MOLECULAR WEIGHTS FROM MICRO QUANTITIES OF MATERIALS

1949 ◽  
Vol 27b (3) ◽  
pp. 151-157 ◽  
Author(s):  
I. E. Puddington

A method is proposed for the determination of the molecular weight of chemical compounds in which the unknown substance may be used successfully m quantities of 1 mgm. or less. The method depends on the accurate measurement of the difference in vapor pressure between a solution of the unknown compound and the pure solvent, and this is accomplished with a modified mercury U-tube manometer. The results presented indicate that the difference between the experimental and theoretical molecular weights is of the order of 2%. Determinations require from two to three hours and the sample may be recovered.

1955 ◽  
Vol 33 (5) ◽  
pp. 755-762 ◽  
Author(s):  
A. F. Sirianni ◽  
I. E. Puddington

The molecular weights of organic compounds of known constitution have been determined with satisfactory accuracy, using milligram quantities of materials, by a static measurement of the vapor pressure difference between pure solvents and solutions of the compounds. The method may be used over a considerable temperature range. The suitability of solvents is governed by their chemical stability and vapor pressure. Results obtained using compounds in the molecular weight range of 600–1000 are reported.


PEDIATRICS ◽  
1972 ◽  
Vol 50 (5) ◽  
pp. 688-692
Author(s):  
Anatole S. Dekaban ◽  
Kenton R. Holden ◽  
George Constantopoulos

Repeated fresh plasma or whole blood transfusions were given to five patients with either Hurler, Hunter, or Sanfilippo types of mucopolysaccharidosis. Clinical observations and total 24-hour urinary AMPS and their composition and molecular weight distribution were determined before, during, and after transfusions. The two patients who received plasma transfusions showed no noticeable change in the amount of AMPS excreted; of the three patients who received whole blood transfusions, two had slightly less excretion of AMPS while the third showed no difference. The AMPS in the CSF were measured in one patient before and after blood transfusions and found to be unchanged; likewise, the determination of molecular weights in the isolated AMPS was virtually identical. In the patients studied, the transfusions caused no demonstrable difference in the patients' clinical condition.


The difference in the density of states in energy in a dilute solid solution, relative to its value in the pure solvent, is derived. It is shown to be simply related to the energy level shift induced by virtual electron scattering off the solute ions and to the density of states in the pure solvent. The result, which follows from a brief physical argument, is shown to be completely equivalent to that obtained from a far more laborious derivation by means of Green function techniques. An application to the determination of the specific heat of dilute metallic solid solutions is given and a former incomplete result, as derived by Jones from an approximate evaluation of the Green function method, is amended.


1943 ◽  
Vol 16 (3) ◽  
pp. 493-508
Author(s):  
Paul J. Flory

Abstract Experimental methods for fractionating polyisobutylene and for determining osmotic pressures have been described. The ratio π/c of osmotic pressure to concentration has been found in the case of cyclohexane solutions of polyisobutylene to vary nonlinearly with concentration, contrary to recent theories advanced by Huggins and the writer. The slope of this relationship appears to be independent of molecular weight. Reliable methods for extrapolating π/c to c=0 have been established, enabling the determination of absolute molecular weights with satisfactory precision up to values of about 1,000,000. Molecular weights of polyisobutylenes calculated from Staudinger's equation are too low; the discrepancy is more than ten-fold at high molecular weights. On the basis of data for carefully fractionated samples covering a two-hundred-fold molecular weight range, the intrinsic viscosity is found to be proportional to the 0.64 power of the molecular weight. This decided deviation from Staudinger's “law”cannot in this instance be attributed to nonlinear chain structure, as Staudinger has sought to do in other cases. This dependence of molecular weight on intrinsic viscosity leads to the definition of a “viscosity average”molecular weight which is obtained when the relationship is applied to heterogeneous polymers. The viscosity average is less than the weight average molecular weight, which would be obtained if Staudinger's equation were applicable, and greater than the number average obtained by osmotic or cryoscopic methods.


1959 ◽  
Vol 37 (12) ◽  
pp. 1365-1373 ◽  
Author(s):  
W. R. Blackmore

It is shown that a d-c. thermistor Wheatstone bridge may be used in ebulliometry to measure the small temperature differences which are observed between the boiling points of polymer solutions and the pure solvent. A relationship is derived between the thermistor bridge unbalance voltage and the solute molecular weight, which it is desired to measure. It is shown that a bridge composed of suitably matched thermistors may be made independent of the gross changes in boiling point of both solution and solvent produced by changes in atmospheric pressure. The possibility of the current flowing through the thermistors disturbing the measurements is discussed and in situ measurements of thermistor dissipation and time constants are given. The sensitivity attainable with various thermistor bridges and modern amplifiers at full gain is calculated and shown to be much greater than may be employed with the usual type of ebulliometer. The reason for this is the relatively large background noise (random temperature fluctuations) produced in the ebulliometer by the boiling process itself.


2010 ◽  
Vol 104 (3) ◽  
pp. 364-373 ◽  
Author(s):  
Tina Immerstrand ◽  
Kristina E. Andersson ◽  
Caroline Wange ◽  
Ana Rascon ◽  
Per Hellstrand ◽  
...  

In the present study, we evaluated the cholesterol-lowering effects of different oat bran (OB) preparations, differing regarding their peak molecular weight (MWp) of β-glucans (2348, 1311, 241, 56, 21 or < 10 kDa), in C57BL/6NCrl mice. The diets were designed to be atherogenic (0·8 % cholesterol and 0·1 % cholic acid), and they reflected the Western diet pattern (41 % energy fat). All OB preparations that were investigated significantly reduced plasma cholesterol when compared with a cellulose-containing control diet, regardless of the molecular weight of β-glucan. Moreover, the difference in viscous properties between the processed OB (from 0·11 to 17·7 l/g) did not appear to play a major role in the cholesterol-lowering properties. In addition, there was no correlation between the molecular weight of β-glucan and the amount of propionic acid formed in caecum. Interestingly, however, there was a significant correlation between the ratio of (propionic acid+butyric acid)/acetic acid and the MWpof β-glucans: the ratio increased with increasing molecular weight. The results of the present study suggest that the molecular weights and viscous properties of β-glucan in oat products may not be crucial parameters for their cholesterol-lowering effects.


1959 ◽  
Vol 32 (2) ◽  
pp. 428-433
Author(s):  
Fred G. Hewitt ◽  
Robert L. Anthony

Abstract The fractional increase in volume accompanying the isothermal extension of soft gum rubber was measured for four rubber samples at mean extensions of 14, 33, and 51%. The chain molecular weights Mc of the four samples were 5500, 5100, 4400, and 3000, with an estimated uncertainty of about 10% in each value of Mc. The observed fractional increase in volume ranged from 3.2×10−5 to 142×10−5, the latter value being observed for the sample of lowest chain molecular weight and at the extension of 51%. The experimental results for each sample have been represented by theoretical curves based on Gee's expression for the fractional increase in volume as a function of the sample extension. The theoretical curves exhibit good agreement with those of Gee, Stern, and Treloar. The process of fitting the theoretical curves to the experimental points constituted a determination of Young's modulus E for each rubber specimen. As a check on the experimental results, and also on the theory employed, determinations of E were also made by two additional methods, namely, from rough stess-strain curves, and from the relation E=3γρRT/Mc. With one exception, the internal agreement between the three determinations of E for the four different samples was satisfactory. The exception noted can probably be ascribed to the use of too small a value of Mc for the sample of lowest chain molecular weight.


1939 ◽  
Vol 12 (4) ◽  
pp. 789-793 ◽  
Author(s):  
W. Harold Smith ◽  
Henry J. Wing

Abstract Some investigators believe that rubber consists of associated molecules, and others accept Staudinger's view that long-chain molecules are formed by polymerization. Pummerer, Andriessen and Gündel have obtained a molecular weight as low as 600. Meyer and Mark believe that it is approximately 5,000, although they calculated on the basis of osmotic pressures values as high as 350,000. They, as well as Pummerer, consider that rubber is an associated colloid and that high molecular weights are caused by aggregates, sometimes called micelles. Staudinger, however, considers that the long-chain rubber molecule itself has a molecular weight of 200,000 or even 350,000, and that products with lower values, which may be formed in rubber, result from degradation. if the molecules are small it might be possible to distil them if their vapor pressure could be sufficiently increased, but none would distil without decomposition if the molecules are very large. Because the vapor pressure of rubber below its decomposition temperature is low, it appeared of interest to attempt to distil the material in a molecular still. Paraffin wax and sugar, both substances of relatively high molecular weight, have been successfully distilled in this type of apparatus. Subsequent to the work described in this paper, the molecular weight of sol rubber prepared at this Bureau was determined by Kraemer and Lansing of E. I. du Pont de Nemours & Co., Inc. They used the Svedberg method of sedimentation equilibrium in an ultracentrifuge with ethereal solutions of sol rubber. The temperature of the solutions during determinations was approximately 10° C, and an average value of 460,000 was obtained. There was evidenced of a mixture of molecular species.


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