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Chemistry LibreTexts

2.1: Atoms: Their Composition and Structure

Skills to Develop

  • to know the meaning of isotopes and atomic masses.

Atomic and Molecular Weights

The subscripts in chemical formulas, and the coefficients in chemical equations represent exact quantities. \(H_2O\), for example, indicates that a water molecule comprises exactly two atoms of hydrogen and one atom of oxygen. The following equation:

\[ C_3H_{8(g)} + 5O_{2(g)} \rightarrow 3CO_{2(g)} + 4H_2O_{(l)} \label{Eq1}\]

not only tells us that propane reacts with oxygen to produce carbon dioxide and water, but that 1 molecule of propane reacts with 5 molecules of oxygen to produce 3 molecules of carbon dioxide and 4 molecules of water. Since counting individual atoms or molecules is a little difficult, quantitative aspects of chemistry rely on knowing the masses of the compounds involved.

Atoms of different elements have different masses. Early work on the separation of water into its constituent elements (hydrogen and oxygen) indicated that 100 grams of water contained 11.1 grams of hydrogen and 88.9 grams of oxygen:

\[\text{100 grams Water} \rightarrow \text{11.1 grams Hydrogen} + \text{88.9 grams Oxygen} \label{Eq2}\]

Later, scientists discovered that water was composed of two atoms of hydrogen for each atom of oxygen. Therefore, in the above analysis, in the 11.1 grams of hydrogen there were twice as many atoms as in the 88.9 grams of oxygen. Therefore, an oxygen atom must weigh about 16 times as much as a hydrogen atom:

\[ \dfrac{\dfrac{88.9\;g\;Oxygen}{1\; atom}}{\dfrac{111\;g\;Hydrogen}{2\;atoms}} = 16 \label{Eq3}\]

Hydrogen, the lightest element, was assigned a relative mass of '1', and the other elements were assigned 'atomic masses' relative to this value for hydrogen. Thus, oxygen was assigned an atomic mass of 16. We now know that a hydrogen atom has a mass of 1.6735 x 10-24 grams, and that the oxygen atom has a mass of 2.6561 X 10-23 grams. As we saw earlier, it is convenient to use a reference unit when dealing with such small numbers: the atomic mass unit. The atomic mass unit (amu) was not standardized against hydrogen, but rather, against the 12C isotope of carbon (amu = 12).

Thus, the mass of the hydrogen atom (1H) is 1.0080 amu, and the mass of an oxygen atom (16O) is 15.995 amu. Once the masses of atoms were determined, the amu could be assigned an actual value:

1 amu = 1.66054 x 10-24 grams
conversely:
1 gram = 6.02214 x 1023 amu

Average Atomic Mass

Although the masses of the electron, the proton, and the neutron are known to a high degree of precision (Table 2.3.1), the mass of any given atom is not simply the sum of the masses of its electrons, protons, and neutrons. For example, the ratio of the masses of 1H (hydrogen) and 2H (deuterium) is actually 0.500384, rather than 0.49979 as predicted from the numbers of neutrons and protons present. Although the difference in mass is small, it is extremely important because it is the source of the huge amounts of energy released in nuclear reactions.

Because atoms are much too small to measure individually and do not have charges, there is no convenient way to accurately measure absolute atomic masses. Scientists can measure relative atomic masses very accurately, however, using an instrument called a mass spectrometer. The technique is conceptually similar to the one Thomson used to determine the mass-to-charge ratio of the electron. First, electrons are removed from or added to atoms or molecules, thus producing charged particles called ions. When an electric field is applied, the ions are accelerated into a separate chamber where they are deflected from their initial trajectory by a magnetic field, like the electrons in Thomson’s experiment. The extent of the deflection depends on the mass-to-charge ratio of the ion. By measuring the relative deflection of ions that have the same charge, scientists can determine their relative masses (Figure \(\PageIndex{1}\)). Thus it is not possible to calculate absolute atomic masses accurately by simply adding together the masses of the electrons, the protons, and the neutrons, and absolute atomic masses cannot be measured, but relative masses can be measured very accurately. It is actually rather common in chemistry to encounter a quantity whose magnitude can be measured only relative to some other quantity, rather than absolutely. We will encounter many other examples later in this text. In such cases, chemists usually define a standard by arbitrarily assigning a numerical value to one of the quantities, which allows them to calculate numerical values for the rest.

Figure \(\PageIndex{1}\): Determining Relative Atomic Masses Using a Mass Spectrometer. Chlorine consists of two isotopes, \(^{35}Cl\) and \(^{37}Cl\), in approximately a 3:1 ratio. (a) When a sample of elemental chlorine is injected into the mass spectrometer, electrical energy is used to dissociate the Cl2 molecules into chlorine atoms and convert the chlorine atoms to Cl+ ions. The ions are then accelerated into a magnetic field. The extent to which the ions are deflected by the magnetic field depends on their relative mass-to-charge ratios. Note that the lighter 35Cl+ ions are deflected more than the heavier 37Cl+ ions. By measuring the relative deflections of the ions, chemists can determine their mass-to-charge ratios and thus their masses. (b) Each peak in the mass spectrum corresponds to an ion with a particular mass-to-charge ratio. The abundance of the two isotopes can be determined from the heights of the peaks.

The arbitrary standard that has been established for describing atomic mass is the atomic mass unit (amu or u), defined as one-twelfth of the mass of one atom of 12C. Because the masses of all other atoms are calculated relative to the 12C standard, 12C is the only atom listed in Table 2.3.2 whose exact atomic mass is equal to the mass number. Experiments have shown that 1 amu = 1.66 × 10−24 g.

Mass spectrometric experiments give a value of 0.167842 for the ratio of the mass of 2H to the mass of 12C, so the absolute mass of 2H is

\[\rm{\text{mass of }^2H \over \text{mass of }^{12}C} \times \text{mass of }^{12}C = 0.167842 \times 12 \;amu = 2.104104\; amu \label{Eq4}\]

The masses of the other elements are determined in a similar way.

The periodic table lists the atomic masses of all the elements. Comparing these values with those given for some of the isotopes in Table 2.3.2 reveals that the atomic masses given in the periodic table never correspond exactly to those of any of the isotopes. Because most elements exist as mixtures of several stable isotopes, the atomic mass of an element is defined as the weighted average of the masses of the isotopes. For example, naturally occurring carbon is largely a mixture of two isotopes: 98.89% 12C (mass = 12 amu by definition) and 1.11% 13C (mass = 13.003355 amu). The percent abundance of 14C is so low that it can be ignored in this calculation. The average atomic mass of carbon is then calculated as follows:

\[ \rm(0.9889 \times 12 \;amu) + (0.0111 \times 13.003355 \;amu) = 12.01 \;amu \label{Eq5} \]

Carbon is predominantly 12C, so its average atomic mass should be close to 12 amu, which is in agreement with this calculation.

The value of 12.01 is shown under the symbol for C in the periodic table, although without the abbreviation amu, which is customarily omitted. Thus the tabulated atomic mass of carbon or any other element is the weighted average of the masses of the naturally occurring isotopes.

Example \(\PageIndex{1}\)

Naturally occurring bromine consists of the two isotopes listed in the following table:

Isotope Exact Mass (amu) Percent Abundance (%)
79Br 78.9183 50.69
81Br 80.9163 49.31

Calculate the atomic mass of bromine.

Given: exact mass and percent abundance

Asked for: atomic mass

Strategy:

  1. Convert the percent abundances to decimal form to obtain the mass fraction of each isotope.
  2. Multiply the exact mass of each isotope by its corresponding mass fraction (percent abundance ÷ 100) to obtain its weighted mass.
  3. Add together the weighted masses to obtain the atomic mass of the element.
  4. Check to make sure that your answer makes sense.

Solution:

A The atomic mass is the weighted average of the masses of the isotopes. In general, we can write

atomic mass of element = [(mass of isotope 1 in amu) (mass fraction of isotope 1)] + [(mass of isotope 2) (mass fraction of isotope 2)] + …

Bromine has only two isotopes. Converting the percent abundances to mass fractions gives

\[^{79}Br: {50.69 \over 100} = 0.5069\]
\[^{81}Br: {49.31 \over 100} = 0.4931\]

B Multiplying the exact mass of each isotope by the corresponding mass fraction gives the isotope’s weighted mass:

\(\rm^{79}Br: 79.9183 \;amu \times 0.5069 = 40.00\; amu\)

\(\rm^{81}Br: 80.9163 \;amu \times 0.4931 = 39.90 \;amu\)

C The sum of the weighted masses is the atomic mass of bromine is

40.00 amu + 39.90 amu = 79.90 amu

D This value is about halfway between the masses of the two isotopes, which is expected because the percent abundance of each is approximately 50%.

Exercise \(\PageIndex{1}\)

Magnesium has the three isotopes listed in the following table:

Isotope Exact Mass (amu) Percent Abundance (%)
24Mg 23.98504 78.70
25Mg 24.98584 10.13
26Mg 25.98259 11.17

Use these data to calculate the atomic mass of magnesium.

Answer: 24.31 amu

Summary

The mass of an atom is a weighted average that is largely determined by the number of its protons and neutrons, whereas the number of protons and electrons determines its charge. Each atom of an element contains the same number of protons, known as the atomic number (Z). Neutral atoms have the same number of electrons and protons. Atoms of an element that contain different numbers of neutrons are called isotopes. Each isotope of a given element has the same atomic number but a different mass number (A), which is the sum of the numbers of protons and neutrons. The relative masses of atoms are reported using the atomic mass unit (amu), which is defined as one-twelfth of the mass of one atom of carbon-12, with 6 protons, 6 neutrons, and 6 electrons. The atomic mass of an element is the weighted average of the masses of the naturally occurring isotopes. When one or more electrons are added to or removed from an atom or molecule, a charged particle called an ion is produced, whose charge is indicated by a superscript after the symbol.