Pure solvent

See also Part II, 1. Many excellent devices for producing single and double distilled water are available. Ion exchai e purification is suitable for many purposes. For small-scale conversion a makeshift t jparatus of this nature can easily be constructed e.g., a 

Eberius, Water Determination with Karl Fischer Reagent, 2nd edition, Weinheim, 1958. 

Pr aration of absolute ether by shaking with CaClg, allowing it to stand over sodium wire and subsequent distilling is well known. Peroxides, which can be easily detected in ether with a titanium(IV)-sulfuric acid mixture, are removed by shaking with a solution of 600 g. FeSO, 60 ml.HgSO4andll00 ml.water in a separatory fimnel. S aration of the layers is followed by distillation. Equal volumes of ether and solution are used. It is then stored in well-filled bottles over sodium wire. 

For the purification of other organic solvents, consult the well-known textbooks on methods of organic chemistry.  

Mechanical impurities are removed by filtration through leather, a glass suction fuimel, aporcelain filtering crucible or by the makeshift device of filtration through a paper filter, the apex of which has been pierced several times with a pin. 

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It was pointed out at the beginning of this section that ir could be viewed as arising from an osmotic pressure difference between a surface region comprising an adsorbed film and that of the pure solvent. It is instructive to develop... 

To review briefly, the osmotic pressure in a three-dimensional situation is that pressure required to raise the vapor pressure of solvent in a solution to that of pure solvent. Thus, remembering Eq. Ill-16,... 

Let us now suppose that the surface region can be regarded as having a depth T and an area and hence volume V. A volume V of surface region, if made up of pure solvent, will be... 

A film at low densities and pressures obeys the equations of state described in Section III-7. The available area per molecule is laige compared to the cross-sectional area. The film pressure can be described as the difference in osmotic pressure acting over a depth, r, between the interface containing the film and the pure solvent interface [188-190]. 

There are numerous references in the literature to irreversible adsorption from solution. Irreversible adsorption is defined as the lack of desotption from an adsoibed layer equilibrated with pure solvent. Often there is no evidence of strong surface-adsorbate bond formation, either in terms of the chemistry of the system or from direct calorimetric measurements of the heat of adsorption. It is also typical that if a better solvent is used, or a strongly competitive adsorbate, then desorption is rapid and complete. Adsorption irreversibility occurs quite frequently in polymers [4] and proteins [121-123] but has also been observed in small molecules and surfactants [124-128]. Each of these cases has a different explanation and discussion. 

The reference state for the solvent is nomially the pure solvent, so one may write... 

From equation A2.4.38 we can, finally, deduce Walden s rule, which states that the product of the ionic mobility at infinite dilution and the viscosity of the pure solvent is a constant. In fact... 

Anotlier simple way to obtain the molecular weight consists of measuring tire viscosity of a dilute polymer solution. The intrinsic viscosity [q] is defined as tire excess viscosity of tire solution compared to tliat of tire pure solvent at tire vanishing weight concentration of tire polymer [40] ... 

If the thermometer is to be used to determine the elevation of the boiling-point of a liquid on the addition of a solute, it must be remembered that at the boiling-point of the pure solvent the mercury must now be about 1-2 above the bottom of the scale S, and hence for adjustment purposes the temperature of the beaker of water should be 6—7 above the boiling-point of the liquid itself, instead of 1-2 as before. 

Weigh the clean dry tube T, then add about 25 ml. of the pure solvent (i.e., sufficient to ensure that the bulb of the thermometer... 

The angles ot, p, and x relate to the orientation of the dipole nionient vectors. The geonieti y of interaction between two bonds is given in Fig. 4-16, where r is the distance between the centers of the bonds. It is noteworthy that only the bond moments need be read in for the calculation because all geometr ic features (angles, etc.) can be calculated from the atomic coordinates. A default value of 1.0 for dielectric constant of the medium would normally be expected for calculating str uctures of isolated molecules in a vacuum, but the actual default value has been increased 1.5 to account for some intramolecular dipole moment interaction. A dielectric constant other than the default value can be entered for calculations in which the presence of solvent molecules is assumed, but it is not a simple matter to know what the effective dipole moment of the solvent molecules actually is in the immediate vicinity of the solute molecule. It is probably wrong to assume that the effective dipole moment is the same as it is in the bulk pure solvent. The molecular dipole moment (File 4-3) is the vector sum of the individual dipole moments within the molecule. 

Reasonably pure solvents are required for many organic reactions and for recrystaUisations methods for obtaining these from commercial products will accordingly be described. Frequently, the pure solvent (e.g., the analytical reagent) can be purchased, but the cost is usually iiigh, particularly if comparatively large volumes are required. Furthermore, it is excellent practice for the student to purify inexpensive commercial solvents. 

Donor strengths, taken from ref. 207b, based upon the solvent effect on the symmetric stretching frequency of the soft Lewis acid HgBr2. Gutmann s donor number taken from ref 207b, based upon AHr for the process of coordination of an isolated solvent molecule to the moderately hard SbCL molecule in dichioroethane. ° Bulk donor number calculated as described in ref 209 from the solvent effect on the adsorption spectrum of VO(acac)2. Taken from ref 58, based on the NMR chemical shift of triethylphosphine oxide in the respective pure solvent. Taken from ref 61, based on the solvatochromic shift of a pyridinium-A-phenoxide betaine dye. 

Another thing or two to remember when distilling is to wrap aluminum foil around the reaction flask. This will help stop heat loss so that things will distill quicker and at lower temperatures. Sometimes, if one is going to distill a solution that is just solvent and product, all that pure solvent that comes over first is perfectly reusable and should be saved for future extractions. 

In accurate work at low concentrations it is necessary to subtract the conductivity of the pure solvent (Table 8.34) from that of the solution to obtain the conductivity due to the electrolyte. 

In LC, the most common means for monitoring the eluant is to pass it through a cell connected into an ultraviolet spectrometer. As substances elute from the column, their ultraviolet absorption is measured and recorded. Alternatively, the refractive index of the eluant is monitored since it varies from the value for a pure solvent when it contains organics from the column. 

Consider the above result for the case of N2 = 0, that is, for pure solvent The expression in item (6) is proportional to the entropy of the pure solvent Si = 0. 

When either pure component is considered, all Wij terms are zero, as well as the terms containing the volume fraction of the other component. Thus, for pure polymer, item (3) becomes A)z4>2 fJ22, and for the pure solvent item (6) becomes ( /i)z0iNwn. ... 

Figure 8.3b shows that phase separation in polymer mixtures results in two solution phases which are both dilute with respect to solute. Even the relatively more concentrated phase is only 10-20% by volume in polymer, while the more dilute phase is nearly pure solvent. The important thing to remember from both the theoretical and experimental curves of Fig. 8.3 is that both of the phases which separate contain some polymer. If it is the polymer-rich or precipitated phase that is subjected to further work-up, the method is called fractional precipitation. If the polymer-poor phase is the focus of attention, the method... 

Osmotic pressure is one of four closely related properties of solutions that are collectively known as colligative properties. In all four, a difference in the behavior of the solution and the pure solvent is related to the thermodynamic activity of the solvent in the solution. In ideal solutions the activity equals the mole fraction, and the mole fractions of the solvent (subscript 1) and the solute (subscript 2) add up to unity in two-component systems. Therefore the colligative properties can easily be related to the mole fraction of the solute in an ideal solution. The following review of the other three colligative properties indicates the similarity which underlies the analysis of all the colligative properties ... 

This is an expression of Raoult s law which we have used previously. Freezing point depression. A solute which does not form solid solutions with the solvent and is therefore excluded from the solid phase lowers the freezing point of the solvent. It is the chemical potential of the solvent which is lowered by the solute, so the pure solvent reaches the same (lower) value at a lower temperature. At equilibrium... 

In this model we start with pure solvent so an undiminished value of V can be used for the first solute molecule. 

We consider this system in an osmotic pressure experiment based on a membrane which is permeable to all components except the polymeric ion P that is, solvent molecules, M" , and X can pass through the membrane freely to establish the osmotic equilibrium, and only the polymer is restrained. It does not matter whether pure solvent or a salt solution is introduced across the membrane from the polymer solution or whether the latter initially contains salt or not. At equilibrium both sides of the osmometer contain solvent, M , and X in such proportions as to satisfy the constaints imposed by electroneutrality and equilibrium conditions. 

Now we return to consider the energy that must be dissipated in a unit volume of suspension to produce a unit gradient, as we did above with the pure solvent. The same fraction applied to the shearing force will produce the unit gradient, and the same fraction also describes the volume rate of energy dissipation compared to the situation described above for pure solvent. Since the latter was Po, we write for the suspension, in the case of dv/dy = 1,... 

Next let us consider the light scattered by liquids of low molecular weight compounds. We are actually not directly interested in this quantity per se, but in scattering by solutions-polymer solutions eventually, but for now solutions of small solute molecules. The solvent in such a solution does scatter, but, in practice, the intensity of light scattered by pure solvent is measured and subtracted as a blank correction from the scattering by the solution. 

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