INORGANIC CHEMISTRY

Metallurgical Engineering Lecture Series

ATOMIC STRUCTURES
Free atom is composed of three elementary particles: protons 1.60 x 10-19 C charge magnitude
1.6783 x 10-24 g

electrons 1.60 x 10-19 C charge magnitude

9.11 x 10-28 g

neutrons
1.675 x 10-24 C charge magnitude

ATOMIC STRUCTURES
An atom is composed of nucleus (proton + neutron) encircled by orbiting electron Proton and neutron are called nucleons. Atomic Number- number of protons in the nucleus -number of the elements place in the periodic table -represented as Z -for neutral atom: number of protons=number of electrons Atomic Mass- sum of the mass of the proton and neutron -represented as A Configuration: AzMN

ATOMIC STRUCTURES
Isotopes atoms of the same element but having different atomic masses due to variation in number of neutrons e.g. Hydrogen has 3 isotopes 1 H , 2 H, 3 H 1 1 1 Atomic Weight weighted average of the atomic masses of the atoms (most common isotope of carbon) naturally occurring isotope

ATOMIC STRUCTURES
e.g. What is the atomic weight of Ar given the ff percent abundance? 99.60% 40Ar mass is 39.962 amu 0.337% 36Ar mass is 35.968 amu 0.063% 38Ar mass is 37.963 amu Solution: Atomic weight = (99.60% x 39.962 amu) + (0.337% x 35.968 amu)+ (0.063% x 37.963 amu) =39.947 amu

ATOMIC STRUCTURES
amu per atom = atomic mass unit
1/12 of the atomic mass of the most common isotope of C

Grams per mole (mole) the quantity of a substance corresponding to 6.023x 1023 (Avogadros number) atoms/ molecules/ ions

ATOMIC STRUCTURES
Atomic Models: Bohr Model
-QUANTIZED ORBITALS (description in terms of positions and energy) -electrons may jump to a higher or lower energy level

higher: absorption of energy (electromagnetic radiation equal to the difference in the energy levels of the orbit) Lower: emission of energy (emission of phonon)

Wave Mechanical Model

the position of an electron is described by a probability wave function or equation

ATOMIC STRUCTURES
FOUR QUANTUM NUMBERS (specify the energy or state of electrons)
Principal Quantum Number, n

-indicates the size of the orbit -may only have positive non zero values -lower value of n: more stable state n= 1,2,3,4

ATOMIC STRUCTURES
Orbital Quantum Number, l -signifies the subshell -can not be larger than n-1 -restricted by the principal quantum number, n: l= 0 to (n-1) -the letters spdfg and h have also been used to signify l= 0,1,2,3,4,5. Thus the energy level corresponding to n=1 and l=0 is called the 1s level and n=2 and l=1 is called 2p level. -s=sharp, p=principle, d=diffuse, f=fundamental Magnetic Quantum Number, ml -determines the number of energy states for each subshell -related to the component of the angular momentum in a specified direction -can have values from +l to l including zero Spin Quantum Number, ms -related to the spin of the electron about its own axis -can only have a value of +1/2 or -1/2

PROPERTIES OF SOLIDS, LIQUIDS AND SOLUTIONS

Matter- anything that occupies space, displays a property known as mass, and possesses inertia. Composition- refers to the parts or components of a sample of matter and their relative proportions. Properties- qualities or attributes that we can use to distinguish one sample of matter from others. Physical Properties- one that a sample of matter displays without changing its composition (malleability, ductility) Chemical Properties- ability or inability of a sample of matter to undergo a change in composition under stated conditions (combustion)

Element- substance that is made up of single type of atom. Compounds- substances in which atoms of different elements are combined with one another. The composition and properties of an element or compound are uniform throughout a given sample and from one sample to another. Molecule- smallest entity having the same proportions of the constituent atoms as does the compound as a whole. Solutions- or homogeneous mixtures, are uniform in composition and properties throughout a given sample, but the composition and properties may vary from one another. Heterogeneous mixtures- components separate into distinct regions, thus composition and physical properties vary from one part of the mixture to another. A mixture can be separated into its components by appropriate physical changes. A chemical compound retains its identity during physical changes, but it can be decomposed into its constituent elements by chemical changes.

 States of Matter
Solid- atoms or molecules are in close contact, sometimes in a highly organized arrangement called crystal. Liquid- atoms or molecules are usually separated by greater distances than in a solid, movement of atoms gives a liquid its distinctive property- the ability to flow, covering the bottom and assuming the shape of its container. Gas- distances among atoms or molecules are much greater than liquid. A gas always expands to fill its container.

 Law of Conservation of Mass

The total mass of substances present after a chemical reaction is the same as the total mass of substances before the reaction.

Matter can not be created nor destroyed in a chemical reaction. Law of Constant Composition or Definite Proportions
All samples of a compound have the same composition- the same proportions by mass of the constituent elements.

 Potential Well Concept

at large distances, interactions are negligible as two atoms approach each other, two forces develop; a repulsive force, Fr and an attractive force, Fa

when FN = 0 :

at r0

equilibrium state exists; the centers of two atoms will remain separated by the equilibrium spacing r0 :once equilibrium is attained, two atoms will counteract any attempt to separate them :for most atoms equilibrium distance r0 0.3nm (3)
:potential energy is minimum (potential well) :Bonding energy, E0 represents the energy that would be required to separate two atoms that are chemically bonded

E FN dr
r

E FA dr FR dr

E E A ER

Material Properties Depending on E0, Curve Shape and Bonding Type

Melting Temperature
-TM is larger if E0is larger -solid substances are formed for large bonding energies gaseous state have low bonding energies Liquid substances have intermediate bonding energies
-large E0 materials are more difficult to melt

Hardness

-influenced by the height of the total force or sum curve -force gives the stress required to separate the atoms -larger interatomic forces of attraction imply deeper wells -materials with high melting points are the harder material exceptions: materials with more than one type of bonding
e.g. Diamond, Al2O3 TiC

Modulus of Elasticity -related to the slope of the FA+FR curve where FN is

Thermal Expansion

zero -slopes for a relatively stiff material is steep (slope at r=r0) shallower slopes for more flexible materials -a deep, narrow trough (large bonding energies) correlates with a low coefficient of thermal expansion -electrical conductivity is dependent on the nature of atomic bonds
-ionically and covalently bonded materials are poor conductors (electrons are not free to leave their host atoms)

Conductivity of Materials

-thermal conductivity is high in materials with metallic bonds (delocalized electrons are efficient carriers of thermal as well as electrical energy)

BONDING AND PERIODICITY

TYPES OF ATOMIC BONDING IN MATERIALS PRIMARY BONDING
-chemical in nature -arises from the tendency of the atoms to assume stable electron structures by completely filling the outermost shell

 Metallic Bonding
Metals and their alloys

 Covalent Bonding
CH4, carbon, H2, Cl2, H2O, F2, HNO3, HF

 Ionic Bonding
Metallic+non metallic (NaCl)

 SECONDARY BONDING
-physical in nature and generally weaker than the primary ones Van der Waals Bonding inert gases, between molecules that are covalently bonded secondary bonding forces arise from atomic or molecular dipole the two dipoles experience a coulombic force of attraction


Atomic nucleus

Fluctuating Induced dipole bonds

-electrically symmetric atoms or molecules experience a short-lived fluctuations whereby electrons might shift away from positive nucleus in one direction inducing a local negative charge in that spot -this induced dipole gets attracted to one another in a weak type bond resulting to low melting and boiling temperatures -e.g. H2 and Cl2 permanent dipole bonds can exist between molecules like HCl. This molecule gets attracted with other such molecules

Electron cloud

Polar Molecule Induced Dipole

Hydrogen Bonding special type of secondary bonding hydrogen atom is shared between two strongly electronegative atoms such as N, O, F or Cl exists in compounds such as HF, H2O and NH3 hydrogen: positively charged end attracting the negative end of an adjacent molecule strongest secondary bonding and is responsible for relatively high melting temperature (like for water)

Pauli Exclusion Principle:

-determines the manner in which the states are filled -each electron state can hold no more than 2 electrons, which must have opposite spins Ground state when electrons occupy the lowest possible energies Electronic configuration- represents the manner in which states are occupied Valence electrons- electrons that occupy the outermost shell
-responsible for bonding -most chemical and physical properties of elements are based on valence electrons -noble gases (Ne, Ar, Kr, He) -unreactive -filled sp

Stable Electron configuration- states within the outermost or valence electron shell are completely filled

The Periodic Table

introduced by a Russian scientist D. Mendeleev in 1869 elements are classified according to electron configuration elements of any given family, which show a similarity in chemical properties, are arranged in the same column or group trends:
the metallic property elements increases from right to left of a period the metallic property also increases from top to bottom of a group elements along a same group have the same number of valence electrons transition metals have very similar properties; thus a wide variety of alloys can be produced

electropositive elements: readily give up their valence electrons electronegative elements: readily accept electrons

CHEMICAL EQUATIONS (OXIDATION AND REDUCTION)

CHEMICAL COMPOUNDS AND THEIR FORMULAS
Ionic Compounds- combination of metals and nonmetals. The charge (oxidation states) of the cation or anion can be deduced from the group to which an element belongs.

The oxidation state of an individual atom in a free element is 0. The total oxidation states of all atoms in In their compounds, Group IA metals have an OS of +1 and the Group2A metals have an OS of +2. In its compounds, the OS of fluorine is -1 In its compounds, hydrogen has an OS of +1, except when H is bonded to metals. In its compounds, oxygen has an OS of -2, except where O atoms are bonded to one another. In their binary compounds with metals, the Group 7A elements have an OS of -1; the Group 6A elements ,-2, and the Group 5A elements, -3.
A neutral species is 0 An ion is equal to the charge on the ion

NAMING INORGANIC COMPOUNDS

Binary Compounds
One metal + One nonmetal: write the name of the metal followed by the name of the nonmetal, modified to end in ide (NaCl: sodium chloride) 2 Non metals: write the element with the positive oxidation state first, include prefixes such as mono, di, tri, tetra, penta, hexa (N2O3: dinitrogen trioxide) Binary Acids: compounds of H with other nonmetal atoms, use the prefix hydro followed by other nonmetal name modified to an ic ending. (HF: hydrofluoric acid) Cl, N, P, S: form a series of oxoanions containing different numbers of oxygen atoms. Their names are related to the oxidation state of the nonmetal atom to which O atoms are bonded: (ClO- : Hypochloriite; ClO2- :chlorite; ClO3- : chlorate; ClO4- : perchlorate)

Polyatomic Ions

CHEMICAL REACTIONS AND CHEMICAL EQUATIONS

Chemical reaction- a process in which one set of substances called reactants are converted to a new set of substances called products

Chemical equation- formulas of the reactants are written on the left side of the equation and formulas of the products are written on the right. The two sides of the equation are joined by an arrow or an equal sign.
- substitute chemical formulas for names and balance the formula expression to obtain a chemical equation. - in a balanced equation the total number of atoms of each element is the same on both sides. - the coefficients required to balance a chemical equation are called stoichiometric coefficients.

- physical evidences: color change, formation of solid, evolution of gas, evolution or absrorption of heat.

Stoichiometric factor- relates the amounts of any two substances involved in a chemical reaction on a mole basis.

 a. How many moles of O2 are produced from the decomposition f 1.76 moles of potassium chlorate?
(2 KClO3 = 2KCl + 3 O2)

b. How many moles of Ag are produced in the decomposition of 1.kg silver (1) dioxide?
(2 Ag2O = 4 Ag + O2)

 Molarity,

amount of solutein moles volume of solution in liters

Solution Dilution: Mi x Vi = Mf x Vf Solvent- present in greatest quantity, determines whether the solution exists as solid, liquid or gas Solute- part that is dissolved in the solvent Mole fraction, Xi - fraction of all the molecule in a solution
Xi

amount of component iin moles total amount of all solution components in moles

The sum of all mole fractions of all the solution component is 1

 Molality, m- a concentraton unit that is independent of temperature and also proportional to mole fraction in dilute solutions
m amount of solutein moles mass of solvent in kg

Solubility- of solute in the given solvent is the concentration of the saturated solution; increase with increasing temperature. When dissolving and crystallization occur at the same rate, the solution is in a state of dynamic equilibrium, the solution is said to be saturated. When a solute completely dissolves, the solution is unsaturated. When the quantity of solute is greater than in a normal saturated solution, the solution is said to be supersaturated.

 THE NATURE OF AQUEOUS SOLUTION Non electrolyte- a substance that is not ionized and the solution does not conduct electric current Strong electrolyte- substance that is completely ionized in aqueous solution, and the solution is a good electrical conductor Weak electrolyte- the concentration of ions in solution is low, partially ionized in aqueous solution, and the solution is only a fair conductor of electricity.
All soluble ionic compounds and only a few molecular compounds are strong electrolytes Most molecular compounds are either nonelectrolytes or weak electrolytes.
-the reaction does not go into completion, the chemical reaction is reversible

PRECIPITATION REACTIONS Precipitation reactions- occur when certain cations and anions combine to produce an insoluble ionic solid called precipitate
Compounds that are mostly soluble:
Those of the alkali metals (Group 1A and the ammonium ion) Nitrates and acetates Chlorides, bromides, and iodides (those of Pb2+, Ag+ and Hg2+ are insoluble) Sulfates (those of Sr2+, Ba2+, Pb2+, and Hg22+ are insoluble) Hydroxides and sulfides (Group 1A metals are soluble, and sulfides of Group 2A metals are soluble, hydroxides of Ca2+, Sr2+ and Ba2+ are slightly soluble) Carbonates phosphates (Group 1A metals are soluble)

Compounds that are mostly insoluble:

 ACID-BASE REACTIONS
Acids- sour taste, able to react with a variety of metals and carbonate minerals, blue litmus paper turns to red
- substances that provide hydrogen ions (H+) in aqueous solution Strong Acid- molecular compounds that are completely ionized in aqueous solutions
(HCl, HBr, HI, HClO4)

Weak Acid- acids that are incompletely ionized in aqueous solution (acetic acid)

 Bases- bitter taste, slippery feel, turns red litmus paper to blue - substances capable of providing hydroxide ions (OH-) in aqueous solutions. Strong Base- substance that dissociates completely in water solution and yields OHions; hydroxides of Group 1A and some Group 2A metals (LiOH, NaOH, KOH, RbOH, CsOH, Ca(OH)2 ) Weak Base- incompletely ionized in aqueous solution; most basic substances are weak bases Neutralization- an acid and base react to form water and an aqueous solution of an ionic compound called salt.

 OXIDATION-REDUCTION Oxidation- the oxidation state of some element increases, and the electrons appear on the right side of a half-equation Reducing Agent: contains element whose oxidation state increases in redox reaction LEORA: Lose Electron Oxidation Reducing Agent Reduction- the oxidation state of some element decreases, electron appears appear on the left side of a half-equation Oxidizing Agent: contains element whose oxidation state decreases in redox reaction GEROA: Gain Electron Reduction Oxidizing Agent

 Oxidation and reduction half-reactions must always occur together, and the total number of electrons associated with the oxidation must equal the total number associated with reduction.
e.g. Reaction of iron with hydrochloric acid

 Balancing Redox Reactions in Acidic Medium (** in basic medium**) Divide the equation into an oxidation half-reaction and a reduction half-reaction Balance these
Balance Balance Balance Balance the the the the elements other than H and O O by adding H2O H by adding H+ charge by adding e-

Multiply each half-reaction by an integer such that the number of e- lost in one equals the number gained in the other Combine the half-reactions and cancel **Add OH- to each side until all H+ is gone and then cancel again**