CHAPTER

Atomic Structure

The existence and properties of individual molecules, atoms, and ions in the gaseous state provide a fundamental basis for elemental spectrometric analytical determinations. Classical techniques based on these principles have been utilized for decades for the major, minor, and trace analysis of substances in virtually every field of science. The enhancement of techniques based on these properties has recently resulted in technology that exhibits ultratrace analysis sensitivity (sub-part-per-million detectability) and allows expansion of the scope of analysis to the rarer and more exotic elements. A basic understanding of some of the fundamental atomic properties of the elements that are used for mass spectrometric analysis is required to fully utilize this technology. Dalton,in 1803, introduced the concept of atoms and molecules and established the following postulates regarding the laws of chemical composition: 1. Each chemical element is composed of discrete atoms, which are identical in all respects.

Chapter 2

Atomic Structure

2. Atoms cannot be broken dovv^n by known chemical processes, and they maintain their unique identity after undergoing these processes. 3. Atoms of different elements may associate or bond together to form chemical compounds which have properties different from those of the atoms. These principles were used to establish a theory regarding the properties, structure, and behavior of atoms. This chapter provides a basic introduction to these principles. Atoms are the most fundamental building blocks of matter. Composed of subatomic components including electrons, protons, and neutrons, atoms are the smallest units having characteristics and properties that are unique and identifiable to individual elements. Table 2.1 Usts the mass and electrical charge of the most common subatomic particles. Electrical charge is defined here, by convention, as a positive or negative integer.

2.1 B O H R M O D E L Models are often used to describe the structure of atoms, the configuration of their subatomic particles, and their interactive behavior. Of the several models for atomic structure, including those of J. J. Thomson in 1907 and Lord Rutherford in 1911, the Bohr model, proposed in 1913, is used here to illustrate atomic principles.Two assumptions made by Bohr are critical to using his model: (1) Stationary energy states exist such that an atom in one of these states is stable and the atom in this state is populated for a finite period of time and (2) the emission or absorption of radiation from an atom is exactly equal to the difference between two of the discreet energy states. Although the Bohr model employs a simplified concept that is insufficient to explain the chemical behavior of an element, it provides an illustration to

TABLE 2.1 Particle Electron Neutron Proton

Physical Properties of Subatomic Particles Rest mass (g) 9.110 X 10-^1 1.675 X 10--^ 1.673 X 10--^ <Charge'' -1 0

+1

" Equivalent to the electrostatic charge of one electron (1.6 X 10 ^^ C). ^

2.1 Bohr Model

assist in the elementary understanding of their atomic characteristics. The atom appears to consist of an extremely small nucleus surrounded by one or more electrons, which in themselves are very small. The nucleus of the atom is made up of both protons and neutrons. As can be seen from Table 2.1, by far the bulk of the mass of the atom is made up by the nucleus (the mass of the electrons is insignificant compared to that of the protons or neutrons). Because each electron, which is negatively charged, resides a substantial relative distance from the positively charged nucleus, the atom must have associated with it considerable energy to prevent the electron from being attracted to the nucleus. A balance of forces keeps the electrons, which are in constant motion from collapsing into the nucleus. Identification of these forces is a complex matter and is beyond the scope of this discussion. The description of each electron in an atom with respect to its energy is fundamental in understanding the atom's electronic structure. Figure 2.1 shows a simplified diagram for two elements, the simplest elemental structure, hydrogen, and a more complex element, fluorine. Hydrogen has an atomic number of 1, which means that it has 1 electron and 1 proton (in its nucleus). Because the electron has a charge of 1 and the proton has a charge of + 1 , this hydrogen atom is overall electrically

Hydrogen

Fluorine

protons neutrons mass

1 0 1

protons neutrons mass

9 10 19

FIGURE 2.1

Bohr model of the atoms of hydrogen and fluorine.

10

Chapter 2

Atomic Structure

neutral. Also in Figure 2.1, we see that fluorine has an atomic number of 9, which means it consists of 9 electrons and 9 protons in its nucleus. Appendix 2 lists common isotopes of the elements and their abundances.

2.2 I S O T O P E S It is possible for separate atoms of the same chemical element to have different masses. These entities were observed in the study of the transformation of radioactive atoms. In 1913 Soddy named these atoms, which have the same chemical properties but different masses, isotopes. The absolute mass of an isotope can be computed by summing the individual masses of the subatomic particles (see Table 2.1) and reporting the total number of grams that an isotope must weigh; however, it is more convenient to quote masses in relative terms using the atomic mass unit (amu). By definition, the most abundant isotope of carbon is exactly 12.000 amu. All other isotope masses are reported relative to carbon-12. Appendix 1 lists the average atomic mass (i.e, the average of the abundances of the stable isotopes) of each element in atomic mass units. Some elements such as arsenic, sodium, manganese, and cobalt are monoisotopic, meaning they only have one stable isotope. Other elements, which have multiple isotopes, usually have constant isotopic abundances of each isotope. The exceptions are elements such as lead, which have one or more isotopes that are the decay products of other precursor elements that are radioactive. The isotopic abundances of these elements will vary depending on the concentration and history of the concomitant radioactive elements. In Figure 2.1 we observe that fluorine, which has 9 electrons and 9 protons, has an atomic mass of 19 (see Appendix 1). Since the relative mass of the proton is approximately 1 amu, then by difference, the nucleus of fluorine is required to have 10 neutrons, which also have an approximate atomic mass of 1 amu each. The various isotopes of a given element have different numbers of neutrons; therefore, their atomic masses vary accordingly The atomic structure of the two chlorine stable isotopes is shown in Figure 2.2. Chlorine, which has an atomic number of 17, has 17 electrons and 17 protons. It also has two stable isotopes one with 18 neutrons, resulting in an atomic mass of 35 amu and the other with 20 neutrons resulting in an atomic mass of 37 amu. The relative abundances of these two isotopes are 75.8% for 35 and 24.2% for 37, almost three to one.

2.3 Ionization

11

-CI
protons neutrons mass 17 18 35

37CI
17
protons neutrons mass 17 20 37

FIGUPJE 2.2

Chlorine isotopes.

2.3 I O N I Z A T I O N By adding excess external energy, an electron can be removed from a neutral atom. The removed electron has a unit negative charge, resulting in the formation of an ion with a net unit positive charge. Since the relative mass of the electron is negligible compared to the mass of the atomic nucleus, the ion has the same characteristic atomic mass as the original isotope of the element. By application of additional energy, a second electron can be removed from the ion, resulting in a doubly charged species.This ionization process is shown for the element iron in Figure 2.3. Each element has characteristic first and second ionization potentials that are dependent on the electronic structure of that specific element. The higher the ionization potential, the more externally applied energy is required to induce ionization. First and second ionization potentials for the elements are tabulated in Appendix 1. Energy for ionization can be applied

12

Chapter 2

Atomic Structure

56Fe

+ 7.87 eV

m/z = 56

Fe+^ + e'

+ 16.24 eV - >
m/z = 28

Fe^2+ g-

F I G U P ^ 2.3

First and second ionizations of iron-56.

by a thermal radiation process, by collision with other ions or electrons, or by exposure to high-energy photons. By carefully controlling the magnitude of the energy applied, singly charged ions can be efficiently generated with minimal production of doubly charged species. Molecular species are also formed in the plasma or in the ion beam formed by ions produced in the plasma. These molecular species are predominantly diatomic in structure, although triatomic and larger molecular species are possible. For most triatomic and higher molecular species, the energy required to break them up into simpler molecules is sufficiently small that the probability of them remaining stable in the high-temperature plasma is very low. Therefore, the absence of the majority of these species in the spectrum is expected and observed. A notable exception occurs when the individual components of the polyatomic molecule are present at high

2.3 Ionization

13

concentrations, or their dissociation potential is sufficiently high that the formation of triatomic molecules is observed. Because the formation of these molecules is an equilibrium process, by the law of mass action, components that are present at high concentration have the higher probability of forming molecular species. Both homogeneous diatomic molecules, such as Ar2"^, and mixed composition heterogeneous diatomic molecules, such as ArO"^, are formed. A common triatomic molecule that is observed is ArOH"^. Molecular ions composed of atoms from the plasma support gas, atoms from solvent that is introduced into the plasma as a carrier for the sample, and atoms from major components of the sample matrix are commonly observed. Polyatomic molecular species usually form single charged ions in the plasma.