Atomic Structure and Atomic Bonding in Solid

Callister Chap. 2.2 2.8

 To understand the properties of the materials, we need to understand atomic bonding. To understand the atomic bonding, we need to understand the atomic structure.

ATOMS
Each atoms consists of a very small nucleus composed of neutrons and protons, encircled by moving electrons. Charges: Electrons: -1.60 10-19 C (Coulomb) Protons: +1.60 10-19 C Neutron neutral Generally, an atom is electrically neutral, thus the number of protons equals the number of electrons. Each chemical element is characterized by the atomic number (Z), which represent the number of protons in the nucleus. Masses: Electrons: 9.11 10-31 kg Protons: 1.67 10-27 kg Neutron: 1.67 10-27 kg The mass of the electrons are relatively small thus negligible. The atomic mass (A) of a specific atom is expressed as the sum of the masses of protons and neutrons within the nucleus. Illustration of an atom

ATOMS contd.
Isotopes
No. of protons is the same for all atoms of a given element, but the number of neutrons (N) may be different, thus the atoms of the same element may have different atomic masses. These are called isotopes.

Atomic weight
Weighted average of the atomic masses of the atoms isotopes.

Atomic mass unit (amu)

To compute atomic weight, Mproton = Mneutron = 1.66 x 10-24 g = 1 amu. 1g= 0.6023x1024 amu 0.6023x1024 amu is known as AVOGADROS NUMBER. In one mole of a substance there are 6.023x1023 atoms or molecules.

Illustration of carbon isotopes

1 amu/atom (or molecule) = 1 g/mol and

AZ+N

ELECTRONS IN ATOMS
Bohr Atom Model
Electrons are assumed to revolve around atomic nucleus in discrete orbitals. The position of any particular electron is more or less well defined in terms of its orbital. Electrons at the outermost orbital (or valence orbit) are called valence electrons. Valence electrons determine the following properties of an element: 1.Electrical 2.Optical 3.Thermal 4.Chemical

Illustration of Bohr Atom Model

ELECTRONS IN ATOMS contd.

Wave-mechanical Model
The limitations of Bohr model in which several phenomena involving electrons cannot be explained, can be explained by a wavemechanical model.

Electron is considered to exhibit wave-like and particle-like characteristics. Position of electrons is described by probability distribution or electron cloud.

Comparison of (a) Bohr and (b) wave-mechanical atom models in terms of electrical distribution. (Adapted from Z.D. Jastrezbski, The Nature and Properties of Engineering Materials, 1987, John Wiley & Sons, New York)

ELECTRONS IN ATOMS contd.

Quantum Numbers
The shells are identified by a principal quantum number n, which can be related to the size of the shell, n = 1 is the smallest; n = 2, 3 .. are larger. They are also designated by the letters K, L, M, N, O, and so on. The second quantum number l, defines subshells within each shell, denoted by s, p, d, and/or f with the energy increases accordingly (energy of s < p < d < f). The number of energy states for each subshells is determined by the third quantum number. The electrons will fill the state with the lowest energy, starting with the lowest principal quantum number, followed with the lowest subshell.

Schematic representation of the relative energies of the electrons for the various shells and subshells.

ELECTRONS IN ATOMS contd.

ELECTRONS IN ATOMS contd.

Electron Configurations
The values of energy that are permitted for electrons are called electron states. To determine the manner which these states are filled with electrons, Pauli exclusion principle is adapted. Pauli Exclusion Principle

Each electron state can hold NO MORE than TWO electrons, which MUST have opposite spins.

The electron configuration or structure of an atom represents the manner in which these states are occupied, which is animated here. When the outermost or valence shell are completely filled, the atoms have what is called stable electron configurations. Schematic representation of the filled and lowest unfilled energy states for a sodium atom.

ELECTRONS IN ATOMS contd.

PERIODIC TABLE
Periodic Table
Elements are classified according to electron configuration in this table. The elements are placed with increasing atomic number in seven horizontal rows, called periods. All elements in the same column, or group, have similar valence electron configurations, as a result, similar properties. These properties change gradually and systematically across each period moving horizontally. Most of the elements are under metal classifications, or, electropositive elements (capable of giving up their few valence electrons to become positively charged ions). Elements on the right side are electronegative (readily accept electrons to form negatively charged ions, or sometime share electrons with other atoms). Electronegativity increases from left to right and from bottom to top.

PERIODIC TABLE

Increasing Ionization Energy

High Energy

Increasing Ionization Energy

Low Energy

More electropositive

More electronegative

PERIODIC TABLE
Group explanation
Group IA Name Alkali Electrons Configurations Examples 1 electron in excess of stable structure Na, K

IIA
IIIB - IIB

Alkaline earth metals

Transition metals

2 electrons in excess of stable structure

Have partially filled d electron states - Depending on the groups

Mg, Ca
Zn, Cu, Ag, Au, Zr, Pt Si, B, P,O,Cl

IIIA, IVA, IVA VA Semiconductor, VIIA - halogens 0 (zero) Inert gases

Have filled electron shells and stable electron configurations

Ar, He

BONDING FORCES AND ENERGIES

Atomic bonding originated considering the interaction between two isolated atoms as they are brought into proximity from an infinite separation. When the atoms are infinitely far apart, the interactions are negligible, but the atoms approach each other, each exerts forces; namely attractive FA and repulsive FR forces on each other. The magnitude of each is a function of the separation or interatomic distance. The net force FN between the two atoms is the sum of both FA and FR. FN = FA + FR

When the FA and FR become balance or equal, there is no net force, the state is equilibrium.
FA + FR = 0 As the inter-atomic distance become larger, the forces and the potential energy are weaker, and vice versa.

BONDING FORCES AND ENERGIES

Bonding between atom is highly depending on the attractive, repulsive and net potential energies, in which, are the function of interatomic separation for two atoms. Bonding energy the energy that would be required to separate these two atoms to an infinite separation. The magnitude of the bonding energy depends on the material and the type of bonding. Example : materials having large bonding energy have high melting temperature, solid state at room temperature materials having small bonding energy favor gaseous state, low melting temperature Types of bonding: Primary bonding ionic, covalent, metallic Secondary bonding / Van der Waals bonding

Ionic Bonding

PRIMARY INTERATOMIC BONDING

It is always found in compounds that are composed of both metallic and nonmetallic elements. Metallic elements easily transfer (give up) their valence electrons to the nonmetallic elements. In the process all the atoms acquire stable or inert gas configurations, and they become ions. Then the coulombic force (attractive) acts upon these two oppositely charge ions.

PRIMARY INTERATOMIC BONDING

Ionic Bonding
Electron transfer (Eg. Na and Cl)

Ionic bonding is nondirectional (i.e. the magnitude of the bond is equal in all directions around an ion). The bonding energy is relatively large. Characteristics of ionic materials: high melting temperature hard and brittle electrically and thermally insulative.

PRIMARY INTERATOMIC BONDING

Covalent Bonding
It is found in nonmetallic molecules of similar atoms (eg. H2, F2) or dissimilar atoms (eg. CH4, HF) and also in elemental solids (eg. C, Si). Stable electron configuration is achieved by the sharing of electrons between the adjacent atoms. The covalently bonded atoms will contribute at least one electron to the bond and the shared electrons may be considered to belong to both atoms. Covalent bonding is directional (i.e. between specific atoms and may exist only in the direction between one atom and another). The covalent bonding is very strong. Characteristics of covalently bonded materials: very hard (eg. C) very high melting temperature (>3550 oC for C) OR can be very weak and has low melting temperature (eg. Bismuth, 270 oC). Electron Sharing (Eg. C and H)

H shared electrons from carbon atom shared electrons from hydrogen atoms

PRIMARY INTERATOMIC BONDING

Metallic Bonding
It is found in Group IA and IIA materials, in fact all elemental metals and their alloys. Metallic materials have one, two or at most three valence electrons which are not bound to any particular atom in the solid. They are free to drift throughout the entire metal. They belong to the metal as a whole, forming sea of electrons or electron clouds, which act as a glue to hold the positively charge ion cores together. Characteristics of metallic bonded materials: Good conductor to both electricity and heat due to the existence of the free electrons. ductile in room temperature ( fracture occurs after the materials have experienced significant degree of permanent deformation). The valence electrons of the metals are so weakly bound to the atoms that they are free to roam across the entire metal, leaving the atoms as a positive ion core. The delocalised electrons act as a glue to hold the ion cores together. Illustration of metallic bonding

SECONDARY BONDING
Secondary Bonding OR Van der Waals Bonding
Exists between virtually all atoms and molecules, especially in inert gases which have stable electron configurations, or between molecules in molecular structures that are covalently bonded.

Arise from atomic or molecular dipoles. The bonding is a result of the coulombic attraction between the positive end of one dipole with the negative region of an adjacent one.

Electric dipole exists whenever there is some separation of positive and negative portions of an atom or molecules.

Two types of dipole: 1.Fluctuating Induced Dipole Bonds 2.Polar Molecule-Induced Dipole Bonds

SECONDARY BONDING
Secondary Bonding OR Van der Waals Bonding
Fluctuating Induced Dipole Bonds A dipole can be created in an atom or molecule that is normally electrically symmetry when the atoms are experiencing constant vibrational motion that can cause instantaneous distortions of this electrical symmetry. Electric dipole exists whenever there is some separation of Infinitely positive and negative separated portions of an atom or molecules.

Moves closer
Van der Waals Bonding

Moves closer

SECONDARY BONDING
Secondary Bonding OR Van der Waals Bonding
Polar Molecule-Induced Dipole Bonds Exist in some molecules by virtue of an asymmetrical arrangement of positively and negatively charge regions in molecules.

Schematic representation of a polar hydrogen chloride molecule.

MOLECULES
Many common molecules are composed of atoms that are bound together by strong covalent bonds. Example : F2, O2, H2 - elemental diatomic molecules, or H2O, CO2, CH4 compounds

In condensed liquid and solid states, bond between molecules are secondary bonding. Hydrogen bonding is the strongest secondary bonding type.

TUTORIAL
1) Define / explain the terminologies below: i. Electron configuration ii. Stable electron configuration iii. Bonding energy iv. Dipoles 2) Give the electron configurations for the following elements and ions: 1) P 2) P33) Na 4) Na2+ 5) K 6) K1+
3) Explain and give examples of the primary and secondary bonding.