Quincke's researches (1904) have demonstrated that when a 20 per cent gelatin gel is allowed to swell in water it gives rise to positive double refraction, as if the gel were under tensile stresses. If, on the other hand, the gel shrinks on being placed in alcohol it becomes negatively double refractive, as if it were compressed. But the double refraction as found by Quincke lasts only during the process of swelling or shrinking, and disappears as soon as the gel reaches a state of equilibrium.
This phenomenon was investigated here and it was found that the reason for the disappearance of the double refraction is due to the fact that at equilibrium the percentage change in the size of a gel is equal in all three dimensions and the strain is therefore uniform. Double refraction persists as long as there is a difference in the elastic strain in the three dimensions of the strained material.
It was found that when gels are cast on glass slides or in glass frames, so as to prevent swelling in certain directions, the double refraction produced by swelling at 6°C. persists permanently in the gel as long as it is swollen, and is proportional to the percentage change in the linear dimensions of the gel.
Gels made up of various concentrations of isoelectric gelatin of less than 10 per cent when placed in dilute buffer of the same pH as that of the isoelectric point of the gelatin shrink and give rise to negative double refraction, while gels of concentrations of more than 10 per cent swell and give rise to positive double refraction. The double refraction produced in either case when divided by the percentage change in the dimensions of the gel and by its changed concentration gives a constant value both for swelling and shrinking. This constant which stands for the double refraction produced in a gel of unit concentration per unit strain is termed here the optical modulus of elasticity since it is proportional to the internal elastic stress in the swollen gelatin.
It was found that the optical modulus of elasticity is the same both for gels cast on slides and in frames, although the mode of swelling is different in the two forms of gels.
Gels removed from their glass supports after apparent swelling equilibrium, when placed in dilute buffer, begin to swell gradually in all three dimensions and the double refraction decreases slowly, though it persists for a long time. But the double refraction per unit change in dimension and per unit concentration still remains the same as before, thus proving that the internal elastic stress as indicated by the double refraction is brought about by the resistance of the gel itself to deformation.
A study was also made on the effect of salts, acid and base on the double refraction of a 10 per cent gel during swelling. The experiments show that below M/8 salts affect very slightly the optical modulus of elasticity of the gel. At higher concentrations of salts the elasticity of the gel is reduced by some salts and increased by others, while such salts as sodium acetate and sodium and ammonium sulfates do not change the elasticity of the gels at all during swelling. The investigated salts may thus be arranged in this respect in the following approximate series: CaCl2, NaI, NaSCN, NaBr, AlCl3, NaCl, Na acetate, Na2SO4, (NH4)2SO4, Al2SO4 and MgSO4. The first five in the series decrease the elasticity while the last two in the series increase the elasticity of the gels during swelling. Acids and bases in higher concentrations exert a powerful influence on the reduction of the elasticity of the gel but in the range of pH between 2.0 and 10.0 the elasticity remains unaffected.
The general conclusions to be drawn from these studies are as follows:
1. Swelling or shrinking produces elastic stresses in gels of gelatin, tensile in the first case and compressive in the second case, both being proportional to the percentage change in the dimensions of the gel.
2. Unsupported gels when immersed in aqueous solutions swell or shrink in such a manner that at equilibrium the percentage change in size is equal in all three dimensions, and the stresses become equalized throughout the gel.
3. Gels cast on glass slides or in frames when immersed in aqueous solutions swell or shrink mostly in one direction, and give rise to unidirectional stresses that can be determined accurately by measuring the double refraction produced.
4. The modulus of elasticity of swelling gelatin gels, as calculated from the double refraction measurements, is the same both for compression and for tension and is proportional to the concentration of gelatin in the gel.
5. The modulus of elasticity of gels during swelling is affected only slightly or not at all by salts at concentrations of less than M/8 and is independent of the pH in the range approximately between 2.0 and 10.0.
6. Higher concentrations of salts affect the modulus of elasticity of gelatin gels and the salts in their effectiveness may be arranged in a series similar to the known Hoffmeister series.
7. Acid and alkali have a strong reducing influence on the elastic modulus of swelling gels.
8. The swelling produced in isoelectric gelatin by salts is due primarily to a change brought about by the salts in the osmotic forces in the gel, but in high concentrations of some salts the swelling is increased by the influence of the salt on the elasticity of the gel. This agrees completely with the theory of swelling of isoelectric gelatin as developed by Northrop and the writer in former publications.
9. The studies of Loeb and the writer on the effect of salts on swelling of gelatin in acid and alkali have been in the range of concentrations of salts where the modulus of elasticity of the gelatin is practically constant, and the specific effect of the various salts has been negligible as compared with the effect of the valency of the ions.
In concentrations of salts below M/4 or M/8 the Hoffmeister series plays no rôle.