. light. Atomic, molecular, specific river. 2. In acoustics: curvature of the propagation of sound waves in an inhomogeneous medium. ◁ Refractive, oh, oh. R y… … encyclopedic Dictionary

refraction- And; and. (from Latin refractio) see also. refractive 1) In optics: a range of phenomena associated with the refraction of light. Refraction / ction of light. Atomic, molecular, specific refraction. 2) In acoustics: curvature of the propagation of sound waves in an inhomogeneous medium... Dictionary of many expressions

molar refraction- molar refraction; industry molecular refraction The product of the value (ν 1)/(ν+1) (where ν is the refractive index for rays of the visible part of the spectrum) by the molar volume of the substance ... Polytechnic terminological explanatory dictionary

Books

• Fundamentals of molecular optics, N. B. Rozhdestvenskaya. This monograph is devoted to issues of molecular optics. The book contains the experience of more than half a century of work of the author in the field of molecular light scattering in pure liquids, solutions and...