Osmotic pressure measuring

Osmotic pressure measurements and the NMR spectra of dilute solutions of the aminoaldehyde (6) indicated that the primary species in solution was the dimeric enamine (7) (29). 

Molar masses can also be determined using other colligative properties. Osmotic pressure measurements are often used, particularly for solutes of high molar mass, where the concentration is likely to be quite low. The advantage of using osmotic pressure is that the effect is relatively large. Consider, for example, a 0.0010 M aqueous solution, for which... 

A biochemist isolates a new protein and determines its molar mass by osmotic pressure measurements. A 50.0-mL solution is prepared by dissolving 225 mg of the protein in water. The solution has an osmotic pressure of 4.18 mm Hg at 25°C. What is the molar mass of the new protein ... 

WEB The molar mass of a type of hemoglobin was determined by osmotic pressure measurement A student measured an osmotic pressure of 4.60 mm Hg for a solution at 20°C containing 3.27 g of hemoglobin in 0.200 L of solution. What is the molar mass of hemoglobin ... 

The van t Ho ff equation is used to determine the molar mass of a solute from osmotic pressure measurements. This technique, which is called osmometry, involves the determination of the osmotic pressure of a solution prepared by making up a known volume of solution of a known mass of solute with an unknown molar mass. Osmometry is very sensitive, even at low concentrations, and is commonly used to determine very large molar masses, such as those of polymers. 

Theta temperature is one of the most important thermodynamic parameters of polymer solutions. At theta temperature, the long-range interactions vanish, segmental interactions become more effective and the polymer chains assume their unperturbed dimensions. It can be determined by light scattering and osmotic pressure measurements. These techniques are based on the fact that the second virial coefficient, A2, becomes zero at the theta conditions. 

For determination of the molar mass of an unknown compound, a measured mass of material is dissolved to give a measured volume of solution. The system is held at constant temperature, and the osmotic pressure is determined. Osmotic pressure measurements are particularly useful for determining the molar masses of large molecules such as pol3TTiers and biological materials, as Example illustrates. 

The results of osmotic pressure measurements are shown in Fig. 145 for poly-(4-vinyl-N-butylpyridinium bromide) in alcohol, and for the parent uncharged polymer, poly-(4-vinylpyridine), likewise in alcohol. The value of /c for the former (note difference in scales) is much larger than for the latter, and it increases with dilution. The... 

Equation (22) has been confirmed by a variety of techniques including neutron scattering, dynamic light scattering, and osmotic pressured measurements [23]. As concentration increases the concentration blob decreases in size until the Kuhn length is reached and the coil displays concentrated or melt Gaussian structure. The coil accommodates concentrations between the overlap and concentrated through adjustment of the concentration blob size. 

Fraenkel-Conrat H, Mecham DK. The reaction of formaldehyde with proteins demonstration of intermolecular cross-linking by means of osmotic pressure measurements. J. Biol. Chem. 1949 177 477-486. 

Temperature of measurement varies between 22.5 and 35°C. 4 O. P. = osmotic-pressure measurements S. D. = sedimentation and diffusion measurements. 

The density correction is extremely important in such low osmotic-pressure measurements, but has been infrequently applied. 

Osmotic pressure is one of the colligative properties of solutions containing both low-Molecular weight compounds and high polymers. The major difficulty faced in the study of the behaviour of low Molecular weight compounds in solution by the Osmotic pressure measurement method is the selection of a suitable semi-permeable membrane. 

Equation 3.27 forms the basis for determination of Molecular weight from light scattering data. Like Osmotic pressure measurements, it is essential to consider the non-ideality of solutions and the concentration dependence. Following Debye, eq. 3.27 gets modified to... 

In this equation, u is the osmotic pressure in atmospheres, n is the number of moles of solute, R is the ideal gas constant (0.0821 Latm/K mol), T is the Kelvin temperature, V is the volume of the solution and i is the van t Hoff factor. If one knows the moles of solute and the volume in liters, n/V may be replaced by the molarity, M. It is possible to calculate the molar mass of a solute from osmotic pressure measurements. This is especially useful in the determination of the molar mass of large molecules such as proteins. 

To get from the amino acid analysis of the protein to its structure, its molecular weight had to be estimated. As early as 1885 Zinoffsky had reported a minimum molecular weight for hemoglobin of 16.73 kDa based on its elementary composition and assuming one atom of iron/ mole, a remarkably accurate figure. For most proteins because of their large size and ease of denaturation, classical cryoscopic or ebulliscopic methods were impracticable. Osmotic pressure measurements were... 

The experimental techniques for the study of conformational branched properties in solution are the same as used for linear chains. These are, in particular, static and dynamic light scattering, small angle X-ray (SAXS) and small angle neutron (SANS) scattering methods, and common capillary viscometry. These methods are supported by osmotic pressure measurements and, nowadays extensively applied, size exclusion chromatography (SEC) in on-line combination with several detectors. These measurements result in a list of molecular parameters which are given in Table 1. 

In all hydrodynamic methods we have the effect of both the hydrodynamic and thermodynamic interactions and these do not contribute additively but are coupled. This explains why the theoretical treatment of [77] and of the concentration dependence of has been so difficult. So far a satisfactory result could be achieved only for flexible linear chains [3, 73]. Fortunately, the thermodynamic interaction alone can be measured by static scattering techniques (or osmotic pressure measurement) when the scattering intensity is extrapolated to zero scattering angle (forward scattering). Statistical thermodynamics demonstrate that this forward scattering is given by the osmotic compressibility dc/dn as [74,75]... 

In this section, we present a few examples of instruments available for visual observation and imaging of colloids and surfaces, for measurement of sizes and for surface force measurements. Such a presentation can hardly be comprehensive in fact, that is not our purpose here. Throughout the book, we discuss numerous other techniques such as osmotic pressure measurements, light and other radiation scattering techniques, surface tension measurements,... 

EXAMPLE 3.1 Molecular Weights from Osmotic Pressure Measurements. To what molecular weights do the limiting reduced osmotic pressures obtained from Figure 3.5 correspond The data in Figure 3.5 are presented in such a way that unit problems do not enter the picture. We are not usually so lucky Consider some possible combinations of units for tt, V, and R that are compatible with the units of the ordinate in Figure 3.5. 

EXAMPLE 3.3 Excluded Volume of Bovine Serum Albumin from Osmotic Pressure Measurements. A plot of 7r/c versus c for an aqueous solution of the bovine serum albumin molecule at 25°C and pH = 5.37 is shown in Figure 3.6. The molecule is known to be nearly spherical and uncharged at this pH. Evaluate the molecular weight and the excluded volume of this protein from the intercept and slope of this line, 0.268 torr (g kg-1)-1 and 1.37 10 3 torr kg2 g 2, respectively. From the particle mass and volume, estimate the partial specific volume of the solute in solution. The specific volume of the unsolvated protein is about 0.75 cm3 g 1 does the solute appear to be solvated ... 

How does one use osmotic pressure measurements to determine the molecular weight of a solute How does polydispersity in molecular weight affect such a measurment ... 

Molecular weight from osmotic pressure measurements Degree of polymerization and molecular weight distribution Excluded volume from osmotic pressure measurements Theta temperature from second virial coefficient data Evaluation of charges on macroions from osmotic pressures... 

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