Molecular weight (redirected from molecular weights)

molecular weight, weight of a molecule of a substance expressed in atomic mass units (amu). The molecular weight may be calculated from the molecular formula of the substance; it is the sum of the atomic weights of the atoms making up the molecule. For example, water has the molecular formula H₂O, indicating that there are two atoms of hydrogen and one atom of oxygen in a molecule of water. Rounded to three decimal places, the atomic weight of hydrogen is 1.008 amu and that of oxygen is 15.999 amu. The molecular weight of water is thus (2×1.008)+(1×15.999)=2.016+15.999=18.015 amu. Since atomic weights are average values, molecular weights are also average values. On the average, a molecule of ordinary water weighs 18.015 amu. Both hydrogen and oxygen are made up of several isotopes. One isotope of hydrogen is deuterium, or heavy hydrogen. Atoms of deuterium are about twice as massive as the average for all hydrogen atoms in ordinary water. Therefore water that contains only atoms of deuterium, called heavy water, has a higher molecular weight than ordinary water. Some substances, especially ionic compounds such as common salt, are not made up of molecules and thus have neither a molecular formula nor a molecular weight.

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.

---

molecular weight

Mass of a molecule of a substance, based on 12 as the atomic weight of carbon-12. It is calculated in practice by summing the atomic weights of the atoms making up the substance's molecular formula. The molecular weight of a hydrogen molecule (chemical formula H₂) is 2 (after rounding off); for many complex organic molecules (e.g., proteins, polymers) it may be in the millions.

---

Molecular weight

The sum of the atomic weights of all atoms making up a molecule. Actually, what is meant by molecular weight is molecular mass. The use of this expression is historical, however, and will be maintained. The atomic weight is the mass, in atomic mass units, of an atom. It is approximately equal to the total number of nucleons, protons, and neutrons composing the nucleus. Since 1961 the official definition of the atomic mass unit (amu) has been that it is 1/12 the mass of the carbon-12 isotope, which is assigned the value 12.000 exactly. See Atomic mass, Atomic mass unit

A mole is an amount of substance containing the Avogadro number, N_A, approximately 6.022 × 10²³, of molecules or atoms. Molecule, in this definition, is understood to be the smallest unit making up the characteristic compound. Originally, the mole was interpreted as that number of particles whose total mass in grams was numerically equivalent to the atomic or molecular weight in atomic mass units, referred to as gram-atomic or gram-molecular weight. This is how the above value for N_A was calculated. As the ability to make measurements of the absolute masses of single atoms and molecules has improved, however, modern metrology is tending to alter its approach and define the Avogadro number as an exact quantity, thereby changing slightly the definition of the atomic mass unit and removing the need to define atomic weight with respect to a particular isotopic species. The latest and most accurate value for the Avogadro number is 6.0221415(10) × 10²³ mol^-1.

As the masses of all the atomic species are now well known, masses of molecules can be determined once the composition of the molecule has been ascertained. Alternatively, if the molecular weight of the molecule is known and enough additional information about composition is available, such as the basic atomic constituents, it is possible to begin to assemble structural information about the molecule. Thus, the determination of the molecular weight is one of the first steps in the analysis of an unknown species. Given the increasing emphasis on the study of biologically important molecules, particular attention has been focused on the determination of molecular weights of larger and larger units. There are a number of methods available, and the one chosen will depend on the size and physical state of the molecule. All processes are physical macroscopic measurements and determine the molecular weight directly. Connection to the absolute mass scale is straightforward by using the Avogadro number, although, for extremely large molecules, this connection is often unnecessary or impossible, as the accuracy of the measurements is not that good. The main function of molecular weight determination of large molecules is elucidation of structure.

Molecular weight determination of materials which are solid or liquid at room temperature is best achieved by taking advantage of one of the colligative properties of solutions, boiling-point elevation, freezing-point lowering, or osmotic pressure, which depend on the number of particles in solution, not on the nature of the particle. The choice of which to use will depend on a number of properties of the substance, the most important of which will be the size. All require that the molecule be small enough to dissolve in the solution but large enough not to participate in the phase change or pass through a semipermeable membrane. Freezing-point lowering is an excellent method for determining molecular weights of smaller organic molecules, and osmometry, as the osmotic pressure determination is called, for determining molecular weights of larger organic molecules, particularly polymeric species. Boiling-point elevation is used less frequently.

The basis of all the methods involving colligative properties of solutions is that the chemical potentials of all phases must be the same. (Chemical potential is the partial change in energy of a system as matter is transferred into or out of it. For two systems in contact at equilibrium, the chemical potentials for each must be equal.)

Another measurement from which molecular weights can be obtained is based on the scattering of light from the molecule. A beam of light falling on a molecule will induce in the molecule a dipole moment which in its turn will radiate. The interference between the radiated beam and the incoming beam produces an angular dependence of the scattered radiation which depends on the molecular weight of the molecule. This occurs whether the molecule is free or in solution. While the theory for this effect is complicated and varies according to the size of the molecule, the general result for molecules whose size is considerably less than that of the wavelength λ of the radiation (less than λ/50) is given by the equation below;

I() is the intensity of radiation at angle , I₀ the intensity of the incoming beam, M the molecular weight, and c the concentration in grams per cubic centimeter of the molecule. If the molecules are much larger than λ/50 (about 9 nanometers for visible light), this relationship in this simple form is no longer valid, but the method is still viable with appropriate adjustments to the theory. In fact, it can be used in its extended version even for large aggregates. See Scattering of electromagnetic radiation