Molecular weights of substances may be determined experimentally in various ways, the method employed usually depending on the state (solid, liquid, or gas) of the substance. Methods for determining the molecular weights of gaseous substances are based on Avogadro's law, which states that under given conditions of temperature and pressure a given volume of any gas contains a specific number of molecules of the gas; thus a comparison of the weights of equal volumes of different gases under the same conditions of temperature and pressure is equivalent to a direct comparison of the weights of molecules of the gases. The molecular weights of substances that are not normally gaseous and do not evaporate without decomposition are sometimes determined from their effects on the melting point, boiling point, vapor pressure, or osmotic pressure of some solvent (see colligative properties). However, if the substance ionizes or does not completely separate into molecules, the molecular weight so determined will be erroneous. Highly accurate molecular weights are sometimes determined by using the mass spectrograph.
Some substances, e.g., proteins, viruses, and certain synthetic polymers, have very high molecular weights. These molecular weights may be determined by measurement of sedimentation rate in an ultracentrifuge, by light-scattering photometry, or by other methods. The methods may give different results, since usually the molecules of a substance such as a polymer do not all have exactly the same molecular weight. These methods determine an average molecular weight for the molecules in the sample. The number-average molecular weight determined by the ultracentrifuge method gives a value that is equal to the weight of the sample divided by the number of molecules in the sample. This number-average molecular weight can also be determined by other methods based on measurement of colligative properties. The light-scattering method determines what is called the weight-average molecular weight. Although this may be the same value as the number-average molecular weight if all the molecules have nearly the same weight, it will be higher if some of the molecules are heavier than others.
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