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Philippine Handbook General Inorganic Chemistry

in Chemical Engineering Vergel Bungay

B.1. GENERAL INORGANIC CHEMISTRY

B1.1. INTRODUCTION

Inorganic Chemistry is the branch of chemistry that deals with the study of non-carbon
containing compounds or compounds classified other than organic. This section covers
the development of the atomic theory and periodic table of elements, chemical bonding
and reactions, gases and solutions, and nuclear chemistry.

B1.2. THEORY OF ATOMS

As early as the time of the Greek thinkers like Democritus, matter was believed to be
composed of tiny indestructible particles called atoms. The word atom was derived from the
Greek word atomos meaning uncut or indivisible.

The invention of the analytical balance enabled chemists to study the composition of
substances and discover that matter is formed from combination of elements in a definite
mass. This observation, made by Joseph Louis Proust, is known as the law of definite
composition.

In 1803, John Dalton proposed that an atom is composed of tiny indivisible particles and all
atoms of a given element are of the same shape, size and properties. However, atoms of
different elements differ chemically. Secondly, if elements combine to form two or more
compounds, the ratio of the mass of the other elements necessary to combine
stoichiometrically with a fixed amount of the other is either a whole number or a simple
fraction. Lastly, chemical reactions only involve rearrangement, combination and separation
of atoms.

Daltons concept of the indestructibility of atoms was believed for a century. But it was
upturned completely by the discovery of subatomic particles and radioactive elements, and the
phenomena of radioactivity. On the other hand, Daltons theory was found to support other
universal laws that helped to stimulate the works of modern chemists. The second statement
in his theory is known as the Law of Multiple Proportions. The third statement is the Law of
Conservation of Mass, which states that, matter is neither created nor destroyed in a given
chemical reaction.

B1.2.1. Discovery of the Subatomic Particles and Radioactivity

At the end of the 19th century, scientists devoted so much effort on the study of the
phenomenon of radioactivity where some substances were found to transmit and emit energy
in the form of waves through space.

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One device used to study radioactivity was a cathode ray tube. This evacuated glass tube
contained two metal plates connected across a high-voltage source. When current passed
through the metal plates, a ray was emitted from the negatively charged plate (cathode) and
drawn towards the positive plate (anode). This ray, called the cathode ray, was invisible but
produced a bright light upon striking a fluorescent screen. Some experiments further
characterized the nature of the ray by adding two charged plates and a magnet. In the
experiment, the ray deflected towards the positive plate and was repelled by the negative
plate. Moreover, in the presence of a magnetic field the ray deflected and appeared to interact
with the magnetic field in such a manner that indicated a negative charge on the particle.
Furthermore, the nature of the cathode ray was found unaffected with the material of which
the cathode was constructed, the type of metal wires used to conduct the current, the type of
gas present in the tube and irrespective of the materials used to generate the current. This
showed that the negatively charged particles are basic components of atoms.

In 1897, Joseph John Thomson determined the ratio of the charge of an electron to its mass to
be 1.76 x 108 coulomb per gram electron through the cathode ray tube. He was then
recognized as the discoverer of this negatively charged subatomic particle called the electron.
In line with this experiment, Robert Andrews Millikan determined the charge of an electron to
be 1.6 x 1019 coulomb through his oil-drop experiment.

In the same year, Wilhelm Rontgen discovered that cathode rays caused metals to emit unusual
rays that penetrated matter, and are highly fluorescent. He called these rays X-rays. After the
discovery of these rays, Antoine Becquerel happened to wrap an unexposed photographic
plate with a uranium compound that eventually darkened the plate spontaneously. This
phenomenon was called radioactivity to explain the spontaneous emission of highly energetic
radiation.

Before the discovery of the electron, Eugene Goldstein identified the presence of a bright light
within the cathode in the cathode ray tube. This signifies that positive rays were also present
in the tube. Studies show that there are different positive particles present depending on the
gas used in the tube. The lightest of these positive particles was obtained when hydrogen gas
was used. The particles had an electric charge to mass ratio of 9.5791 x 10 4 coulomb per gram
and its absolute charge is the same to that of an electron. This positively charged particle is
known as the proton.

In 1910, Ernest Rutherford with his associates, Johannes Geiger and Ernest Marsden,
performed an experiment that involves bombardment of a thin sheet of gold foil with alpha
particles in an evacuated tube. In the said experiment, most of the alpha particles were
observed to pass through the thin gold foil, some particles deflected and very few particles
bounced back as shown in a zinc sulfide coated glass tube. These observations led to the
explanation of the nature of the nucleus. The atom, based on this experiment, is almost an
empty space. The nucleus is the central core of the atom where the mass of an atom is deeply
concentrated and acquires a positive charge.

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After the discovery of the nature of the nucleus, it was known that a hydrogen atom contains
one proton and a helium atom with two protons. Therefore the latter is twice as much heavy
as the former. On the contrary, the helium atom was found to be four times heavier than the
hydrogen atom and therefore another particle must be responsible for such difference. In
1932, James Chadwick was able to identify a neutral particle known as the neutron by
bombarding a beryllium atom with an alpha particle.

B1.2.2. Atomic Number, Atomic Weight, Mass Number and Isotopes

With the discoveries described in the last section, the atom of an element can be identified
with the number of protons and neutrons in its nucleus. The atomic number is the number of
protons and the mass number of an atom is the number of protons and neutrons in the nucleus.
For a neutral atom, the number of electron is equal to the number of protons. However, in
nature, elements were found to exist with different mass numbers. These elements with
different mass numbers are called isotopes. Hydrogen atom has three isotopes as follows:

Table B1 1. Isotopes of Hydrogen.


proton neutron electron
Protium 1 0 1
Deuterium 1 1 1
Tritium 1 2 1

B1.2.3. Quantum Theory and Photoelectric Effect

In 1900, Max Planck discovered that when solids are heated, they emit a discrete quantity, or
quantum, of energy in the form of electromagnetic radiation. The energy of a single quantum
of energy is given by:

E hf (B1 1)

where h is Plancks constant, 6.626176 x 1034 J-s and f is the frequency of radiation, s-1.

In 1905, Albert Einstein proposed the photoelectric effect theory, which explained the
phenomenon in which electrons are released when a minimum frequency of light strikes the
surface of certain metals. He was also able to establish a direct relationship between the
number of electrons ejected from metals exposed to light and the intensity of the light. He
called these particles of light photons. Einstein further suggested that these photons carry
energy equal to hf and the higher the intensity of the light, the greater number of electrons was
emitted of high kinetic energy.

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B1.2.4. Quantum Numbers


The distribution of electrons in an atom is described by quantum numbers derived from the
Schrodinger equation for the hydrogen atom. The following quantum numbers are used to
describe the electron distribution on hydrogen atom and other atoms:

1. Principal Quantum Number (n) gives the distance of an electron from the nucleus
residing in an orbital. It has integral values 1,2,3 that correspond to the energy level
the electron is located. The maximum number of electrons for every value of n is 2n2.
2. Secondary or Angular Momentum Number (l) describes the shape of the atomic
orbital. It has integral values of 0 to n1. When l = 0, the shape of the orbital is
spherical or the s orbital. All s orbitals have the same shape but differ in size as the
value of the principal quantum number increases. When l = 1, the orbital is a p orbital
and so on.
3. Magnetic Quantum Number (m) has integral values from l to +l and describes the
orientation of the orbital in space. When l = 1, the values of m are 1,0,+1. This means
that there are three p orbitals with the same energy but differ in orientation in space
4. Spin Quantum Number (s) denotes the spin of electron in an orbital that are proposed
to act like magnets. It has values of + (clockwise) or (counter clockwise)

B1.2.5. Electronic Configuration


In distributing the electron in the atomic orbitals, the following rules are followed:
1. Aufbau Principle. Electrons are distributed to subshells of lower energy to higher
energy.
2. Paulis Exclusion Principle. No two electrons will have the same set of quantum
numbers or if an electron occupies the same orbital, these electron must have opposite
spins
3. Hunds Rule of Multiplicity. The most stable arrangement of atoms in degenerated
orbitals is the one with the most parallel spins. In filling electrons in subshells, the
electrons are placed singly before any pair is made.

The following methods are used for writing the electronic configuration:

1. Orbital Method
8O 1s2 2s2 2p4

1s 2s 3s 4s 5s 6s 7s
2p 3p 4p 5p 6p 7p
3d 4d 5d 6d
4f 5f
2. Shell Method. In this method, the valence shell electron or the electron in the
outermost shell is shown. The first shell corresponds to the first energy level, second
shell to second energy level and so on.
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8O 2e 6e

3. Rectangular Arrow Method. This method shows the degenerate orbitals of p, d and f in
a rectangle and the opposite spins of electrons in each orbital.
8O

1s
2s 2p

4. Core Method. The noble gas of lower atomic number is used and the remaining
electrons are listed using the orbital method.

8O [He] 2s2 2p4

B1.2.6. Development of the Modern Periodic Table

The development of the modern periodic table started when chemists observed similar
properties of elements. In 1829, Johann Dobereiner arranged the elements into triads. These
elements of similar properties are LiNaK, ClBrI and CaSrBa. The first attempt to
arrange the elements in increasing atomic weight was done by John Newlands. He found out
that every eighth element has similar properties. The modern periodic table is based on the
independent works of Dmitri Mendeleev and Julius Lothar Meyer. The list of elements
published by Mendeleev is arranged in columns and elements with similar properties are in
the same row. He concluded that when elements are arranged in increasing atomic weight,
their properties follow a certain periodic pattern. On the other hand, Henry Gwyn-Jeffreys
Moseley did the arrangement of the elements with respect to its atomic number in the early
20th century. This conclusion was made when he performed experiment involving X-ray
emissions of elements bombarded by highly energetic electrons that showed how protons in
the nucleus varied for every element. Today, the chemical and physical properties of elements
are found to be periodic functions of their atomic numbers, the modern periodic law.

B1.2.7. Classification of Elements in the Periodic Table

In Figure B1-1, elements are arranged in the periodic table according to their similarities in
properties. The vertical column of elements is known as the family and horizontal row of
blocks are called periods or series. The elements in the left most portions are metals and on
the right portion are nonmetals. The elements in the ladder-like line are called metalloids
whose properties are intermediate between metals and nonmetals. Group 1A is called alkali
metals because these metals form hydroxides that are alkaline in aqueous solutions. Group 2A
is called alkaline earth metals since they can be found in the earths crust and also forms
alkaline solutions in water. Group 3A, 4A, and 5A are known as the boron, carbon and
nitrogen family, respectively. The group led by oxygen is called chalcogens and fluorine
group are collectively known as halogens.

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Aside from periods and families, elements can be classified according to how subshells are
filled. They are classified as representative elements or main group elements (s and p block
elements), transition elements (d block elements), noble gases (group 8A or 18) and the
lanthanide and actinide series (f block elements).

1A 2A 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B 3A 4A 5A 6A 7A 8A
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

s block
p block
1 2
H He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 d block 13 14 15 16 17 18
Na Mg Al Si P S Br Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Cl Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Rf Ha Sg Ns Hs Mt Uun Uuu Uub [] Uuq [] [116] [] [118]

f block

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Figure B1 1. The Modern Periodic Table of Elements.

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B1.2.8. Periodic Trends in Physical and Chemical Properties

The electronic configurations of elements show a periodic trend as the atomic number
increases in the periodic table. Physical and chemical behaviors of these elements also vary
the same way. The following atomic properties are observed in this section:

1. Atomic Size. This is one half the distance between two adjacent nuclei in the
crystalline form of the elements and molecules of gaseous elements. Generally, the
atomic radius increases down a group and decreases across a period. The increase in
atomic size down a group is due to the increase in energy level or shell compared to
the element above it. On the other hand, the increased nuclear charge decreases the
radii of the atom by drawing the electron shells together. For elements across a given
period, the element with the higher atomic number has a greater nuclear charge than
the element prior to it. The greater the nuclear charge implies greater attraction
between the electrons and the nucleus that result in the shrinking of the atoms across a
given period.

2. Ionic Size. This is the radius of a cation or anion measured using X-ray diffraction. If
an atom forms a cation, the nuclear charge is unaffected but the electron-electron
repulsion is reduced. This results in the shrinkage of the electron cloud. Thus, the
cation formed is smaller than the atom. On the other hand, when an atom forms an
anion by accepting an additional electron, the electron cloud increases making the
anion larger than the parent atom.

3. Ionization Energy. This refers to the energy required to knock off an electron from a
gaseous atom in its ground state. Metals have low ionization energy and nonmetals
have relatively high ionization energy. Such high ionization energy of nonmetals
particularly of noble gases explains its relative inertness or unusual stability. Down a
group, ionization energy decreases due to the increase in energy level that results in
the decrease in attraction between the nucleus and the outer-most electrons. Within a
given series, an increase in the ionization energy is observed but not in a regular
manner. Fluctuations are due to the stability attained when subshells are being filled.

4. Electron Affinity. The energy change that accompanies the acceptance of an electron
by a gaseous atom to form an anion. It indicates how bound an additional electron is to
an atom. If the electron affinity is negative or energy is released when an atom accepts
an electron, the ion formed is less stable than the neutral atom. Generally, electron
affinity decreases from top to bottom and from right to left.

The following general observations are summarized on Figure B1-2 for the representative
elements. Note that fluctuations may occur due to the filling of subshells.

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B1.2.9. Chemical Bonding

The concept of electronic distribution in an atom and the development of the modern periodic
table aided chemists to fully explain the formation of compounds and molecules. Gilbert
Newton Lewis proposed that atoms combine to form a more stable electronic configuration
resembling that of the noble gases. This rule is known as the octet rule. Lewis proposed a
symbol of an element with their valence electrons as dots called the Lewis dot notation.
Elements in the same family have the same valence electrons. Figure B1-3 shows the dot
symbol for representative elements and the noble gases.

1 5 6 7 8 9 10
H B C N O F Ne
3
Li
11 From right to left
Na
19
K Increasing
37 From top to bottom Atomic Size
Rb Ionic Size (anions) / (cations)
55 Metallic Property
Cs Decreasing
87 Ionization Energy
Fr Electron Affinity

Figure B1 2. Periodic Trends in the Atomic Properties.

H He
Li Be B C N O F Ne
Na Mg
Ca

Figure B1 3. Lewis Dot Symbols of Representative Elements and Noble Gases.

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B1.2.10. Ionic Bond

The formation of this bond involves loss and gain of electron between atoms. An ionic bond
results in the electrostatic attraction between ions. It usually involves metals and
nonmetals. A concrete example is the reaction between sodium and chlorine to form
sodium chloride. When the two atoms come in contact, the outer electron of sodium is
transferred to the chlorine atom. The reaction is shown below:

+
Na + Cl Na Cl

1s1 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p5

2e 8e 1e 2e 8e 7e

B1.2.11. Covalent Bond

If the formation of compounds from a metal and a nonmetal is due to the electrostatic
attraction between two ions, the formation of a molecule is due to sharing of electrons
forming a covalent bond. Lewis proposed the formation of a hydrogen molecule resulted from
equal sharing of electrons of two hydrogen atoms. The reaction is as follows:
H + H H H or H H

With such sharing of electrons, the hydrogen atom in the molecule is said to be more stable
than its atom by depicting the electronic configuration of the noble gas helium.

In some cases, atoms in a covalent bond do not equally share electrons. The ability of an atom
to attract towards itself the electron in a covalent bond is known as electronegativity. Atoms
of elements with high electronegativity tend to attract an electron in the covalent bond more
than atoms with low electronegativity. Thus the chemical bond between such atoms is a polar
covalent bond. A polar covalent bond is the bond formed due to unequal sharing of electrons
between atoms that results in a shift of electron density towards the atom of greater
electronegativity. In the periodic table of elements, the same trend as ionization energy and
electron affinity is observed for electronegativity. Electronegativity is low for metals and high
for nonmetals. It decreases from top to bottom and from left to right. Figure B1-4 shows the
electronegativity of the representative elements as devised by Pauling:

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2.1
H
1.0 1.5
Li Be
0.9 1.2 2.0 2.5 3.0 3.5 4.0
Na Mg B C N O F
0.8 1.0 1.5 1.8 2.1 2.5 3.0
K Ca Al Si P S Br
0.8 1.0 1.6 1.8 2.0 2.4 35
Rb Sr Ga Ge As Se Cl
0.7 0.9 1.7 1.8 1.9 2.1 2.5
Cs Ba In Sn Sb Te I
0.7 0.9 1.8 1.9 1.9 2.0 2.2
Fr Ra Tl Pb Bi Po At

Figure B1 4. Electronegativity of Representative Elements.

Relatively, covalent bonds are weaker than ionic bonds. Covalent compounds are usually low-
melting point solids, liquids or gases and ionic compounds are high melting point solids. Most
ionic compounds are soluble in water, and their aqueous solutions conduct electricity. On the
other hand, covalent compounds are insoluble or may be slightly soluble in water. Their
solutions in water do not conduct electricity or are non-electrolytes.

B1.2.12. Formal Charge and Resonance

An atoms formal charge is given by the equation:

number of number of number of


Formal
= valence electrons nonbonding bonding (B1 2)
Charge
or group number electrons electrons

To write the formal charge of an atom in a molecule, the sum of the charges in the neutral
molecule must be equal to zero. For ions like CO 32 and NH4+, the sum of the formal charges
of the atom must be equal to the charge of the anion or cation.
In some cases, molecules can be represented by more than one Lewis structures. These
structures are called resonating structures or resonance structures. Not one of these structures,
however, adequately represents the structure of the molecule. A concrete example is the
resonating structures of the carbonate ion.

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O O O


O C O
O C O O C O

I II III

B1.2.13. Types of Chemical Reactions

A chemical reaction is the combination of atoms or molecules to form an entirely new


substance. A chemical equation is used to denote the chemical change taking place between
atoms and molecules. The following are general types of chemical reactions:

1. Combination Reaction or Synthesis (A + B AB)


a. metal + O2 metallic oxide (basic anhydride)
Na + O2 Na2O
b. nonmetal + O2 nonmetallic oxide (acid anhydride)
S + O2 SO2
c. metallic oxide + H2O base
Na2O + H2O 2 NaOH
d. nonmetallic oxide + H2O acid
SO2 + H2O H2SO3
2. Decomposition Reaction (AB A + B)
a. metal oxide metal + O2
HgO Hg + O2
b. metal carbonates metal oxide + CO2
Na2CO3 Na2O + CO2
c. metal bicarbonates metal carbonate + CO2 + H2O
2 NaHCO3 Na2CO3 + CO2 + H2O
d. metal nitrates metal nitrite + O2
KNO3 KNO2 + O2
e. metal oxyhalides metal halide + O2
2 KClO3 2 KCl + 3 O2
3. Single Replacement (AB + C CB + A)
a. Halogen Replacement (according to halogen activity series)
2 KI + Cl2 2 KCl + I2
2 KCl + I2 no reaction
b. Hydrogen Displacement Reaction (according to metal activity series)
HCl(aq) + Zn(s) ZnCl2(aq) + H2(g)
HCl(aq) + Au(s) no reaction

Activity Series of Metals (arranged in decreasing activity)


Li K Na Ca Mg Al Mn Zn Cr Fe Ni Sn Pb H Cu Bi Sb Hg Ag Pt Au

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Activity Series of Halogens (arranged in decreasing activity)


F2 Cl2 Br2 I2

4. Double Replacement or Metathesis Reaction


a. Precipitation Reaction. Reaction that involves formation of precipitate or insoluble
solid in aqueous solution
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)
b. Neutralization Reaction. Reaction of an acid and a base forming salt and water
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

B1.2.14. Molar Mass and Avogadros Number


The atomic mass is a relative scale of mass of elements. One atomic mass unit (amu) is equal
to one-twelfth of the mass of one carbon (C12) atom. The atom in one mole of C-12 atom or
12 grams of C-12 atom is 6.022 x 1023, known as the Avogadros number. The molecular mass
of a molecule is the sum of the atomic masses of elements making up the molecule. The
relationship between masses, number of moles and number of atoms can be obtained as
follows:
divide multiply

MASS MOLES Atoms


Molecules
multiply divide

MOLAR AVOGADROS
NUMBER
MASS

B1.3. SOLUTIONS

Many chemical reactions take place between ions and molecules dissolved in water or in any
other solvents. Numerous reactions in nature takes place in water solutions like in rivers, lakes
and oceans. Aqueous solutions are of great interest to scientists since water is considered to be
a universal solvent.
This section includes properties of solutions, methods of expressing concentration of solutions
and reactions in solutions. Colligative properties of solutions are also included in this section
both for solutions of electrolyte and non-electrolyte.

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B1.3.1. Types of Solutions

Solutions can be classified based on their capacity to dissolve a solute. A saturated solution is
a solution that contains the maximum amount of solute dissolved in a given amount of
solvent. This maximum amount of solute a solvent can hold is known as the solubility and is a
fixed value for a given temperature. An unsaturated solution contains less amount of solute a
given solvent can dissolve. A supersaturated solution contains more than the maximum
amount of solute a solvent can hold. This type of solution is unstable and dissolved solute
crystallizes out of the solution.

B1.3.2. Mechanism of Dissolution

When a solute dissolves in a solvent, its particles disperse throughout the solvent. The ease of
dissolution is dependent on the strength of solute-solvent interactions, solute-solute
interactions and solvent-solvent interactions. The separation of solute and solvent molecules
requires energy to break intermolecular forces between them. The combination of solute and
solvent molecules can either require (endothermic) or release (exothermic) some amount of
energy. The dissolution is said to be exothermic if the solute-solvent interaction overcomes
the solvent-solvent and solute-solute interactions and is therefore favorable.

B1.3.3. Concentrations of Solutions

Concentration of a solution is the measure of the amount of solute dissolved in a given solvent
or solution. The following are common methods of expressing this amount of solute in
solutions or solvents:

1. Weight percent, %w/w

wt solute
% wt solute 100% (B1 3)
wt solution

2. Weight by volume percent, %w/v

wt solute (gram)
% wt solute 100% (B1 4)
vol solution (mL)

3. Volume Percent, %v/v

vol solute
% vol solute 100% (B1 5)
vol solution

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4. Mole Fraction, X

mol solute
X solute 100% (B1 6)
mol solute mol solvent

5. Molarity, M

mol solute
M (B1 7)
vol solution (L)

6. Molality, m

mol solute
m 100% (B1 8)
wt solvent (kg)

7. Normality, N

equiv solute
N (B1 9)
vol solution (L)

B1.3.4. Colligative Properties of Solutions

These properties depend on the amount of solute present on the solution and the nature of the
solvent used. The following properties are as follows:
1. Boiling Point Elevation/Rise
TB TB,solution - TB,solvent K B m (B1 10)
where TB boiling point elevation/rise
KB ebullioscopic constant / molal boiling point constant
m molality

2. Freezing Point Depression


TB TF, solvent - TF,solution K F m (B1 11)
where TF freezing point depression
KB cryoscopic constant / molal freezing point constant
m molality

3. Vapor Pressure Lowering


P solvent - Psolution solvent X solute (B1 12)
where P vapor pressure lowering
vapor pressure
X mole fraction of solute in solution
4. Osmotic Pressure
MRT (B1 13)

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where osmotic pressure


M molarity, mol/L
R universal gas constant, 0.08205 L-atm / K-mol
T temperature of solution, K

The behavior of the colligative properties of an aqueous solution can be studied using a phase
diagram of both water and solution.

P
H2O
L
1 atm solution

V
T
TF TB

Figure B1 5. Phase Diagram of Water and an Aqueous Solution.

B1.4. IDEAL GASES

Matter can exist in three forms namely solid, liquid and gases. Water exists as solid ice, liquid
water or even water vapor. Elements that exist as gases at standard ambient condition include
the noble gases, and the diatomic molecules such as H 2, O2, N2, F2, and Cl2. The physical
characteristics of a gas include:

1. It assumes the volume and shape of its container


2. It has lower density compared to solids and liquids
3. It is compressible and mixes completely with other gases in a container

In this section, ideal gases and mathematical expressions describing its behavior are
discussed.

B1.4.1. Kinetic Molecular Theory of Gases


James Maxwell and Ludwig Boltzmann proposed that the physical properties of gases could
be correlated to the motion of individual molecules. Such observations lead to some

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generalizations about the behavior of gases called kinetic molecular theory of gases. Gases
that behave according to the kinetic molecular theory are called ideal gases. The assumptions
are given as follows:

1. Gases are composed of molecules separated from each other at a distance very much
greater than its size. It has mass but negligible volume.
2. Gas molecules move in random motion and collide with each other. The collision is
said to be perfectly elastic. This type of collision results in the conservation of
momentum and kinetic energy.
3. The individual gas molecules neither exert attractive nor repulsive forces with one
another.
4. The average kinetic energy of molecules varies directly with the absolute temperature.

B1.4.2. Ideal Gas Laws

Based from experiments on the physical properties of gases, several generalizations was made
to explain the macroscopic behavior of ideal gases as temperature, volume, pressure and its
amount in moles are varied.

1. At constant temperature (isothermal condition), the pressure of a gas varies inversely


to its volume. Robert Boyle using a U-tube filled with mercury observed this
relationship of pressure-volume as the temperature of a gas is fixed.
P1V1 = P2V2
(B1 14)
Boyles Law

2. At constant pressure (isobaric condition), Jacques Charles and Joseph Louis Gay-
Lussac proposed that the volume of a fixed amount of gas varies directly to its
temperature in Kelvin.
V1 V2

T1 T2 (B1 15)
Charles Law

3. At constant volume (isochoric condition), the pressure of a fixed amount of gas


increases as the temperature increases. This study was done by Guillaume Amonton.
P1 P
2
T1 T2 (B1 16)
Amontons Law

4. At constant pressure and temperature, volume of a gas is directly proportional to the


number of moles of the gas. At 1 atm and 0C, one mole of a gas occupies 22.414 L.
The mathematical expression of Avogadros Law is

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Philippine Handbook General Inorganic Chemistry
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V1 V2

n1 n2 (B1 17)
Avogadros Law

Combining these laws, the relationship of pressure, volume, temperature, and the amount of
gas in moles can be expressed as
PV nRT (B1 18)
The values of the universal gas constant, R is given in Table B.2.

Table B1 2. Universal Gas Constant.


m 3 Pa m 3 bar
8.314 0.08314
gmol K gmol K
L atm L mm Hg
0.08205 62.36
gmol K gmol K
cal ft 3 psia
1.987 10.73
gmol K lbmol R

For mixture of ideal gases at constant temperature and volume, the total pressure of an ideal
gas mixture is equal to the sum of the partial pressures of the individual gases in the mixture.
This is a statement of the Daltons Law of Partial Pressure. Consider a mixture of three ideal
gases with nA, nB and nC number of moles at temperature, T and occupying a volume V.

PT PA PB PC (B1 19)
nA n
PA PT A PT y A PT (B1 20)
nA nB nC nT

Similarly at constant temperature and pressure (Amagats Law of Partial Volume),


VA
yA (B1 21)
VT

For the diffusion of gases, Thomas Graham in 1830 states that rates of diffusion of two gases
is inversely proportional to the square root of their densities. Since the density of an ideal gas
is directly proportional to its molecular weight, Grahams Law of Diffusion can be expressed
as:

rA B MWB
(B1 22)
rB A MWA

B1.5 NUCLEAR CHEMISTRY

A special type of reaction that involves the change of atoms to different types of atoms is a
called a nuclear reaction. A branch of chemistry that deals with the study of changes

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Philippine Handbook General Inorganic Chemistry
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occurring in radioactive substances is Nuclear Chemistry. A radioactive element is one that


spontaneously emits radiation. Most of the radioactive elements are not found free in nature
but are made synthetically. Of the 3000 nuclides, 280 are stable and the rest are unstable and
said to change to a different nuclide. Such change is known as radioactive decay. Table B.3
summarizes different emitted particle or radiation in a radioactive decay.

Table B1 3. Types of Emitted Particle/Radiation.


PARTICLE CHARGE SYMBOL
beta particle / electron -1 0
1 or 0
1 e
positron +1 0
1 or 0
1 e
1 1
proton or a hydrogen nucleus +1 1 p or 1 H
1
neutron 0 0 n
gamma ray 0
0
0
alpha particle or helium nucleus +2 4
2 or 4
2 He

B1.5.1. Types of Radioactive Decay

There are three emissions characteristic of most radioactive decay. These are alpha (), beta
() and gamma () emission. Typical examples of radioactive decay are as follows:

1. Alpha Emission
211
83 Bi 207
81 Tl 4
2
2. Beta Emission
10
4 Be 10
5 B
0
-1

3. Electron Capture
50
23 V 0
-1 e Ti X - ray
50
22

4. Gamma Ray Emission


211
83 Bi 207
81 Tl 4
2 0
0
5. Neutron Emission
87
36 Kr 86
36 Kr 1
0 n
6. Positron Emission
54
27 Co 54
26 Fe 0
1

B1.5.2. Application of Radioactivity


Radioactive decay follows first order kinetics such that the amount of substance left at any
time, t is given by

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Philippine Handbook General Inorganic Chemistry
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A t A o e kt (B1 23)

The specific rate constant, k can be obtained using the half-life of the radioactive substance.
ln2
k (B1 24)
t 1/2
The half-life of a substance is the time required for 50% of the original amount to decay.
Typical half-life of radioactive materials are given in Table B1 4.

Table B1 4. Half life of Radioactive Substances and Uses.


HalfLife, t Uses
Determination of organic objects to over 70,000 years
C14 5730 yrs
or older
9
U238 4.51 x 10 yrs Estimation of ages of rocks and extraterrestrial objects
Used in geochemistry for age of specimens by electron
K40 1.2 x 109 yrs
capture
Used in ionization chambers of smoke-detecting
Am241 433 yrs
devices
Sr90 28 yrs Used as power sources for instruments in space or sea
Cm247 18 yrs explorations
I131 8 days Used for treatment of thyroid cancers
Used for the detection of damaged or malfunctioning
Tl201 74 hrs
cells in the heart or blood vessel cells
Tc99 6 hrs Used in the detection of diseased tissues

General Inorganic Chemistry, B1 - 1

atomic number, B1 - 3
atomic weight, B1 - 3

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Philippine Handbook General Inorganic Chemistry
in Chemical Engineering Vergel Bungay

atoms, theory of, B1 - 1


Avogadros number, B1 - 12
chemical bonding, B1 - 8
chemical reactions, types of, B1 - 11
colligative properties of solutions, B1 - 14
covalent bond, B1 - 9
dissolution, mechanism of, B1 - 13
electronic configuration, B1 - 4
formal charge, B1 - 10
ideal gas laws, B1 - 16
ideal gases, B1 - 15
ionic bond, B1 - 9
isotopes, B1 - 3
kinetic molecular theory of gases, B1 - 16
mass number, B1 - 3
molar mass, B1 - 12
nuclear chemistry, B1 - 18
periodic table, classification of elements in the, B1 - 5
periodic table, development of the, B1 - 5
periodic trends in physical and chemical properties, B1 - 7
photoelectric effect, B1 - 3
quantum numbers, B1 - 4
quantum theory, B1 - 3
radioactive decay, types of, B1 - 18
radioactivity, application of, B1 - 19
radioactivity, discovery of, B1 - 1
resonance, B1 - 10
solutions, B1 - 12
solutions, concentrations of, B1 - 13
solutions, types of, B1 - 13
subatomic particles, discovery of, B1 - 1

B1 - 20