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TRAINING & DEVELOPMENT

OPERATIONS TRAINING

MODULE 8670 018


ADVANCED SCIENCE
INDEX
SECTION 1: CHEMISTRY
SECTION
18.1.
18.1.1.
18.1.2.
18.1.3.
18.1.4.
18.1.5.
18.1.6.
18.2.
18.2.1
18.2.2
18.2.3
18.3.
18.3.1.
18.3.2.
18.3.3.
18.4.
18.4.1.
18.4.2.
18.4.3.
18.4.4.
18.4.5.

SUBJECT

PAGE

CHEMICAL BONDING
Ionic bond.
Covalent bond.
Inter-molecular forces.
Vandar Valls forces.
Hydrogen bonding.
Metallic bonding.
PERIODIC TABLE
The general properties of the first 26 D-block
Period.
Catalyst.
The chemistry of selected transition metals.
CHEMICAL EQUILIBRIUM
The equilibrium constants Kc and Kp.
Altering the state of equilibrium.
Calculate Kc and Kp from concentrations and
partial pressures.
REACTION KINETICS
Chemical kinetics.
Example of first order reaction.
Fast rates of reaction.
Slow rates of reaction.
The rate determining step in reaction
mechanism.

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SECTION
18.4.6.
18.4.7.
18.4.8.
18.5.
18.5.1.
18.5.2.
18.5.3.
18.5.4.
18.5.5.
18.5.6.
18.5.7.
18.5.8.
18.5.9
18.6.
18.6.1.
18.7.
18.7.1.
18.7.2.
18.7.3.
18.7.4.
18.7.5.
18.8.
18.8.1.
18.9.2.
18.8.3.

SUBJECT

PAGE

The experimental determination of reaction


rate.
Factors affecting the rate of a chemical
reaction.
The collision theory of chemical reaction for
gases.
CATALYSIS
Catalyst definition.
Selectivity of catalyst.
Catalyst and rate of reaction.
Activity of different D-block element catalyst.
Catalyst deactivation.
Adsorption.
Kinetics and mechanism of NH3 synthesis.
General definition of catalysis.
Determination of surface area.
IONIC REACTIONS and EQUILIBRIUM.
The function of buffer solution and the
composition of different solutions.
CORROSION
Definitions.
The corrosion reaction.
The requirements for corrosion.
Forms of corrosion.
Corrosion control.
WATER TREATMENT
Introduction.
Selection of water treatment processes.
Water treatment unit.

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SECTION 2: MATHEMATICS

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SECTION 2: MATHEMATICS
SECTION
18.9.
18.9.1.
18.9.2.
18.9.3.
18.10.
18.10.1.
18.10.2.
18.11.
18.11.1.
18.11.2.
18.11.3.
18.11.4.
18.11.5.
18.12.
18.12.1.
18.12.2.
18.12.3.
18.12.4.
18.12.5.
18.12.6.
18.13.
18.13.1
18.13.2
18.13.3.
18.13.4.
18.14.
18.14.1.
18.14.2.
18.14.3.
18.15.
18.15.1.
18.15.2.
18.15.3.
18.15.4.
18.15.5.
18.15.6.

SUBJECT

PAGE

LOGARITHMS
Definition of logarithms.
The laws of logarithms.
Solution of index or exponential equations.
LINEAR EQUATIONS.
Linear simultaneous equations with three
unknowns.
The linear law.
QUADRATIC EQUATIONS
Multiplying binomials on sight.
Factorization.
The difference of to squares.
Solution by factors.
Solution by formula.
EXPONENTIAL FUNCTION
The distinguishing property of v = ex.
The exponential function.
Growth and decay laws.
Rates of change.
Natural logarithms.
Solution of equations involving ex.
DIFFERENTIATION.
Rate of change.
Functional notation.
Negative n values.
Zero and unity n values.
INTEGRATION.
The primitive.
Integration.
Direct rule.
TRIGONOMETRY
Introduction
Sine values.
Cosine values.
The tangent function.
The tangent curve.
Combined rules.

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SECTION 3: ELECTRICAL PRINCIPLES.


SECTION
18.16
18.16.1.
18.16.2.
18.16.3.
18.16.4
18.17.
18.17.1.
18.17.2.
18.17.3.
18.17.4.
18.17.5.
18.17.6.
18.17.7.
18.17.8.
18.17.9.
18.17.10.
18.17.11.
18.17.12.
18.17.13.
18.18.
18.18.1.
18.18.2.
18.18.3.
18.18.4.
18.18.5.
18.18.6

SUBJECT

PAGE

THE ELECTRIC CIRCUIT


Kirchoffs laws.
Sources.
Resistivity and calculation of resistance.
Voltage drop in a cable.
ELECTROSTATIC
Electric charges.
Coulombs law.
Electric fields, field intensity or electric force.
Capacitance.
Relationship between electric force and
potential gradient.
Electric flux density.
Relationship between D and E permitivity.
Capacitance between parallel plates.
Definition of relative permitivity.
Capacitors in parallel.
Calculation of capacitance of multi-plate
capacitors.
Capacitors in series.
Energy stored in a capacitor.
CAPACITANCE and CAPACITORS
Variable air capacitors.
Paper capacitors.
Mica capacitors.
Plastic capacitors.
Ceramic capacitors.
Electrolytic capacitors.

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SECTION
18.19.
18.19.1.
18.19.2.
18.19.3.
18.19.4.
18.19.5.
18.19.6.
18.19.7.
18.19.8.
18.19.9.
18.19.10.
18.20.
18.20.1.
18.20.2.
18.20.3.
18.20.4.
18.20.5.
18.20.6.
18.20.7.
18.21.
18.21.1.
18.21.2.
18.21.3.
18.21.4.

OPERATIONS TRAINING

SUBJECT

PAGE

ELECTROMAGNETIC INDUCTION
Magnetic fields produced by an electric
current.
Force on a conductor.
Magnitude of force on a conductor in magnetic
field is directly proportional to three factors.
The motor principle.
The conductor moving through a magnetic
field.
Lenzs law.
The generator principle.
Inductance.
Mutual inductance.
The energy stored in inductive circuits.
SINGLE PHASE SERIES CIRCUITS.
Pure resistance in the AC circuit.
Pure inductance in the AC circuit.
Pure capacitance in the AC circuit.
Series RLC circuit.
Power in AC circuit.
Series resonance.
Calculation of resonant frequency.
SINGLE PHASE TRANSFORMERS
The two coil transformer.
Phaser diagrams for the ideal transformer.
The transformer on load.
The practical transformer.

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SECTION 4: PROGRAMMED CONTROL IN PROCESS AND


MICRO PROCESSOR.
SECTION
18.22.
18.22.1.
18.23.
18.23.1.
18.23.2.
18.23.3.
18.24.
18.24.1.
18.24.2
18.25.
18.25.1.
18.25.2.
18.25.3.
18.25.4.
18.26.
18.26.1.
18.26.2.
18.26.3.
18.26.4.
18.26.5.
18.26.6.
18.26.7.
18.26.8.
18.26.9.

SUBJECT

PAGE

INTRODUCTION
ANALOGUE CONTROL
Types of controller.
APPLICATION OF A CLOSED LOOP
CONTROL SYSTEM
Ratio control.
Cascade system.
Feed forward control system.
DIGITAL CONTROL SYSTEM
The nature of analogue and digital control
systems.
Digital to analogue and analogue to digital
convertors.
NUMBERS and CODES FOR DIGITAL
SYSTEMS.
Decimal number system.
Binary number system.
Hexadecimal.
The octal number system.
DIGITAL SYSTEM COMPONENTS
Logic gates.
The Flip-Flop - FF.
Logic circuits from NAND or NOR gates.
The arithmetic function.
Binary counter.
Decoders.
Encoder.
Multiplexer (data selector).
Demultiplexer (data distributers).

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SECTION
18.27.
18.27.1.
18.27.2.
18.27.3.
18.27.4.
18.28.
18.28.1.
18.28.2.
18.28.3.
18.28.4.
18.28.5.
18.29.
18.29.1.
18.29.2.
18.29.3.
18.29.4.
18.29.5.
18.30.
18.30.1.
18.30.2.
18.31.
18.31.1.
18.31.2.
18.31.3.
18.31.4.

OPERATIONS TRAINING

SUBJECT

PAGE

THE MICROPROCESSOR
Internal architecture of a microprocessor.
Arithmetic/logic unit, ALU.
Accumulator and registers.
Programme control, PC.
THE MICROPROCESSOR SYSTEM or THE
MICROCOMPUTER.
Components of microprocessor system or
microcomputer.
The organization of microprocessor.
Memory.
Input/output devices.
Inter-connection buses.
DEVELOPMENT OF COMPUTER
CONTROL
Digital supervisory control.
Direct digital control.
Distribution computer control.
Programmable logic control. PLC.
Main parts of PLC system.
THE INSTRUCTION SET and
ADDRESSING MODES OF
MICROPROCESSOR
Instruction classification.
The addressing modes.
MACHINE CODE PROGRAMMES.
Assembly language.
Implementing an instruction.
The flo chart example.
Translate flow chart to assembler code.

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18. 1. CHEMICAL BONDING


Chemical bonds can be divided into two general categories:
a. Ionic bonds (or electrovalent).
b. Covalent bonds.
1.1.

Ionic Bond:

An ionic bond occurs when one or more electrons are transferred


from the valence shell of one atom to the valence shell of another. The
atom that loses electrons becomes a positive ion (a cation) while the atom
that acquires electrons becomes negatively charged (an anion).
The ionic bond results from the attraction between the oppositely
charged ions. Any given ion tends to attract as many neighboring ions
opposite charge as possible. When large numbers of ions gather together,
they form an ionic solid. The solid normally has a regular, crystalline
structure that allows for the maximum attraction of ions.
To understand why ionic bonding occurs, consider the transfer of a
valence electron from a sodium atom (electron configuration [Ne] 3s 1) To
the valence shell of the chlorine atom ([Ne] 3s 2 3p5). We can represent the
electron transfer by the following equation:
Na ([Ne] 3s1) + Cl ([Ne] 3s2 3p5)

Na+ ([Ne]) + Cl ([Ne] 3s2 3p6)

As a result of the electron transfer, ions are formed, each of which


has a noble-gas configuration. The sodium ion has lost its 3s electron and
has taken on the neon configuration, [Ne].
The chloride ion has accepted the electron into its 3P sub-shell and
has taken on the argon configuration, [Ne] 3s2 3p6. Such noble gas
configuration and the corresponding ions are particularly stable.
This stability of the ions accounts in part for the formation of the
ionic solid NaCl. Once each cation or anion forms, it attracts ions of
opposite charge. Within the sodium chloride crystal, NaCl, every Na + ion
is surrounded by six Cl- ions, and every Cl- ion by six Na+ ions. As shown
in Fig. (1.1)

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Fig. 1.1
The sodium chloride crystal. (Top) A photograph showing the cubic shape of sodium
chloride crystals. (Right) A model of a portion of the crystal detailing the regular
arrangement of sodium ions and chloride ions. Each sodium ion is surrounded by six
chloride ion and each chloride ion by six sodium ions.

Another example of the formation of an ionic substance is the


reaction between atoms of lithium and fluorine. The electronic structure
of these is: Li (1s2 2s1), F (1s2 2s2 2p5). When they react the lithium atoms
loses the electron from its 2S sub-shell and becomes Li+.
Notice that the lithium ion has an electron configuration that is the
same as the noble gas helium.
Li (1s2 2s1)

Li+(1s2) + e

The electron lost by the lithium atom is picked up by the fluorine


atom, which becomes a fluoride ion. F. This ion has an electron
configuration identical to that of the noble gas neon.
F (1s2 2s2 2p5) + e

F (1s2 2s2 2s6)

Once formed, the Li+ and F ions attract one another because of
their opposite charges. It is this attraction between the ions that
constitutes the ionic bond.
When a reaction between lithium and fluorine actually takes place
in real life, huge numbers of atoms are involved and equally huge
numbers of ions are formed.

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These ions pack them selves together to form the ionic solid, LiF. It
is important to remember that an ionic solid such as this does not contain
discrete molecules, but instead contains ions packed so that the attractive
forces between ions of opposite charge are maximized. While repulsive
forces between ions of the same charge are minimized.
Lewis Electron Dot symbols:
The preceding equation for the electron transfer between Na and Cl
can be simplified by writing Lewis electron dot symbols for the atoms
and monatomic ions (ions formed from a single atom).
In these symbols, the electrons in the valence shell of the atom or
ion are represented by dots placed a round the letter symbol of the
element. Table (1.1) lists the Lewis symbol and corresponding valence
shell electron configurations for the atoms of the second and third
periods.
Note that the dots are placed one to each side of the letter symbol
until all four sides, are occupied.
Table 1.1
Lewis Electron-Dot Symbols and Valence-Shell Electron Configurations for Atoms of
the Second and Third Period

Second period
Third period

Then the dots are written to a side until all valence electrons are
accounted for. (The exact placement of the single dots is immaterial. For
example, the single dot in the Lewis symbol for chlorine can be written
on any one of the four sides.)
The equations representing the transfer of an electron from the
sodium atom to the chlorine atom is written.
..
..
_
+
Na . + . Cl :
Na + | : Cl : |
..
..

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The noble-gas configurations of the ions are apparent from the


symbols. No dots are shown for the cation (all valence electrons have
been removed, leaving the noble-gas core). There are eight dots shown in
brackets for the anion (noble gas configuration ns2 np6).
Example 1.1:
What is the Lewis symbol for germanium (Z = 32)?
Solution:
Germanium is in group IVA and therefore has four valence
electrons. Its Lewis symbol has four dots that we arrange symmetrically
around the chemical symbol.
.
. Ge .
.

Example 1.2:
What is the formula of an ionic compound formed between Mg and P?
Solution:
Magnesium is in-group IIA and therefore will lose two electrons to
achieve a noble gas configuration. The ion formed is Mg2+.
Phosphorus is found in group VA and must acquire three electrons
to attain a noble gas structure. This produces that ion P 3. To make the
compound neutral, the total positive or negative charges must be a
multiple of both the 2+ and 3. The smallest number that is divisible by
both 2 & 3 is 6, so
(2+) x 3 = 6+
(3-) x 2 = 6net
0
The formula has to be Mg3P2.
1. 2. The Covalent Bond:
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Many substances, however, are molecular gases, liquids, or low


melting solids consisting of molecules. A molecule is a group of atoms
strongly linked by chemical bonds; often the forces that hold the atoms
together in a molecular substances cannot be understood solely on the
basis of attraction of oppositely charged ions.
An obvious example in the molecule H2, where the two H atoms
are held together tightly and no ions are present. It is proposed that the
strong attractive force between two atoms in a molecule resulted from a
covalent bond.
The formation of a bond between H and Cl to give an HCl
molecule can be represented as follows:
..
H . + . Cl :
..

..
H : Cl :
..

As the two atoms approach, unpaired electrons on each atom pair


up to form a covalent bond. The pair of electrons is shared by the two
atoms. Each atom then acquires a noble gas configuration of electrons,
the H atom having two electrons about it (as in He), and the Cl atom
having eight valence electrons about it (as in Ar). Bonding pairs are often
represented by dashes rather than by double dots.
Frequently, the number of covalent bonds formed by an atom
equals the number of unpaired electrons shown in the Lewis symbol.
Consider the formation of the molecules H2O, NH3 and CH4 from atoms.

In each case, a bond is formed between an unpaired electron on one


atom and an unpaired electron on another.

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Coordinate Covalent Bond:


A coordinate covalent bond is formed when both electrons of the
bond are donated by one atom as follows:
A+ : B

A: B

A coordinate covalent bond is not essentially different from other


covalent bonds, since it involves the sharing of a pair of electrons
between two atoms.
An example is the formation of the ammonium ion:

H ++

: NH

H. .
: N : H
..
H

Multiple Bonds:
So far, the molecules we have described have had only single
bonds, that is, covalent bonds in which a single pair of electrons is shared
by two atoms. But it is possible for two atoms to share two electron pairs
to give a double bond or three pairs to give a triple bond. As examples,
consider ethylene, C2H4, and acetylene, C2H2. Their Lewis formulas are

H
or

C=C

C::C

Ethylene

H:C:::C:H

or

HC CH
Acetylene

Double bonds form primarily to C, N, O and S atoms. Triple bonds


form mostly to C and N atoms.

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De-localized Bonding; Resonance:


It often happens that a single satisfactory electron dot formula,
for a molecule or ion cannot be drawn. Suppose, for example, that we try
to write an electron dot formula for sulfur dioxide, SO2. We find that we
can write two formulas:
:

:
S
and

These structures have their nuclei in identical positions but differ in


the arrangement of electrons. In both, one oxygen atom is bound through
a single bond to the sulfur while the other oxygen atom is connected via a
double bond.
We get around this problem by the concept of resonance. We say
that the actual electronic structure of SO2 does not correspond to either
(A) or (B) but, in stead, to a structure somewhere in between that has
properties of both.
Example 1.3:
Describe the bonding in carbonate ion, CO 32- using resonance
formulas.
Solution:
One possible electron dot formula for the carbonate ion is:
2-

C
O

2-

2-

2-

Since we expect all carbon oxygen bonds to be equivalent, we


must describeC the electron structure Cin resonance terms: C
O

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We expect that one electron pair will be de-localized over the


region of all three carbon oxygen bonds.
Bond order and Some Bond Properties:
The bond order is the number of covalent bonds that exist between
a pair of atoms. Or defined in terms of the Lewis formula, is the number
of pairs of electrons in the bond. For example, in C : C, the bond order is
1 (single bond); in C : : C, the bond order is 2 (double bond).
We have to describe three properties of covalent bonds; bond length,
bond energy and vibration frequency
Bond length (or bond distance): Is the distance between the centers of the
nuclei of the two atoms in a bond.
Bond energy: Is the amount of energy necessary to break the bond to
produce natural fragments. For a diatomic molecule such
as H2 this represent the process.
H : H(g)

H . (g) + H . (g)

While in a molecule such as C2H6.


H H
|
|
HCCH
|
|
H H (g)

H
H
|
|
HC. + .CH
|
|
H (g)
H (g)

The vibrational frequency of the atoms joined by the bond shows


that the atoms within a molecular are not stationary; they are in constant
motion. This motion can be resolved into two basic types, vibration and
bending.
There are two factors that affect the frequency of vibration (number
of vibration per second) one is the masses of the atoms bonded together
and the other is the bond order.
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As the order increases, the bond length decreases, and the strength
of the bond increases and so does the vibrational frequency and bond
energy.
Data that illustrate this are shown in Table (1.2)
Table 1.2
Bond
CC
C=C
CC
CO
C=
O
CN
C
N

Bon
d
order

Average
Bond length
(A)

Average
Bond energy
kJ/mol

Average
vib.
frequency

1
2
3
1
2

1.54
1.37
1.20
1.43
1.23

370
699
960
350
750

3.0 x 1013
4.9 x 1013
6.6 x 1013
3.2 x 1013
5.2 x 1013

1
3

1.47
1.16

300
730

3.7 x 1013
6.8 x 1013

1. 3. Intermolecular forces:
The attractive forces between molecules are much weaker than the
chemical bonding forces that exist between atoms in a molecule. We can
classify intermolecular forces into two types.
a. Vander waals forces.
b. Hydrogen bonding.
Table (1.3) lists the types of intermolecular forces and compares
their energies with those of chemical bonds.

Table 1.3
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Type of force

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Approximate energy
kJ/mol

Intermolecular
Vander waals
Hydrogen bonding

0.1 - 10
10 - 40

Chemical bonding
Ionic
Covalent

100 1000
100 1000

1. 4. Vander waals forces:


They are one kind of attractive force between molecules. They
arise from London forces, which exist between any two molecules and
from dipole dipole forces, which are present only between polar
molecules.
For example, consider a simple substance like neon, which
consists of molecules that are single atoms. Even though a chemical bond
does not form between two neon atoms, a weak attractive force exists and
it becomes stronger as the two atoms are brought near each other.
The attraction between neon atoms is about a thousand times
smaller than the attraction between atoms in a chemical bond. But
although it is small, it is responsible for the fact that at low temperature
neon gas liquefies. This attractive force holds the atoms together to form
the liquid. The nature of this attractive force is as a result of varying
positions of the electrons during their motion about their nuclei.
Because the theory was first developed by London, these attractive
forces are called London forces (they are also known as dispersion
forces). These forces tend to increase with molecular weight for the
following reasons.
1. Molecules with larger molecular weight usually have more
electrons, and London forces increase in strength with the
number of electrons.

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2. Larger molecular weight often means larger atoms, which


are more easily distorted to give instantaneous dipoles.
1. 5. Hydrogen bonding:
Is a weak to moderate attractive forces that exists between certain
covalently bonded hydrogen atoms and the lone pairs of electrons of
another atom. Hydrogen bonding occurs when the hydrogen atom is
covalently bonded to a highly electronegative atom, particulary fluorine,
oxygen, and nitrogen.
Water provides a common example of this kind of intermolecular
force Fig.(1.2). The electrons of a hydrogen oxygen bond are attracted
to the electronegative atom (oxygen), leaving the positive charge of the
proton (the hydrogen nucleus) partially exposed.
As a result, this proton is strongly attracted to the lone pairs of
other atoms. In the case of water, the proton of one water molecule is
attracted to the lone pairs on the oxygen atom of another water molecule
A hydrogen bond is usually represented by a series of dots, for example,
O. . . .H, Fig.(1.2b).

Fig. 1.2
Hydrogen bonding in water, (a) the electrons in the O-H bond of H 2O molecules are
attracted to the oxygen atoms, leaving the positively charged protons partially
exposed. A proton on one molecule will be attracted to a lone pair on an oxygen atom
in another water molecule. (b) Hydrogen bonding between water molecules is
represented by a series of dots.

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Although this type of interaction is called hydrogen bonding, the


strength of the interaction is usually much less than that of normal
chemical bonding.
The energies of most hydrogen bonds lie in the range of 10 to 40
kJ/mol. Thus, the hydrogen bonding interaction is stronger than Vander
waals forces, but less than one tenth that of covalent bonds. It is usual
to think of the hydrogen bonding attraction as a strong intermolecular
force, rather than as another form of chemical bonding.
Formic Acid, HCOOH, Ammonia, NH3 provide an examples of the
type O H . . . O formed between the carboxyl groups ( COOH) and an
N H. . . N type of hydrogen bond.
Example:
What kinds of intermolecular forces are expected in:
a. Methane.
b. Methanol.
Solution:
a. Methane is a non-polar molecule, hence, the only intermolecular
attraction are London forces.
b. Methanol has a hydrogen atom attached to an oxygen atom.
Therefore, we expect hydrogen bonding. Since the molecule is
polar (from the O H bond), London forces exist too, because such
forces exist between all molecules.
1.6. Metallic bonding:
In this kind of bonding, positively charged atomic cores are
surrounded by de-localized electrons. Example: iron, copper, silver.
Metals are examples of extremely de-localized bonding. A sodium metal
crystal, for example, can be regarded as an array of Na+ ions surrounded
by a (sea) of electrons, Fig (1.3).
The valence or bonding electrons are de-localized over the entire
metal crystal. The freedom of these electrons to move throughout the
crystal is responsible for the electrical conductivity of a metal.
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Fig. 1.3
Delocalized bonding in sodium metal. The metal consists of positive sodium ions in a
sea of valence electrons. Valence (bonding) electrons are free to move throughout
the metal crystal (colored area)

18. 2. PERIODIC TABLE


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2. 1. The General Properties of the first D-Block Period:


The transition elements are strictly defined as those elements
having a partially filled (d) or (f) sub-shell in any common oxidation state
[including (o) oxidation state]. For example, copper, which has the
configuration [Ar]3d10 4s1 in the (o) oxidation state, has the configuration
[Ar]3d9 in the common +2 oxidation state.

Period

Thus, copper has a partially filled d sub-shell, and therefore copper


is a transition element. Fig (2.1) shows the various divisions of the
transition elements.

d-block transition elements


(transition elements)

f-block transition elements


(inner transition elements)

Fig. 2.1
Classification of the transition elements.

The d-block transition elements are those transition elements with


an unfilled d sub-shell in common oxidation states. These elements are
frequently referred to simply as the transition elements.
Although zinc, cadmium, and mercury, in-group IIB, are not dblock transition elements by the strict definition. They are often included
with them because of their similar properties. We will accept this broader
definition and concentrated our attention on these elements in the centre
of the periodic table. The elements with a partially filled (f) sub-shell in
common oxidation states are known as f-block transition elements or
inner transition elements.

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The f-block transition elements are the two rows of elements at the
bottom of the periodic table. The elements in the first row are called the
lanthanides or rare earths; the elements in the second row are called
actinides.
All of the actinides are radioactive and from neptunium (element
93) onwards are synthetic. They have been produced in nuclear reactors
or by using particle accelerators.
The transition elements have a number of characteristics that set
them apart from the maingroup elements.
1. All of the transition elements are metals and, except for the
IIB elements, have high melting point, high boiling points,
and are hard solids. Thus in the fourth period elements from
scandium to copper, the lowest melting metal is copper
(1083C) and the highest melting point is vanadium
(1890C). In the main group metals, only beryllium melts
above 1000C, and the rest melt at appreciably lower
temperatures.
2. With the exception of the IIIB and IIB elements, each
transition element has several oxidation states. Chromium,
for example, exists in all oxidation states from 0 to +6. Of
the maingroup metals, only the heavier ones display several
oxidation states. Because of their multiplicity of oxidation
states, the transition elements are often involved in oxidation
reduction reactions.
3. Transition-metal compounds are often colored, and many are
Para-magnetic. Most of the compounds of the main group
metals are colorless and diamagnetic.
Melting points, Boiling points, and Hardness, are shown in Table
(2.1). All of these properties depend on the strengths of metal bonding,
which in turn depend roughly on the number of unpaired electrons in the
metal atoms.

Table 2.1
Properties of the fourth-period transition elements

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Oxidation states (variable valency):


The table (2.2) gives oxidation states in compounds of the fourth
period transition elements. The multiplicity of oxidation states in due to
the varying involvement of the (d) electrons in bonding.
Table 2.2
Oxidation states of the fourth-period transition elements

Note:
Common oxidation states are in bold face, asterisks denote the
stables states. Additional oxidation states, particularly zero and negative
values, may be observed in complexes with CO and with organic
compounds.
Colored Ions:

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Most transition elements form cations of several different charges.


For example, iron has the cations Fe+2 and Fe+3, Neither of these ions has
noble gas configurations; that would require the energetically impossible
loss of eight electrons. The 2+ ions are common for the transition
element, and are obtained by the loss of highest energy (s) electrons from
the atom, many transition elements also forms 3+ ions by losing one (n
1) (d) electron in addition to the two (ns) electrons.
Ions with a partially filled (d) sub-shell exhibit various types and
intensities of coloration in aqueous solutions. This is due to absorption of
visible light involving (d) electrons (photons of this absorbed light
provide the energy required to raise the (d) electrons from one energy
level to a higher one). Table (2.3) lists common Transition-Metal ions.
Table 2.3
Common transition-metal cations

Complex Ions:
Many metal ions, especially those of the transition elements, form
coordinate bonds with molecules or anions having lone pairs of electrons.
For example, the silver ion, Ag+, can react with NH3 to form the
Ag(NH3)2+ ion. The lone pair of electrons of the N atom of NH 3 form a
coordinate covalent bond to the silver ion:
Ag+ + 2(: NH3)
(H3N : Ag : NH3)+
The formation constant, or stability constant, K, of a complex ion
is the equilibrium constant for the formation of the complex ion from the
aqueous metal ion and the ligands (NH3 molecules). Thus the formation
constant of Ag(NH3)2+ is.

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Ag[NH3]2+
K =
[Ag+] [NH3]2
The large value of K means that the complex ion is quite stable.
Table (2.4) lists values for the formation constants of some complex ions.
Table 2.4
Formation constants of complex ions at 25C

Para magnetic:
Among the first complexes studied were those of chromium (III).
There are a great number of these, including the violet complex hexaaqua chromium chloride, [Cr(H2O)6]Cl3, and the yellow complex hexaamine chromium chloride [Cr(NH3)6]Cl3.
Almost all chromium complexes have the coordination number 6,
and thus are octahedral complexes. All are paramagnetic, displaying
magnetism equivalent to that of three unpaired electrons.
The orbital diagram for the metal atom in the complex, [Cr(NH3)6]Cl3:

Ar


3d

4s

4p

4d

d2 sp3 bonds to ligands

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If we examine any transition-metal ion that has configurations d 4,


d5, d6 or d7, we will find two bonding possibilities. In one case, the
bonding is sp3d2. In the other, some electrons are paired and the bonding
is sp3.
The number of unpaired electrons in the latter type of complex is
lower than that with sp3d2 bonding. For that reason, it is called a low-spin
complex ion. The complex ion with more unpaired electrons is called a
high-spin complex ion. Since low-spin complex ions require energy for
pairing of electrons, they are expected to occur with ligands that bond
relatively strongly. Weakly bonding ligands form high-spin complex ions.
As an example, Cobalt (II) has both high-spin and low-spin
octahedral complex ions. Most of the octahedral complex ions are highspin, such as the pink ion Co(H 2O)62+. There are also a few low-spin
complex ions such as Co(CN)64-. Describe the bonding in both Co(H2O)62+
and Co(CN)64- using valence bond theory.
How many un-paired electrons are there in each complex ion? The
solution: The electron configuration of cobalt is [Ar]3d 74s2, and that of
the cobalt(II) ion is [Ar]3d7. A high-spin complex ion such as Co(H2O)62+
would be obtained from sp3d2 hybrid orbitals. The complex ion would be
paramagnetic, with three unpaired electrons.
Bonding of the cobalt (II) ion using d 2sp3 hybrid orbitals would
required that two unpaired electrons in the 3d sub-shell be moved. One
could pair up with another electron in a 3d orbital, but the other would
have to be promoted to higher unoccupied orbital (4d). The orbital
diagram for a low-spin complex ion, such as Co(CN)64-:
The complex is paramagnetic, with one unpaired electron.
Co(H2O)62+:

Ar


3d

4s

4p


4d

Co(CN)63-:

Ar


4s

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Although coordination number 6 (octahedral complexes) is very


common, coordination number 4 is nearly so. In this case, the geometries
are either tetrahedral or square planar. Table (2.5) lists the hybrid orbitals
used to describe various geometries.
Table 2.5
Hybrid orbitals for various coordination numbers and geometries

Coordination
number
2
4
6

Geometry
Linear
Tetrahedral
Square
planer
Octahedral

Hybrid
orbital
sp
sp3
dsp2
d2sp3 or sp3d2

2. 2. Catalyst:
1. Fe with K2O and Al2O3.
In Haber process for ammonia

N 2 3H 2 2NH 3
2. Pt Rh mixture.
In Ostwald process for nitric acid (NO reacts with O2 and H2O to give
HNO3)

4NH 3 5O 2 4NO 6H 2 O
3. Pt, V2O5.
Contact process for sulfuric acid (SO3 reacts with H2O to give H2SO4).
2SO 2 O 2 2SO 3

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4. Ni, Pt, Pd.


Hydrogenation of compounds with C = C (such as unsaturated vegetable
oils).
C H
2

C H
2

5. ZnO CuO mixture.


Water gas shift reaction (to produce H 2 or synthesis gas with higher
concentration of H2).
CO H 2 O CO

H2

6. Ni.
Catalytic methanation (preparation of substitute natural gas).
CO 3H 2 CH 4 H 2O

7. Fe CO mixtures.
Fischer Tropsch process (preparation of synthetic gasoline).
8CO 17H 2 C8H18 8H 2O

8. ZnO Cr2O3 mixture


Industrial synthesis of methanol.
CO 2H 2 CH 3OH

9. Al2O3.
Industrial synthesis of carbon disulfide.
CH 4 2S2 CS3

10. Pt, Pd, V2O5.

2H 2S

Automobile catalytic converter (to reduce pollutants in exhaust gases).


2CO O 2 2CO 2

C 7 H16 11O 2 7CO 2 8H 2 O

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The above catalysts used in some important gaseous reactions.


Note that carbon monoxide and hydrogen react to give various products
depending on the catalyst. Mixtures of CO and H 2 can be made from
many organic, or carbon-containing, substances by reaction with steam.
For example,
CH 4 g H 2 O g CO g 3H 2 g

Natural gas
C S H 2 O g CO g H 2 g

Coal
In the presence of ZnO and Cr 2O3, carbon monoxide and hydrogen
give methanol, CH3OH. Methanol is the starting material for
formaldehyde, CH2O, which is used to make plastics, carbon monoxide
and hydrogen also react in catalytic methanation to give methane for
substitute natural gas, the catalyst is nickel.
Study of the catalysts and reaction conditions for the various
reactions of CO and H2 has become an active research area. These
reactions make it possible to convert a variety of organic materials,
including coal and organic wastes, to gaseous and liquid fuels and all of
the industrial chemicals presently obtained from petroleum.
2. 3. The chemistry of selected transition metals:
Iron and titanium are the most abundant of the transition elements.
In fact, iron is the fourth most abundant element in the earths crust, after
oxygen, silicon, and aluminum. The transition elements occur in most
cases as oxide or sulfide ores. Table (2.6) lists some of these ores. The
least reactive elements, such as gold, silver, copper, and platinum, are
found as uncombined metals.
Table 2.6
Some ores of the transition metals

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Many of the transition metals are used commercially in alloys. The


most important of these are the steels, which are alloys of iron with small
amounts of carbon and often other transition elements such as chromium,
manganese, and nickel.
Steels:
Steels are alloys containing over 50% iron and up to about 1.5%
carbon. The iron obtained from a blast furnace (called pig iron) contains a
number of impurities, including 3-4% carbon, that make it brittle.
The first step in the production of steel is to remove these
impurities and reduce the carbon content of the iron through the
controlled oxidation. In the basic oxygen process, this is accomplished by
blowing oxygen into the molten iron until the amount of carbon is
reduced to the required level.
Carbon in the molten iron reacts to give carbon monoxide. Other
metals may be added to the steel.
18. 3. CHEMICAL EQUILIBRIUM
3. 1. The equilibrium constants Kc and Kp:
Definition of the equilibrium constant Kc:
Consider the general reaction

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aA bB cC dD

Where A, B, C, and D denote reactants and products and a, b, c,


and d are coefficients in the balanced chemical equation.
The equilibrium constant expression for the reaction is obtained
by multiplying the concentrations of products together, dividing by the
concentrations of reactants, and raising each concentration term to a
power equal to the coefficient in the chemical equation.
The equilibrium constant Kc is the value obtained for the
equilibrium constant expression when equilibrium concentrations are
substituted. For the general reaction, we have.
Kc =

[C]c [D]d
[A]a [B]b

Here, the molar concentration of a substance is denoted by writing


the formula of that substance in square brackets. The subscript c on the
equilibrium constant denotes that it is defined in terms of molar
concentrations.
According to the law of mass action, the value of Kc is a constant
for a particular reaction at a given temperature, whatever equilibrium
concentrations are substituted. As the following example illustrates, the
equilibrium-constant expression is defined in terms of the balanced
chemical equation. If the equation is rewritten with different coefficients,
the equilibrium-constant expression is changed.
Example:
a. Write the equilibrium-constant expression, Kc, for catalytic
methanation:
CO g 3H 2 g CH 4 g H 2 O g

b. Write the equilibrium-constant expression, Kc, for the reverse of


the reaction in (a), that is
CH 4 g H 2 O g CO g 3H 2 g

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c. Write the equilibrium-constant expression, Kc, for the synthesis of


ammonia:

N2

3H 2
g 2NH 3 g

d. Write the equilibrium-constant expression, Kc, when the equation


for the reaction in (c) is written
1N
3 H2
NH 3 g
2 2 g
2 g

Solution:
a. The expression for the equilibrium constant is:
Kc =

[CH4] [H2O]
[CO] [H2]3

Note that the concentrations of products are on the top and


concentrations of reactants are on the bottom. Also note that each
concentration term is raised to a power equal to the coefficient of the
substance in the chemical equation.
b. When the equation is written reverse order, the expression for K c is
inverted:
[CO] [H2]3
Kc =
[CH4] [H2O]
c. The expression for the equilibrium is:
[NH3]2
Kc =
[N2] [H2]3
d. If the coefficients in the equation in (c) are multiplied by to give
1N
3 H2
NH 3 g
2
2 g
2 g
the equilibrium constant expression becomes
Kc =

[NH3]
[N2] [H2]

Which is the square root of the previous expression.

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Exercise:
Write the equilibrium-constant expression, Kc, for the equation

2NO 2

7H 2
g 2NH 3 g 4H 2 O g

Write the equilibrium-constant expression, Kc, if this reaction is written


NO

2 g

7 H2
2

NH

3 g

2H O
2

The equilibrium constant Kp:


The concentration of gas is proportional to its partial pressure at a fixed
temperature, Fig. 3.1.
We can see this by looking at the ideal gas law, PV = nRT. This can
be solved for n/V, which is the molar concentration of the gas. We get n/V
= P/RT. In other words, the molar concentration of the gas equals its
partial pressure divided by RT, which is constant at a given temperature.

pressure
gauge

Fig. 3.1
The concentration of a gas at a given temperature is proportional to the pressure.

Equilibrium constants for gaseous reactions are often written in


terms of partial pressures (in atmospheres).
This equilibrium constant, denoted Kp, is defined exactly like Kc,
except that partial pressures are used in place of concentrations. For
example, for catalytic methanation,
CO g 3H 2 g CH 4 g H 2 O g

The equilibrium expression in terms of partial pressures becomes


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PCH4 PH2O
PCO PH2 3

Kp =

3. 2. Altering the state of equilibrium:


a. Effect of pressure change.
A pressure change obtained by changing the volume can affect the
yield of product in a gaseous reaction, if the reaction involves a change of
total moles of gas, synthesis reaction of ammonia from hydrogen and
nitrogen i.e.
3H 2 N 2 2NH 3

Is an example of a change of moles of gas. When the reaction goes


in the forward direction, four moles (3H2 + N2) become two moles of
product gas (2NH3).
The effect of any pressure changes and or the temperature, changes
is better explained by Lechateliers principle, which will be considered at
a later stage.
b. Effect of temperature change:
Similarly, temperature has a profound effect on most reactions. In
the first place, reaction rates usually increase with an increase in
temperature, meaning that equilibrium is reached sooner.
Many gaseous reactions are sluggish or have imperceptible rates at
room temperature but speed up enough at higher temperatures to become
commercially feasible processes.
Secondly, equilibrium constants vary with temperature. For
example, changing values of Kc for methanation at various temperatures
is shown below:
Temperature
(K)

298

800

1000

1200

Kc

4.9 x 1027

1.38 x 105

2.54 x 102

3.92

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Altering the state of equilibrium:


A chemical system in equilibrium is finely balanced when under
fixed conditions of temperature, pressure, and concentration. A slight
change in one, or both, of these conditions will disturb the equilibrium by
promoting the forward or reverse reaction.
The move to the new equilibrium mixture will be accompanied by
a change in the concentrations of reactants and products.
Important industrial processes, which involve equilibrium states,
are ammonia and sulphur trioxide production.
Conditions are chosen to produce equilibrium states in which there
is the maximum yield of product at the lowest cost. In these gaseous
equilibrium reactions, an increase in pressure reduces the gas volume and,
effectively, increases concentration, so change of pressure has an
important effect on equilibrium.
Le Chateliers principle.
A French chemist, H.E. Le Chatelier, investigate the effect of
temperature and concentration changes on many different chemical
reactions at equilibrium. From the data obtained he concluded:
If a chemical reaction at equilibrium is subjected to a change
(temperature or concentration), processes occur that reduce the effect of
the change.
For example, in gas reaction at equilibrium, an increase of pressure
promotes that reaction which leads to system of smaller volume.
Le Chateliers principle is used to predict the direction of the effect
of a change on the equilibrium state.
For example, does a change in temperature favour the formation of
more product or more reactant?
The principle does not predict the magnitude of the effect so it
cannot be used to quantify the increase in the yield of a product.
Temperature change and Le Chateliers principle:
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According to Le Chatelier, an increase in temperature of the


equilibrium state favours the chemical reaction, which absorbs heat
energy (endothermic).
e.g.
H 9.6 kJ H

2 g

2 g

exothermic
2HI

H 9.6 kJ

g
endothermic

Here, an increase in temperature promotes the formation of


hydrogen and iodine so that their concentrations increase. From the
equation, we can see that the position of equilibrium has moved to the
left.
Concentration change and Le Chateliers principle
The addition of the chemical, which increases the concentration of
one of the reactants or products in the equilibrium system leads to a new
equilibrium state in which the concentration of the added substance is
reduced by chemical reaction.
e.g.
N2 g O2 g

2NO g H 180 kJ

The addition of more oxygen to the equilibrium state results in


more nitrogen monoxide, NO, being formed, thus reducing the effect of
the addition.
Example:
Sulphuric acid is added to yellow aqueous solution of chromate ions.

acid

alkali

add acid
chromate
(yellow)

dichromate
(orange)

add alkali
equilibrium state (A)

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equilibrium state (B)

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Fig. 3.2
Equilibrium is soon formed. A further increase in the concentration
of H ions leads to a new equilibrium state (B), which has a more intense
orange colour. There has been an increase in the concentration of
dichromate ions due to a chemical reaction, which reduced the
concentration of H+ ions.
+

When alkali OH- ions are added, the concentration of H+ is reduced


by a neutralization reaction [H+ + OHH 2O]. Consequently, the
equilibrium shifts to counteract the reduction in H+ concentration and the
yellow color intensifies in equilibrium state (A).
2CrO 2 4

aq

2H

aq

Chromate
yellow

Cr O 2 2 7

acid

H O

aq

alkali

acid
(ex H2SO4)

dichromate
orange

Pressure change and Le Chatelier s principle


When the gaseous chemicals in a reaction at equilibrium are
subjected to an increase in pressure, the equilibrium moves in a direction
such that the volume is reduced. This applies to those reactions where
there is a change in the number of gas molecules.
e.g. Synthesis of ammonia
3H 2 g N 2 g

4 gas molecules

2NH 3 g

2 gas molecules ammonia

An increase in pressure produces a new equilibrium state, which


has a reduced volume and higher concentration of ammonia.
Decrease in pressure would move the position of equilibrium to a
new state containing more nitrogen and hydrogen.
Look at the equation representing the synthesis of nitrogen
monoxide. There is no change in the number of gas molecules after
reaction.
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N 2 g O2 g

OPERATIONS TRAINING

2NO g

2 gas molecules

2 gas molecules
nitrogen monoxide

An increase of pressure reduces the gas volume but does not affect
the position of equilibrium, according to Le Chatelier, because a
movement towards products or reactants will not reduce the effect of the
increased pressure since there are equal numbers of N2, O2 and NO
molecules.
Haber process for the manufacture of ammonia:
Nitrogen reacts with hydrogen and forms ammonia. The reaction is
reversible.
N 2 g 3H 2 g

nitrogen

hydrogen

2NH 3 g

H 91 kJ

ammonia

At room temperature and pressure, the equilibrium state contains a


low concentration of ammonia.

How could concentration of ammonia be increased?


Temperature:
Applying Le Chateliers principle to the equilibrium, the effect of
lowering the temperature of the equilibrium mixture would be to promote
the formation of ammonia since this reaction release heat and by doing so
opposes the temperature reduction.
Pressure:
The equation shows that four molecules (or volumes) of reactants
form 2 molecules (or volumes) of ammonia. Applying Le Chateliers
principle, an increase in pressure will lead to a new equilibrium state of
reduced volume containing a higher concentration of ammonia.

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So, by lowering the temperature and increasing the pressure, a


higher concentration is obtained.
It is important to note that, in some industrial processes, a catalyst
is used which increases the rates of forward and reverse reactions equally.
Although the position of equilibrium is not altered, the equilibrium state
is reached more quickly and this has economic importance.
The subject of catalysts is dealt with in more detail in a separate
lesson.
The table shows the percentage of ammonia present in an
equilibrium state over a range of temperature and pressures.
100C
200C
300C
400C

100 atm 200 atm 400 atm


96.7
98.6
99.5
82.0
89.1
94.4
53.0
66.8
79.5
25.5
40.0
55.6

What conditions would you choose to obtain the best yield of


ammonia?
Using the table it would seem that the best conditions for
producing ammonia are a temperature of 100C and a pressure of 400
atmospheres.
In practice, leakage problems during operation and cost of highpressure equipment make this high yield of ammonia expensive.
A better economic performance is obtained by accepting a reduced
yield of ammonia using a lower pressure, 250 350 atmospheres.
Furthermore, a higher temperature of 550C is used to speed up the
reaction whilst maintaining the economic performance. The unchanged
nitrogen and hydrogen gases are recycled through the reactor, which
contains an iron catalyst.
3. 3. Calculate Kc & Kp for equilibrium from concentrations and
partial pressure values.

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It was stated earlier that for reactions involving gases, Kp and Kc are not
necessarily equal. For the general equation
aA bB cC dD

PCc PDd
Kp =
PAa PB b
and
Kc =

[C]c [D]d
[A]a [B]b

Concentration, you recall, has the units moles per liter, or n/V.
Assuming ideal gas behaviour, we can use the ideal gas law,
PV = n R T
To obtain the concentration of a gas, x, in a mixture as,
[x] =

nx
Px
=
V
RT

Where Px is its partial pressure. From this it follows that,


Px = [x] R T
Substituting this relationship into the expression for Kp, we have,
PCc PDd
[C]c (R T)c [D]d (R T)d
Kp =
=
PAa PB b
[A]a (R T)a [B]b (R T)b
This can be rearranged to give
Kp =

[C]c [D]d
(R T)(c + d) (a + b)
[A]a [B]b

or
Kp = Kc (R T)(n)
where n is the change in the number of moles of gas when going from
reactants to products.
n = number of moles of products number of moles of reactants

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Thus, Kp and Kc are related in a very simple fashion for reactions


between ideal gases, a relationship that also holds adequately for many
real gases.
Example:
What is Kc for the reaction of SO2 with O2 to produce SO3 at 25C?
If Kp = 3 x 1024 at the 25C.
Solution:
The chemical equation we are dealing with is

2SO 2 g O 2 g

2SO 3

Kp = Kc (R T)(n)
Solving equation for Kc , we obtain
Kc = Kp (R T)(-n)
n = (2 3) = - 1
T = (25 + 273) = 298 K
R = 0.0821 liter.atm/mol.K
Kc = (3 x 1024 atm-1) [(0.0821 liter.atom.mol-1.K-1) (298K)]- (-1)
Therefore, Kc = 7 x 1025 mol/liter
Exercise:
Phosphorus pentachloride dissociates on heating:

PCl 5 g

PCl 3 g

Cl 2

-2

If Kc equals 3.26 x 10 at 191C, what is Kp at this temperature?

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18. 4. REACTION KINETICS


Introduction:
Chemical reactions require varying lengths of time for application,
depending on the characteristics of the reactants and products and the
conditions under which the reaction is run.
Many reactions are over in a fraction of second. Whereas others
can take much longer.
When an industrial process involving the formation of acid,
polymer or fertilizer is studied, it is noticeable that the reaction
conditions-temperature, concentration and catalyst are invariably stated.

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These are the factors, which after a lengthy period of research on a pilot
plant, are known to affect the speed or rate at which products are formed.
However, the final choice of conditions, such as the operational
temperature or concentration, is always based on those, which produce an
economic yield and not on those, which provide the greatest rate of
reaction.
4. 1. Chemical kinetics:
Is the study of how reaction rates change over varying conditions
and what molecular events occur during the overall reaction.
a. Rate of reaction:
Defined as the rate of decrease of concentration of one of the
reactants or the rate of increase in concentration of one of the products.
Rate units are expressed in term of mol/(l.sec).
The study of the rate, or speed, of reaction has important
applications. In the manufacture of ammonia from nitrogen and
hydrogen, we may wish to know what conditions will help the reaction to
proceed in a commercially feasible length of time.
Further reason for studying reaction rates is to understand how
chemical reaction occurs. By notting how the rate of reaction is affected
by changing condition.
Example:
The following example will illustrate the meaning and concept of
reaction rate.
When zinc granules are adds to 1M hydrochloric acid solution,
bubbles of hydrogen gas quickly form. After starting a stopclock, the
hydrogen gas evolved is collected and its volume measured in a gas
syringe at different times. The results are plotted on a Volume Time
graph.

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Fig. 4.1
The shape of the graph indicates that the rate of formation of
hydrogen is greatest at the start of the reaction and slowly decreases with
time.
Eventually, when all the zinc has reacted, no more hydrogen is
formed and its volume remains constant. At this point, the rate of
formation of hydrogen is zero.
For gas reactions, pressures are used as a measure of concentration.
The higher the pressure of a gas, the greater is the number of (gas
particles/unit volume) and hence the greater the concentration.
Progress of the zinc-hydrochloric acid reaction would also have
been followed by plotting the concentration of HCl against time.
Note that this graph looks different to the hydrogen graph. Here,
the acid is being consumed and its concentration decreases with time.

Fig. 4.2

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The slope, or gradient of the graph, at time t, represents the rate of


decrease of hydrochloric acid concentration at that time.
Rate of reaction
gradient
at time t
= at time t =

change in HCl
concentration
mol/l
=
time change
sec

It is obvious that the gradient values decrease with time because


the reaction rate. R, decreases as the acid is consumed.
R1

>

R2 >

R3

In general, the rate of reaction decreases with time.


Example:
Zn (s) + 2HCl (aq)

ZnCl2 (aq) + H2 (g)

2 mol

1 mol

Rate of decrease of concentration of hydrochloric acid 2


= Rate of increase of concentration of hydrogen 1
Because 2 moles of HCl are needed to form 1 mole H2.
b. Reaction order:
We can classify a reaction by its order. The Reaction Order with
respect to a given reactant species is equal to:
The exponent of the concentration of that species in the rate law
as determined experimentally.
For the reaction of NO2 with F2 to give NO2F:
The reaction is first order with respect to the NO2 because the
exponent of [NO2] in the rate law is 1. Similarly the reaction is first order
with respect to F2.
The Overall Order of a reaction equals the sum of the exponents
in the rate law. In this example the overall order is 2, that is, the reaction
is second order overall.
Example:
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Nitric oxide, NO, reacts with hydrogen according to the equation:


2NO (g) + 2H2 (g)

N2 (g) + 2H2O (g)

The experimentally determined rate law is


Rate = k [NO]2 [H2]
Thus, the reaction is second order in NO, first order in H2, and third
order overall.
Exercise:
What are the reaction order with respect to each species for the
following reaction:
NO2 (g) + CO (g)

NO (g) + CO2 (g)

The rate law is:


Rate = k [NO2]0
Also, what is the overall order?

Dependence of rate on concentration Rate law:


Experimentally, it has been found that a reaction rate depends on
the concentration of certain reactants (and the concentration of catalyst, if
there is one).
Consider the reaction of nitrogen dioxide, (NO2), with fluorine, (F2)
to give nitryl flouride, NO2F:
2NO2 (g) + F2 (g)

2NO2F (g)

The rate of this reaction is observed to be proportional to the


concentration of nitrogen dioxide. If the concentration of NO 2 is doubled,

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the rate doubles. The rate is also proportional to concentration of flourine,


F2. So that doubling the concentration of flourine double the rate.
Rate law:
Relates the reaction rate to the concentration of reactants (and
catalyst) raised to various powers, for the above reaction:
Rate [NO2] [F2]
Rate = k [NO2] [F2]
Here, K, called proportionality constant, it has a fixed value at a
given temperature, but will vary with temperature.
Note that in this rate law both reactant concentrations have exponent of 1.
Generally, consider the following reaction:
aA + bB

dD + eE

c = catalyst

Rate law = k [A]q [B]r [C]s


The exponents q, r, and s are frequently, but not always integers.
They must be determined experimentally and they cannot be obtained by
looking at the balanced equation.
For example, note that the exponent in the equation Rate = K [NO2]
[F2] have no relation to the coefficients in the balanced equation;
2NO2 (g) + F2 (g)

2NO2F (g)

Once we know the rate law for a reaction and have found the value
of the rate constant, we can calculate the rate of reaction for any value of
reactant concentrations.
Knowledge of the rate law is also useful in understanding how the
reaction occurs at the molecular level.
c. Molecularity:

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Elementary reactions are classified according to their molecularity.


The molecularity of an elementary reaction is the number of molecules on
the reactant side.
A Unimolecular reaction is one that involves one reactant molecule.
A Bimolecular reaction is one that involves two reactant molecules.
Bimolecular reactions are the most common.
A Termoleculer reaction is one that involves three reactant molecules.
Example:
NO2 + CO

NO + CO2

(previous example).

Each of the steps in the mechanism of the reaction of NO 2 with CO


is Bimolecular.
Consider the first step:
NO2 + NO2

NO3 + NO

When these two NO2 molecules come together, they form an


activated complex of the six atoms, (NO2)2, which immediately breaks
into two molecules, NO3 and NO.
Theoretical reaction mechanism:
A balanced chemical equation is a description of the overall results
of a chemical reaction. However, what actually happens at the molecular
level may be more involved than represented by this single equation.
The reaction may take place in several steps. In this section we will
examine some reactions and see how the rate law can give us information
about these steps, or elementary reactions.
Elementary reactions:
Consider the reaction of nitrogen dioxide with carbon monoxide:
NO2 (g) + CO (g)

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NO (g) + CO2 (g)

(net chemical equation)

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At temperature below 500K, this gas-phase reaction is believed to


take place in two steps:
NO2 + NO2

NO3 + NO

(elementary reaction)

NO3 + CO

NO2 + CO2 (elementary reaction)

Each steps, called an elementary reaction, represents the result of a


collision occurring at the molecular level. The set of elementary reactions
whose overall effect is given by the net chemical equation is called the
reaction mechanism.
According to the reaction mechanism just given, two NO2
molecules collide and react to give the product molecule NO and the
reaction intermediate NO3.
Reaction intermediate:
Is a species produced during a reaction that does not appear in the
net equation because it reacts in a subsequent step in the mechanism.
Often it has a fleeting existence and cannot be isolated from the reaction
mixture.
The NO3 molecule is known only from its visible light spectrum. It
reacts immediately with CO to give the product molecules NO2 and CO2.
The net chemical equation, which represents the overall result of
these two elementary reactions in the mechanism, is obtained by adding
these steps together and canceling species that occur on both sides:
NO2 + NO2

NO3 + NO

(elementary reaction)

+
NO3 + CO

NO2 + CO2 (elementary reaction)

NO2 + CO

NO + CO2

(net chemical reaction)

4. 2. Example for first order reaction:


Aceton, CH3COCH3, reacts with iodine in acidic solution:

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CH3COCH3 (aq) + I2 (aq)

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H+

CH3COCH2I (aq) + HI (aq)

The experimentally determined rate law is:


Rate law = k [CH3COCH3] [H+]
The reaction is first order in acetone. It is zero order in iodine, that
is the rate law contains the factor [I2]0 = 1. Therefore the rate does not
depend on the concentration of iodine. I2 is present.
Note that the reaction is first order in the catalyst. H +. Thus the
overall order is 2.
Although, reaction order frequently have whole numbers value
Particularly 1 or 2), they can be fractional. Negative orders are also
possible.
4.3. Fast rates of reaction:
The burning of methane, natural gas in a gas cooker.
CH4 (g) +

2O2 (g)

methane

oxygen

ignite

CO2 (g) +

2H2O (g)

carbon dioxide + water

4. 4. Slow rates of reaction:


The weathering of rocks. Buildings and walls made from limestone
slowly crumble due to attack by acid rain, which contains the dissolved
gases carbon dioxide, and sulphur dioxide.
CaCO3 (g) + CO2 (g) + H2O (l)

Ca (HCO3)2

Fortunately, the change takes place slowly so the effect is noticed


only when looking at old buildings.
In contrast, however, many chemical reactions proceed at a
moderate rate and can be followed by measuring the extent of the reaction
at various times.
The difference between the above two reactions is the speed or rate
of which reactants change to product.
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The study of the rate, or speed of a reaction has important


applications. In the manufacture of ammonia from nitrogen and
hydrogen, we may wish to know what conditions will help the reaction to
proceed in a commercially feasible length of time.
4. 5. The rate determining step in reaction mechanism:
The overall balanced equation for a reaction represents the net
chemical change that occurs as the reaction proceeds to completion. This
does not mean, however, that all the reactants must come together
simultaneously to undergo a change that produces the products. In fact,
the net change can (and usually does) actually represent the sum of a
series of simple reactions.
These simple reactions are referred to as elementary processes.
The sequence of elementary processes that ultimately leads to the
formation of the products is called the reaction mechanism. For
example, it appears that the reaction
2NO +

2H2

2H2O

N2

proceeds by the three-step mechanism.


2NO

N2O2

H2

N2O + H2O

N2O +

H2

N2 + H2O

N2O2

The sum of these steps in the sequence does give us the overall
balanced equation.
Reaction mechanism, such as the one just described, are usually
arrived at by bringing together both theory and experiment. For instance,
suppose we wish to study the following hypothetical reaction in hopes of
discovering the mechanism.
2A + B

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C + D

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We begin by first determining the rate law, perhaps by studying


how rate changes as we vary the concentrations of A and B as
described earlier. Let us say it turned out to be.
rate = k [A]2 [B]
Next, we attempt to propose a mechanism that, by the application
of the principles of collision theory, gives us a predicted rate law that is
the same as the one found by experiment.
Since we are beginners at proposing mechanisms, we might be
tempted to propose a one-step mechanism in which two molecules of A
and one of B come together simultaneously that is, a three-body or
termolecular collision. This is process,
2A + B

C + D

indeed leads to the rate law


rate = k [A]2 [B]
when we take the coefficients to be equal to the exponents, and it is the
same as the rate law found from experiment.
But we must now ask ourselves, is this a realistic mechanism? A
simultaneous three-body (termolecular) collision is statically a very
unlikely event, and it has been generally found that reactions that must
proceed by such a path are very slow.
As a result, a third-order reaction such as this, if it is fairly rapid, is
usually interpreted as taking place by way of a series of simple
bimolecular processes. One possible sequence of reactions is
2A
A2 + B

A2
C + D

Here we have two steps in which we propose that some relatively


unstable intermediate, A2, is first formed by the collision of two
molecules of A. In a second step a reaction between A2 and B produces
the product C and D. Again the sum of these elementary processes gives
us our net overall change.

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Both of these reactions are unlikely to occur at the same rate, so


lets suppose that the first reaction is slow, and that once the intermediate,
A2, is formed it reacts rapidly with B in the second step to produce the
products. If this were true, the rate at which the final products appear is
actually determined by how fast A2 is produced.
This first step serves as a bottleneck in the reaction bath. We refer
to this slowest step as the rate-determining step in the reaction because
it governs how rapidly the overall reaction takes place.
Because the rate determining step is an elementary process (in this
instance bimolecular collision between two A molecules), we can predict
with the aid of collision theory that the rate law should be
rate = k [A]2
If this is the rate law for the rate-determining step, it will also be
the rate law for the overall reaction. However, this rate law cannot be the
correct one because it is not the same as the one determined from
experiment. This does not necessarily mean that our mechanism is wrong,
but it does mean that the first step cannot be the rate-determining step.
Let us see what we would expect to observe if the second step were slow,
instead of the first. In this case the rate law would be
rate = k [A2] [B]
However, this rate law contains the concentration of proposed
intermediate (A2) and the experimental rate law contains only the
concentration of reactants A and B. How can we express the
concentration of A2 in terms of A and B?
Once A2 has been formed, it can react in either of two ways. Since
we propose that A2 is unstable (if it were stable we could isolate it and
there would be no question at all about the path of the overall reaction) it
can undergo decomposition to reform two molecules of A. The other
possibility is that it undergoes a collision with B that leads to the
formation of the products, C and D.
Our mechanism therefore should include a reaction that allows A2
to decompose
A2

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2A

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Our total mechanism is now


2A

A2

A2

2A

A2 + B

C + D

If the rate at which the intermediate is formed from reactant A is


equal to the rate at which A is formed from intermediate A 2, then these
two reactions represent a state of a dynamic equilibrium. We could
therefore write our first two equations as an equilibrium, which would
take the form 2A
A2
We are now back to a two-step mechanism in which the first step is an
equilibrium. Our mechanism is now.
2A
A2 + B

A2

fast

C + D

slow

Since, in an equilibrium situation, the rate of the forward reaction


(rate f) is equal to the rate of the reverse reaction (rate r),
rate f = k f [A]2

= rate r = k r [A2]

or simply
k f [A]2 = k r [A2]
Solving this equation for [A2], we have
k f [A]2
kr
We can now substitute this into equation and combine all the
constants to give still another constant, let us say k. This gives the rate
expression
[A2] =

rate = k [A]2 [B]


which does agree with the rate law found from experiment. Our proposed
mechanism, therefore, appears to be a good one.

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However, a mechanism is , in essence, a theory. It is a sequence of


steps that we dream up to explain the chemistry and to provide a rate law
that agrees with experiment. It frequently happens, though, that more than
one mechanism can be written to satisfy both criteria, so we can never be
certain we have truly discovered the actual path of the reaction.
Nevertheless, studying the kinetics of a reaction gives clues to what
the mechanism may be and allows us to discard many alternatives. After
that, we can only hope to gather further information that either supports
(or proves wrong) our guess.
Example:
The decomposition of NO2Cl is believed to involve the two-step
mechanism,
NO2Cl
NO2Cl + Cl

NO2 + Cl
NO2 + Cl2

What would be the observed experimental rate law if the first step
were slow and the second were fast?
Solution:
If the first reaction is the slow step, it is also the rate-determining
step. The rate law for the overall reaction should be the same as the rate
law for the rate-determining step.
Since only one molecule of NO2Cl is involved, the rate law for the
first reaction as well as for the overall reaction would be
rate = k [NO2Cl]
4. 6. The experimental determination of reaction rate:
Rate of reaction is usually measured by following the change in
concentration per second, of a reactant or product. i.e. we must determine
the concentration of reactants during the course of reaction.
Measurement can be achieved in different ways:

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1. One way to do this for a slow reactions is to take samples from the
reaction vessel at various times and analyze them.
Example:
The rate of reaction of ethylacetate with water in acidic solution.
O
|
|
|| |
C C - O C C + H2O
|
|
| |

H+

O
|
|
||
C C OH + HO C CH3
| |

or
O
||
CH3CH2OCCH3
Ethylacetate

+ H2 O
water

H+

O
||
CH3CH2OH + HOCCH3
Ethanol

Acetic acid

Acetic acid concentration that is produced easily measured by titration.


2. Other way, which is used for fast reactions, is by observing the
change in some physical properties of the system.
a. Pressure change: As example if a gas reaction involves a
change in the number of molecules, the pressure of the
system will change when the volume and temperature held
constant. This pressure can be related to the reaction rate.
b. Color change: An example that if one of the reactants or
products has a color, this may be used to follow the rate.

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Fig. 4.3
An experiment to follow the change of pressure during the decomposition of N2O at
45C. Pressure values can be related to the concentration of N2O5 in the flask.

Example:
The decomposition of dinitrogen pentoxide in the gas phase:
2N2O5 (s)

4NO2 (g) + O2 (g)

N2O5 crystals are sealed in a vessel equipped with a manometer to


measure the pressure. The vessel is then plunged into a water bath at
45C at which temperature the solid vaporizes and the gas decomposes to
NO2 and O2.
Manometers reading are taken at regular interval, and the pressure
values are converted to concentration of N2O5 (in term of partial
pressure).
The experiment being done and the data are given in Table (4.1);
from this table we can calculate the average rate of reaction during each
time interval.

Table. 4.1

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Time
sec

N2O5
Mol/l

0
600

1.65 x 10-2
1.24 x 10-2

Rate
Mol/l.se
c

6.8 x 10-6
5.2 x 10-6
3.7 x 10-6
3.0 x 10-6
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1.7 x 10-6

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0.93 x 10-2
0.71 x 10-2
0.53 x 10-2
0.39 x 10-2
0.29 x 10-2

1200
1800
2400
3000
3600

At time = 600 sec, N2O5 conc. = 1.24 x 10-2 mol/l


At time = 1200 sec, N2O5 conc. = 0.93 x 10-2 mol/l
In the time interval from 600 sec to 1200 sec, the concentration of
N2O5 has changed
[N2O5] = (0.93 1.24) x 10-2 mol/l
= 0.31 x 10-2 mol/l
Note that the ve sign indicates a decrease in concentration.
The rate of reaction during that time involved is obtained by
dividing [N2O5] by the time interval, t = 1200 600 sec = 600 sec.
Rate =

[N2O5]
t

0.31 x 10-2
=
600

= 5.2 x 10-6 mol/l.sec

The rate of reaction during each time interval has been calculated
in this way and given in the above Table (4.1).
Note that the rate slows as the reaction proceeds.

4. 7. Factors affecting the rate of a chemical reaction:


We know from the preliminary stages of a study of chemistry that
the rate of reaction can be changed by changing the conditions of
reaction.

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For example, dry crystals of sodium sulphate and barium chloride


show No reaction when mixed together in a test-tube.
However, when two substances are dissolved separately in water
and the solutions are then mixed, an instantaneous reaction occurs in
which a white precipitate of barium sulphate is formed.
The rate has changed from indeterminably slow to lightning fast.
Na2SO4 (aq) + BaCl2 (aq)

BaSO4 (s) + 2NaCl (aq)

The explanation is that the water by dissolving the solids, separated


the ions in the crystals and allowed them to move through the solution,
approach near together, and then combine.
Dissolving chemicals in water before mixing them is a very
common method of increasing the rate of reaction although most
chemical change take place without the presence of water.
Many chemical changes occur at intermediate reaction rates and
are suitable for rate investigation. By changing the reaction conditions
and noting the new rates of reaction it is possible to show what factors
affect the rate of reaction.
Some chemical reactions are fast, and other are slow. But the rate of
any given reaction is affected by the following factors:
1. Reagent state:
a. Solid: size of particles.
b. Solution: Is the solution dilute or concentrated?
c. Gaseous: Is the gas under low or high pressure.
2. Temperature.
3. Presence of catalyst:
a. Concentration of catalyst.
b. Surface area of a solid reactant or catalyst.
4. Concentration of reactants.

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The experimental approach involves varying one factor in a


reaction and measuring the accompanying rate. All other variables factors
are kept constant.
4. 8. The collision theory of chemical reaction-for-gases:
Collision theory of reaction rates assumes that in order for
reaction to occur reactant molecules must collide.
However. Collision of two reactant molecules is not enough for
their reaction. For the molecules to react they must collide with an energy
greater than a minimum value, called the activation energy, Ea, the value
of Ea will depend on the particular reaction.
Moreover, the two molecules must collide with proper orientation.
The theory estimates that in 1m3 of gas (mol.mass 125, temperature
500C, 10 moles gas molecules) there are 3 x 10 33 collision/sec between
moving gas molecules. Some of the collisions are energetic head-on
while others are merely glancing blows of low energy.
However, this calculated collision rate is a theoretical estimate and
it predicts a rate of chemical reaction, which is much greater than an
experimental measure rate.
So the collision theory needs an adjustment. This is that the energy
of collision must exceed a level known as the activation energy of the
reaction.
When it does so in a head-on collision, reaction follows.

In the above gas container, the adjusted number of energetic


collisions is 3 x 1020 per second.
By comparison of:

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energetic collisions
total number of

= 3 x 1020 = 1
3 x 1033
1013

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collisions
We can see that only one in (1013) collisions results in chemical
change.
The collision theory is useful in that it offers an explanation for
why there is a change in rate of reaction when there is a change in
reaction conditions.
Collision theory explanation of effect on reaction rate:
We can now use that collision theory to explain how the reaction rate
is affected by:
a. Particle size of solids:

Fig. 4.4
The smaller the particle size, the greater the surface area and,
consequently, the greater the number of solid surface atoms
likely to collide within molecules in the surrounding liquid or gas.
Increased collision frequency leads to an increased rate of reaction.
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Fig. 4.5
b. Concentration of solution:
By increasing a concentration of a solution a greater number of
more solute particles are present in unit volume. The reduction in
distance leads to an increased collision frequency and a consequent
increased in reaction rate.
c. Pressure in gases:
An increase of pressure pushes gas particles closer together and
increases the collision frequency. Thus, reaction rate increases with
increase of pressure.

18. 5. CATALYSIS
5. 1. Catalyst-definition:

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Catalysts are substances, which affect the rate of chemical reaction


without themselves being changed in mass or chemical composition
during the reaction. They may increase the rate of reaction (positive
catalysts) but can also decrease the rate (negative catalysts).
The catalyst itself takes part in the reaction and consequently may
undergo physical change (e.g. conversion into powder) and, in certain
circumstances, very small quantities of catalyst can speed up very large
reactions.
Some catalysts are also highly specific in the type of reaction they
catalyze, although a few, particularly platinum, palladium and other
transition metals, catalyze a range of reactions. Catalysts may be inhibited
(poisoned) or improved (promoted) by other substances.
Accordingly, the characteristics of a catalyst can be summarized as
follows:
1. The catalyst affects the rate of reaction.
2. The catalyst is not changed chemically, although it may undergo a
physical change during the reaction (e.g. from pellet to powder
form).
3. There is no change in mass.
4. Only a small amount is required.
5. A substance may only catalyze one reaction, e.g. a nickel catalyst is
always used in the hydrogenation of an alkene; catalysts used in
other reactions are not successful in this reaction.
6. On contact with a catalyst poison, a substance may lose much of
its catalytic activity, e.g. arsenic acts as a poison to a platinum
catalyst.

Type of catalysis:
There are two types of catalysis homogenous and heterogeneous.

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1. Homogeneous catalysis:
This term is applied to reaction in which the catalyst is in the same
phase as the reactants. It usually takes place in the liquid phase, as a
gaseous catalysis is very rare.
Example:
In the commercial preparation of sulfuric acid, its anhydride sulfur
trioxide is obtained by oxidizing sulfur dioxide, SO2.
Sulfuric acid is then obtained from SO 3 is normally very slow. In
an early industrial process, this reaction was carried out in the presence of
nitric oxide. NO, because it is then much faster
2SO2 (g) + O2 (g)

NO

2SO3 (g)

Nitric acid, NO, does not appear in the overall equation, nor does it
in any way affect the final composition of the reaction mixture. Thus, it
act as a catalyst.
A possible mechanism for the nitrite oxide catalyst is
2NO + O2

2NO2

NO2 + SO2

SO3 + NO

The last step occurs twice each time the first step occurs once.
Thus, two molecules of nitric oxide are used up in the first step and are
regenerated in the second step.
This catalytic reaction in a homogeneous phase is called
homogeneous catalysis.

2. Heterogeneous catalysis:

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This refers to reactions in which the catalyst is in a different phase


from the reactants. In many catalyzed two phase reactions, the catalyst
is a solid and the reactants are gaseous.
The solid catalyst is present in the reactor as pellets, lumps, spheres
or even metal gauze (platinum/rhodium gauze in ammonia oxidation).
i.e. Heterogeneous catalyst is the reaction of the substances in gas
or liquid phase at the surface of a solid catalyst. Such surface or
heterogeneous catalysis is thought to occur by chemical adsorption of the
reactants onto the surface of the catalyst.
Example:
An example of heterogeneous catalysis involving chemisorption is
provided with catalytic hydrogenation.
This is the addition of H2 to a compound, such as one with a
carbon-carbon double bond. Using a catalyst of platinum or nickel metal.
Vegetable oils, which contain carbon-carbon double bonds, are changed
to solid fats when the bonds are catalytically hydrogenated.
In the case of ethylene, C2H4, the equation is:
H

H
\
/
C=C
/
\

+
H

H2

Pt

H H
|
|
HCCH
|
|
H H
ethane

A mechanism for this reaction is represented by the four steps


shown in Fig. 5.1.

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Fig. 5.1
The mechanism of the catalytic hydrogenation of C2H4. (a) C2H4 and H2 molecules
diffuse to the catalyst. (b) The molecules form bonds (dotted lines on the catalyst
surface. The H2 molecule dissociates to atoms. (c) These H atoms migrate to the C 2H4
molecule, where they react to form C2H6. (d) C2H6 diffuses away from the catalyst.

In (a), ethylene and hydrogen molecules diffuse to the catalyst


surface, where as shown in (b), they undergo chemisorption. The
electrons of ethylene form bonds to the metal, and hydrogen molecules
break into H atoms that bond to the metal.
In (c) two H atoms migrate to an ethylene molecule bonded to the
catalyst, where they react to form ethane. Then (D), because ethane does
not bond into the metal, it diffuses a way.
Note that the catalyst surface that was used in (B) is regenerated in (d).
Autocatalysis:
Autocatalysis is the process whereby one of the products in the
reaction catalyses the reaction.
For example, when potassium permanganate is added to a mixture
of sulphuric and oxalic acid, a reaction represented by the following
equation takes place:
2MnO-4 (aq) + 16H+ (aq) + 5C2O2-4 (aq)

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2Mn2+ + 8H2O + 10CO2

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Since the concentration of permanganate, hydrogen and oxalate


ions decreasing with time, a decrease in reaction rate is expected.
However, the initial rate of reaction increases after two minutes.
Why should this be so?
An explanation is that the reaction is catalyzed by the manganese
(II) ions, Mn2+, produced in the reaction, in ever-increasing concentration.
Manganese, therefore, is both a product and a catalyst.
In general, an autocatalyzed reaction experiences an increase in
reaction rate due to a newly formed product behaving as a catalyst.
5. 2. Selectivity of catalyst:
The position of equilibrium in a reversible reaction is not changed
by the presence of the catalyst.
An important characteristic of a catalyst is its effect on selectivity.
An illustration is the decomposition of ethanol. Thermal decomposition
gives water, acetaldehyde, ethylene, and hydrogen.
If, however, ethanol vapor is suitable contacted with alumina
particles, ethylene and water are the only products. In contrast, when
ethanol is reacted over a copper catalyst it will undergo dehydrogenation
and produce only acetaldehyde.
C2H5OH
C2H5OH
C2H5OH

Thermal
decomposition
Al2O3
Cu

CH3CHO + H2O + C2H4 + H2


H2O + C2H4
CH3CHO + H2

5. 3. Catalyst and rate of reaction:


A relatively small amount of catalyst can cause conversion of large
amount of reactant. For example, it was found that cupric ions in the
concentration of 10-9 mole/liter appreciably increase the rate of the
oxidation of sodium sulphide by oxygen.

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However, the idea that a small amount of the catalyst can cause a
large amount of reaction does not mean that the catalyst concentration is
unimportant.
In fact, when the reaction does not entail a chain mechanism, the
rate of the reaction is usually proportional to the concentration of the
catalyst, while such a simple relationship may not often exist in solidcatalyzed reactions (heterogeneous reactions), in homogenous catalysis
there is frequently a direct concentration.
For example, the hydrolysis of esters in an acid solution will
depend on the concentration of hydrogen ion acting as a catalyst.
5. 4. Activity of different d-block element catalyst:
1. Metals or metal conductors such as (Fe, Pt, Ag, Ni, etc . . ):
Metals Chemisorb oxygen and hydrogen and therefore are usually
effective catalysts for oxidation- reduction and hydrogenationdehydrogenation reactions, thus platinum is a successful catalyst for the
oxidation of SO2, and Ni is used effectively for hydrogenation of
hydrocarbons.
The Pt catalyst is more active at about 400C, but because of its
susceptibility to poisons and sensitivity to high temperature, the Pt
catalyst has largely been replaced by V2O5.
The Haber process, the industrial process for producing ammonia,
uses an iron catalyst, high temperatures (550 - 600C) and high pressures
(100 - 200 atm).
N2 (g) + 3H2 (g)

2NH3 (g)

2. Metal oxides (semi-conductors, such as NiO, ZnO)


Metals oxides as semi-conductors, catalyze the same kinds of
reactions, but often higher temperatures are required. Because of the
relative strength of the chemisorption bond with which such gases as O 2
& CO2 are attached to metals, these gases are poisons when metals are
employed as hydrogenation catalysts.
The semiconductor oxides are less susceptible to such poisoning.

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3. Oxides of the transition metals:


Such as MoO3 and Cr2O3, are good catalysts for polymerization of
olefins also aluminum alkyl-titanium chloride [for example, Al(C 2H5)3 +
TiCl4] constitutes an excellent catalyst for producing isotactic polymers
from olefins.
5. 5. Catalyst deactivation:
Synthetic catalytic agents suffer a decline in its activity with time
on-stream. For example the life-span of a cracking catalyst is in the order
of seconds, because of coking, so the continuous (or frequent)
regeneration is necessary. The promoted-iron catalyst in NH3 synthesis
enjoys a lifetime of years.
Regeneration processes can restore catalyst activity. For example,
the coked cracking catalysts can restore their activity when an oxygenbearing stream is utilized to burn the coke deposits, from that catalyst.
However other instances of deactivation do not remedied by regeneration,
as in catalyst sintering and/or irreversible phase transformations.
A catalyst can be deactivated in three ways poisoning, fouling and
sinters or phase transformations.
5. 6. Adsorption:
In the system of solid surface and gas, the molecules of gas will be
continually striking the surface and a fraction of these will adhere.
However, because of their kinetic, rotational, and vibrational energy, the
more energetic molecules will be continually leaving the surface.
An equilibrium will be established such that the rate at which
molecules strike the surface and remain for some time, will be exactly
balanced by the rate at which molecules leave the surface. At a fixed
temperature, the number of collisions will be proportional to the pressure
of the gas.
Two types of adsorption may occur:
1. Physical adsorption (or phesisorption):

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The forces attracting the fluid molecules to the solid surface are
relatively weak. The binding forces are equivalent to van der waals
forces. The energy of activation for physical adsorption is small (usually)
no more than 1 kCal/g.mole).
The amount of physical adsorption decreases rapidly as the
temperature increases. This is an evidence that physical adsorption is not
responsible for catalysis, physical adsorption studies are valuable in
determining the physical properties of solid catalysts. Thus the question
of surface area and pore-size distribution in porous catalysts can be
answered from physical-adsorption measurements.
2. Chemical adsorption (chemisorption):
This type of adsorption involves forces much stronger than in
physical adsorption. The binding forces are similar to chemical
compound formation, i.e., the adsorbed molecules are held to the surface
by valence forces of the same type as those occurring between atoms in
molecules.
Because of high heat of chemical adsorption, the energy passed by
chemisorbed molecules can be substantially different from that of the
molecules alone.
Hence the energy of activation for reactions involving chemisorbed
molecules can be considerably less than that for reactions involving gasphase molecules. It is on this bases that chemisorptions offers an
explanation for the catalytic effect of solid surfaces.
Two kinds of chemisorption are encountered:
1. Activated:
It means that the rate varies with temperature.
2. Non-activated:
This type is less frequent. In this case chemisorption occurs very
rapidly, i.e., activation energy near zero.
It is often found that for a given gas and solid the initial
chemisorptions is non-activated, while later stages of the process are slow
and temperature dependent (activated chemisorption).

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The effectiveness of solid catalysts for reactions of stable


molecules is dependent upon chemisorption. There is a relationship
between the extent of chemisorption of a gas on a solid and the
effectiveness of the solid as a catalyst.
For example, many metallic and metal-oxide surfaces adsorb
oxygen easily, and these materials are also found to be good catalysts for
oxidation reactions.
An important feature of chemisorption is that its magnitude will not
exceed that corresponding to a monomolecular layer. This limitation is
due to the fact that the valence forces holding the molecules on the
surface diminish rapidly with distances.
5. 7. Kinetics and mechanism of NH3 synthesis:
While in principle a kinetic model is derivable a priori from a
detailed verified mechanistic understanding, in fact kinetic models
invariably are rooted in empirical observation and correlation.
In NH3 synthesis from its elements N2 + H2
2NH3 the
Temkin-Pyzhey equation adequately describes the net rate of synthesis
over promoted-iron catalyst
rnet

k1 (N2)

H23
NH32

k-1

NH32
H23

Where a and b empirically determined exponents, each varying


with reaction conditions of temperature, pressure and conversion. Surely
it is evident that above equation does not describe the initial rate at zero
partial pressure of NH3.
A rationalization of the equation was naturally sought. As has been
noted above, the first step in the rationalization process is that of
postulating at mechanism or sequence of steps:
Step 1:

N2 + 2S

2NS

N2 chemisorption

Step 2:

3H2 + 6S

6HS

H2 chemisorptions

Step 3: 2NS + 6HS

2NH3 + 8S

surface reaction

Which, as Boudart notes, can be written

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N2 + 2S
2NS + 3H2

OPERATIONS TRAINING

2NS
2NH3 + 2S

The above sequence does not represent elementary steps, except


that of N2 chemisorption. Step2, for example, is surely the sum of three
elementary steps, while step 3 can be dissected. It does indicate the three
possibilities of rate control.
Both NH3 synthesis and N2 chemisorption rates were measured by
Emmett and Brunaure, who found the N2 chemisorptions rate to be slow
and of the same order of magnitude as that of synthesis. More precise
comparison was not possible then as the extent of N 2 coverage during
synthesis was not known. However, the data suggested that step 1 is rate
controlling.
5. 8. General definition of catalysis:
For the overall reaction:
A+ B

(1)

Catalyzed by the catalytic, or actives sites x 1 and x2 fractionally


poisoned by P and deactivated thermally, we can write a mechanism, i.e.,
a sequence of elementary steps,
Chemisorption:

A + x1

Ax1

Chemisorption:

B + x2

Bx2

(3)

Ax1 + Bx2

Cx1

(4)

C + x1

(5)

(6)

Surface reaction:
Desorption of product:
Poisoning:
Thermal deactivation:

Cx1
P + x1,2
x1,2

x1,2

(2)

(7)

Where the fraction of sites poisoned and the fraction thermally


deactivated. The above equations illustrate the key characteristics of
catalysis as follows:

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1. In the absence of poisonening and/or thermal deactivation the


catalytic concentrations of sites x1 and x2 do not suffer consumption
but are regenerated in each reaction cycle (equations 2, 3, 4 & 5),
consequently the catalyst does not appear explicitly in the overall
reaction statement.
2. At least one reactant must be chemisorbed in any heterogeneous
catalytic event. It may also one reactant be chemisorbed while the
other reactant will react from the gas phase as follows:
A + x1
B + Ax1

Ax1
C + x1

3. While x1 & x2 are regenerated in the catalytic cycle, ultimately their


activity is reduced via deactivation over periods of from several
minutes to years, depending upon the particular process. The life of
x1 & x2 is great relative to reaction-cycle time.
4. There is a possibility of using some means to prevent the
deactivation processes caused by poisoning and/or thermal
deactivation. This can be achieved by physicochemical promotion.
5. 9. Determination of surface area:
The standard method for measuring catalyst areas is based on the
physical adsorption of a gas on a solid surface. Usually the amount of
nitrogen adsorbed at equilibrium at the normal boiling point (- 195.8C)
is measured over a range of nitrogen pressure below 1 atm.
Under these conditions several layers of molecules may be
adsorbed on top of each other on the surface. The amount adsorbed when
one molecular layer is attained must be identified in order to determine
the area.
The historical steps in the development of the Brunauer-EmmettTeller method are clearly explained by Emmett. They may be some
uncertainty as to whether the values given by this method correspond
exactly to the surface area.
However, this is relatively unimportant, since the procedure is
standardized and the results are reproducible. It should be noted that the
surface area so measured may not be the area effective for catalysis. Only
certain parts of the surface, the active centers, may be active for
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chemisorption of a reactant, while nitrogen may be physically adsorbed


on much more of the surface.
When the catalyst is dispersed on a large-area support, only part of
the support area may be covered by catalytically active atoms and this
area may be several atoms in depth. Thus, the active atoms may be
together in clusters so that the catalytic surface is less than if the atoms
were more completely dispersed or separated.
For example a nickel-on-kieselguhr catalyst was found to have a
surface of 205 m2/g as measured by nitrogen adsorption. To determine the
area covered by nickel, atoms, hydrogen was chemisorbed on the catalyst
at 25C. From the amount of hydrogen chemisorbed, the surface area of
nickel was calculated to be about 40 m2/g.
It would be useful to know surface areas for chemisorptions of the
reactant at reaction conditions. However, this would require measurement
of relatively small amounts of chemisorptions at different, and often
troublesome, conditions (high temperature and/or pressure). For each
reaction system. In contrast, nitrogen can be adsorbed easily and rapidly
in a routine fashion with standard equipment.
In the classical method of determining surface area an all-glass
apparatus is used to measure the volume of gas adsorbed on a sample of
the solid material.
Examples of catalysis process:
a. Inorganic catalyzed processes:
Solid catalyst

Chemical change

Iron

nitrogen/hydrogen mixture

Vanadium (V) oxide

sulphur (IV) oxide/oxygen

ammonia NH3
sulphur (VI)

oxide
(sulphur dioxide)
Platinum + 10% rhodium

ammonia/air

(sulphur trioxide-for
sulphuric acid
production)
nitrogen oxide, NO
(nitrogen monoxide-for
nitric acid production)

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b. Organic catalyzed processes:

e.g.

Solid catalyst

Chemical change

Nickel at 140C

hydrogenation of alkenes

C2H4 (g) + H2 (g)


ethene
Silica/aluminum oxide
At500C

e.g.

e.g.

C2H6 (g)
ethane
catalytic cracking of alkanes

kerosene vapor

alkenes, cycloalkanes

Nickel catalyst at
900C

production of synthesis gas

naphtha
from crude oil
distillation

alkanes

a mixture of CO and H2

Zinc copper (II) oxides


at 300C
e.g. synthesis gas

production of methanol, CH3OH

Note: a comparison between homogeneous and heterogeneous


catalysts suggests that each particle of homogeneous catalyst in solution
is likely to act catalytically whereas only a small percentage of a solid
heterogeneous catalyst comes into contact with reagent molecules.
However, heterogeneous catalysts are easier to recover and recycle and
this advantage makes them more economically attractive.

18. 6. IONIC REACTIONS AND EQUILIBRUM

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6.1. Explain the function of buffer solution and give the composition
of
typical buffer solution.
What we wish to examine in this section is how and why reactions
between electrolytes take place in solution.
Lets begin by considering the reaction that takes place when a
solution containing 1 mole of sodium chloride is added to a solution of 1
mole of silver nitrate. When these two solutions are combined, 1 mole of
the white solid, silver chloride is formed and the solution that remains
contains 1 mole of sodium nitrate, the chemical equation that represents
the change that has occurred during this reaction is.
NaCl (aq) + AgNO3 (aq)

AgCl (s) + NaNO3 (aq)

This kind of reaction, in which cations and anions have change


partners, is known as metathesis, or double replacement (Cl - has replaced
NO3- or Na+ has replaced Ag+).
The equation we have written to describe the reaction is called a
molecular equation, because all the reactants and products are written as
if they were molecules, A more accurate representation of the reaction as
it actually occurs in solution is given by the ionic equation as
Na+(aq) + Cl-(aq) + Ag+(aq) + NO3-(aq)

AgCl(s) + Na+(aq) + NO3- (aq)

In this equation we have shown all the soluble ionic substances as


being dissociated in solution.
Buffers:
Any solution that contains both a weak acid and a weak base has
the ability to absorb small amounts of either a strong acid or strong base
with very little change in pH.
When a small quantities of a strong acid are added they are
neutralized by the weak base, while small quantities of a strong base are
neutralized by the weak acid. Such solutions are said to be buffers
because they resist significant changes in the pH.
A buffer whose pH is less than 7 generally can be prepared by
mixing a weak acid with the salt of that weak acid, for example, acetic
acid and sodium acetate.

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A buffer whose pH is greater than 7 generally can be prepared by


mixing a weak base with the salt of that weak base, for example,
ammonia and ammonium chloride, when H+ or OH- are add to an acetic
acid-acetate buffer, the following neutralization reactions take place:
H+ + C2H3O2-

HC2H3O2

OH- + HC2H3O2

H2O + C2H3O2-

Similarly, for the NH3, NH4Cl, alkaline buffer we have.


H+ + NH3

NH4+

OH- + NH4+

H2O + NH3

In an acid buffer the H+ concentration and pH is determined by the


relative concentrations of the weak acid and its conjugate base, that is the
union for example, for acetic acid we have.
ka =

[H+] [C2H3O2-]
[HC2H3O2]

Solving for [H+] gives.


[H+] = ka

[HC2H3O2]
[C2H3O2-]

To calculate [H+], and then pH, we must


acid, from Table (6.1). Since salts completely
solution, the numbers of moles of the anion in
source is determined by the formula of the salt
moles of salt dissolved.

6.1
know ka for the weak
dissociate in aqueous
the solution from this
and by the number of

Thus a 1.0 M NaC2H3O2 solution contains 1.0 mol/liter of


C2H3O2- , while a 1.0 M Ca(C2H3O2)2 solution contains 2.0 mol/liter of
C2H3O2-. In the buffer there is also an additional amount of acetate ion
that comes from the dissociation of HC2H3O2.
Table 6.1
Ionization constants for some weak acids and bases

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The amount of H+ and C2H3O2- stemming from this source is very


small even in solutions containing only acetic acid, and this small amount
is reduced even further in the buffer because of the presence of the large
concentration of C2H3O2- from the salt.
The total anion concentration in the buffer is essentially determined
by the salt concentration alone, since the distribution from the
dissociation of the weak acid is negligible in a mixture of 1.0 M
NaC2H3O2 and 1.0 M HC2H3O2, for example the concentrations of both
the molecular acid and the anions are 1.0 M. The H+ concentration in such
a buffer could be found from equation 6.1 using ka = 1.8 x 10-5 (from
table 6.1).
[H+] = (1.8 x 10-5)

1.0
1.0

= 1.8 x 10-5
The pH of this solution is 4.74
Notice that when the concentrations of the acid and anion are the
same in a buffer, the H+ concentration in that solution is equal to the Ka of
the weak acid, and the pH = pka. Thus, if a buffer were prepared by
mixing 0.1 mol of forming acid (ka = 1.8 x 10-4 from table 6.1) and 0.1
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mol of sodium formate into a liter of solution, the resulting H +


concentration would be.
[H+] = 1.8 x 10-4 M
and

pH = 3.74

Let us now see how effective a buffer is at holding the pH nearly


constant. Suppose we have an acetic acid acetate buffer in which the
concentrations of HC2H3O2 and C2H3O2- are each 1.0M. We saw earlier
that its pH will be 4.74 and [H+] = 1.8 x 10-5 M.
What happens to the pH if we add, say 0.20 mol of HCl to a liter of this
buffer?
When a strong acid such as HCl is add, its H+ reacts with acetate ion.
H+ + C2H3O2-

HC2H3O2

This decreases the C2H3O2- concentration and increases the


HC2H3O2 concentration. Below are the numbers of moles per liter of all
species before and after the addition.

[H+] =
[C2H3O2-] =
[HC2H3O2] =

Initial

Final

1.8 x 10-5 M
1.00 M
1.00 M

x
1.0 0.2 = 0.8 M
1.0 + 0.2 = 1.2 M

Substituting these final concentrations into equation (6.1), we have.


[H+] = (1.8 x 10-5) x

1.20
0.80

= 2.7 x 10-5 M
The pH of the buffer after the 0.2 mol of H+ is added is 4.57, a
change of only 0.17 pH units from its initial pH of 4.74.
Suppose now that we were to add 0.2 mol of H+ to 1 liter of a
solution of HCl whose pH = 4.74 (that is, a 1.8 x 10 -5 M HCl solution).
Since Cl- has virtually no tendency to react with H+, the final H+

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concentration will be 0.20 M (0.2 + 1.8 x 10 -5 = 0.20), and the pH of the


solution will be 0.70.
The change in pH in this case is 4.04 pH units, as opposed to a
change of only 0.17 pH units when the same quantity of H + is added to
the buffer.
Additions of strong base are also absorbed by the buffer, when 0.20
mol of OH- is add to the 1 liter of our original buffer, it is neutralized
according to the reaction.
OH- + HC2H3O2

H2O + C2H3O2-

The numbers of moles per liter before the addition are the same as
above, but the number of moles per liter after 0.20 mol of OH - is added
would be
Concentration after addition of 0.2 mol of OH-.
[H+] =
[C2H3O2-] =
[HC2H3O2] =

x
1.0 + 0.2 = 1.2
M
1.0 - 0.2 = 0.8 M

Substituting these values into equation (6.1), we find that the [H +]


concentration after the addition is 1.2 x 10 -5 M and the resulting pH is
4.92, once again, a change of 0.17 pH units.
Finally, note that the addition of an acid to the buffer lowers the
pH, while addition of a base raises the pH. Although the change in pH is
small, the direction of the change is as expected.
Example:
A buffer was prepared by mixing exactly 200 ml of a 0.6 M NH 3
solution and 300 ml of a 0.3 M NH4Cl solution.
a. What is the pH of this buffer, assuming a final volume of 500 ml?
b. What will be the pH after 0.02 mol of H+ is added?
Solution:

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The number of moles of NH3 added to this solution is


0.6 mol/lit x 0.20 lit = 0.12 mol
and the number of moles of NH4+ added is
0.30 mol/lit x 0.30 lit = 0.09 mol
Therefore, the concentrations of these ions in the 500 ml are.
[NH3]

0.12 mol
= 0.24 M
0.50 lit

[NH4+]

0.09 mol
= 0.18 M
0.50 lit

a. The OH- concentration for this alkaline buffer is found by using the
kb for NH3:
NH4+ + OH-

NH3 + H2O

[NH4+] [OH-]
kb =
[NH3]
Rearranging and solving for [OH-] we have.

[OH-] = kb

[NH3]
[NH4+]

Substituting kb for NH3 from Table (6.1) and the concentration of


NH3 and NH4+ for this buffer into this equation gives
[OH-] = (1.8 x 10-5) x

0.24
0.18

= 2.4 x 10-5 M
pOH = 4.62
pH = 9.38
b. The neutralization reaction for H+ in this buffer is:

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H+ + NH3

NH4+

We are adding 0.02 mol of H+ to 500 ml, or 0.04 mol of H+ per


liter. Therefore, the concentrations before and after addition of the acid
are.

[OH-] =
[NH3] =
[NH4+] =

Initial

Final

2.4 x 10-5 M
0.24 M
0.18 M

x
0.24 0.04 = 0.2 M
0.18 + 0.04 = 0.22 M

And the OH- concentration is.


[OH-] = (1.8 x 10-5) x

0.20
0.22

= 1.6 x 10-5 M
pOH = 4.8
The pH is therefore 9.20, a decrease of 0.18 pH units.
Buffers find many important applications. Living systems employ
buffers to maintain nearly constant pH so that biochemical reactions can
follow their correct paths.
For example, blood contains, among other things, H 2CO3/HCO3buffer system that helps maintain the pH at 7.4.
In the laboratory may inorganic & organic chemical reactions are
performed in buffered solutions to minimize any adverse affects caused
by acids or bases that may be consumed or produced during reaction.

18. 7. CORROSION

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7. 1. Definitions:
Destruction of metal by other than mechanical means is defined as
corrosion failure and is the result of a destructive attack by chemical or
electrochemical reaction with its environment or (corrosion is the passage
of the metal into the chemically combined state).
Corrosion is a natural phenomenon which proceeds according to
well understood laws. Plastics and other non metallic substances are not
included in the above definition.
The mechanism of attack for these materials differs from that of
metallic materials.
7. 2. The corrosion reaction:
The most common example is the rusting of iron.
2Fe + 2H2O + O2

2Fe(OH)2

By definition this is a corrosion process since iron (Fe) enters the


chemically combined state Fe(OH)2 undergoes further reactions to form
rust.
An electrochemical mechanism:
1. The metal is oxidized:
2Fe2+ + 4e-

2Fe

Electrochemical oxidation is called an anodic reaction (takes place


at anode).
2. Oxygen in the environment is reduced:
2H2O + O2 + 4e-

4OH-

Electrochemical reduction is called a cathodic process (takes place


at cathode).
Processes (1) & (2) above are electrochemical because they involve
the release or consumption of electrons. Combining equations (1)

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& (2), and canceling the electrons from each side, yields the
chemical reaction equation.
7. 3. The requirements for corrosion:
1. A metal capable of under going an oxidation reaction.
2. An environment containing a corrodent capable of oxidizing the
metal to a chemically combined state. For steel suitable corrodents
are:
a. Dissolved oxygen.
b. Hydrogen ions (e.g. mineral acid HCl).
3. An environment that is electrolytically conducting. This is because
corrosion proceeds by an electrochemical mechanism. If any one of
these requirements in eliminated than there will be no corrosion.
7. 4. Forms of corrosion:
Corrosion

Uniform

Localized

General

Non-mechanical
Galvanic
Crevice
Deposit
Pitting
Intergranular
Biological corrosion

Mechanical
Stress corrosion cracking
Corrosion fatigue
Erosion
Cavitation
Fretting

General corrosion:

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Most metals form a natural protective film on their surface after


being exposed to air for a period of time. In a sense this is corrosion, but
once formed it prevents further corrosion as long as the film remains
intact. Passivation is the name applied to the chemical treatment
procedure used to form this film more rapidly.
A typical illustration is the exposure of austenitic stainless steels to
nitric acid, which will produce such a protective film. The metal is said to
corrode when a chemical attacks this film. This attack will occur at a
specific rate, which will differ between films and chemicals. The usual
terminology for reporting this rate of attack is inches penetration per year
(ipy), milligrams per square decimeter per day (mdd), or mil penetration
per year (mpy). There are three groups or classifications for acceptable
corrosion rates depending on the application. These groups are as follows:
1. < 0.005 ipy (< 5 mpy):
This is indicative of a good corrosion resistance and metals in this
category can be considered for critical parts such as springs, valve
seats, pumps shafts, etc.
2. 0.005 to 0.05 ipy (5 to 50 mpy):
If this degree of corrosion rate can be tolerated, metals in this
group can be considered for piping, the valve bodies, vessels, etc.
3. > 0.05 ipy ( > 50 mpy):
Metals having this degree of corrosion rate are usually not
considered for use in the application. Such interaction between
these chemicals and films can be determined from corrosion tables.
This type of corrosion attack is known as general corrosion and
illustrated by the rusting of iron or the tarnishing of silver.
Galvanic corrosion:
This type of corrosion occurs when two or more dissimilar metals
are in contact, or when metals having the same analysis have different
surface conditions, and an electrolyte is present. This combination
producers an electrolytic cell.
All metals have the ability to act as either an anode or a cathode
depending on their relative positions in the galvanic series. The metal
acting as the anode will be the one to corrode.
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The relative areas between the anode and cathode are important.
Since corrosion is caused by the flow of current from the anode to the
cathode, an unfavorable area ratio is a small anode and large cathode.
For example, steel rivets in a copper plate will corrode much more
quickly than copper rivets in a steel plate. If it is necessary to use
dissimilar metals, an attempt should be made to use two metals as close
as possible to each other in the galvanic series.
The further apart the metals are in the series the greater the
accelerated attack on the more active (anode) metal. Galvanic corrosion
can be prevented by insulating dissimilar metals from each other.
Galvanic series of metals from each other:

Anodic (corroded) End


Magnesium
Zinc
Aluminum
Cadmium
Carbon steel
Cast iron
Stainless steel (Active)
Lead
Tin
Nickel (Active)
Brass
Copper
Bronze
Monel
Silver solder
Nickel (passive)
Stainless steel (passive)
Titanium
Graphite
Zirconium
Gold
Platinum
Cathodic (protected) End.

Anodes and cathodes exist on all metal surfaces as a result of


surface imperfection, lack of homogeneity of the metal, grain orientation,
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and localized torque and sheer resulting from manufacturing operations,


mill scale, and existing red iron oxide rust.
Crevice corrosion:
Occurs in flooded crevices present at a metal surface exposed to an
aerated aqueous environment. It is a problem of the passive metals,
particularly the stainless steel.
With time, oxygen concentration in crevice solution becomes
depleted; outside the crevice refreshment occurs. Produces a lateral
variation in solution composition and a potential difference between
metal surface inside and outside crevice.
later drives corrosion cell; metal inside crevice is anodic
(dissolves). Longer term, other chemical changes occur in crevice that
accelerates local corrosion.
Cr3+ + 3H2O

Cr(OH)3 + 3H-

(acid)

Characteristics:
1. Associated with passivatable metals (particularly stainless steel).
2. Takes time to initiate.
3. Is difficult to stop once started.
4. May occur in crevices formed between:
a. Two similar or dissimilar metals.
b. A metal and non-metal.
c. At a badly made weld.
Typical examples:
1. An austenitic stainless steel shaft in packed gland exposed to saline
water.
2. Many threaded joints.
3. One tube side of many tube/tube plate assemblies in heat
exchangers.
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Sensitive to:
1. Environment composition (especially oxygen and chloride
content).
2. Environment conductivity.
3. Crevice dimensions.
Deposit corrosion:
Analogous to crevice corrosion with many of its characteristics.
The lateral variation in solution composition and potential form between
deposit covered and deposit-free areas. Metal loss occurs under deposit.
Again, it is a problem that particularly affects passive metals.
Typical example:
Austenitic stainless steel in stagnant or low flow areas where environment
contains entrained solids.
Pitting corrosion:
This type occurs on normally passive metals, and corrosion
develops in localized areas, resulting in cavities or pits. These cavities or
pits can range from deep penetration of relatively small diameters to
larger diameter shallow cavities.
The depth of pitting can be expressed by the term pitting factor,
which is the ratio of deepest metal penetration to average metal
penetration. (see Fig. 7.1)

Fig. 7.1
Pitting corrosion

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This is determined weight loss of the specimen. Uniform attack


will have a pitting factor of one. Stainless steel in an aqueous solution
containing chlorides will be subjected to pitting corrosion.
A clean, smooth metal surface will be more resistant to this type of
attack. The addition of inhibitors to the solution will occasionally reduce
or prevent pitting.
Intergranular corrosion:
Occurs when reactive material collects, at grain boundaries of
metal, and/or parent alloy depleted of essential constituent. The grain
boundary material, which is of limited area, act as an anode, and the large
areas of grains act as cathodes.
This results in the flow of energy from the small anode to the large
cathode area, which causes rapid attack penetrating deeply into the metal.
Intergranular corrosion can be caused by the improper heating of
austenitic stainless steel or duralumin-type (4% Cu-Al).
All austenitic stainless steels contain some amount of carbon.
When the metal is heated to its sensitizing range 454C to 899C (850F
to 1650F), as in welding, carbon is precipitated out at the grain
boundaries in the form of chromium carbide.
The composition has been changed by removing chromium from
this area, thus making it susceptible to corrosive attack. If the stainless
steel is annealed after it has been sensitized, this effect can be reduced.
Annealing is accomplished by heating the alloy to 928C (1800F)
or higher (depending on the specific alloy) and quickly cooling it through
the sensitizing range to prevent the carbon from precipitating out.

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Fig. 7.2
Biological corrosion:
Corrosion of metal can be caused by the metabolic activity of
microorganisms either directly or indirectly. There are two types of
microorganisms associated with this type of corrosion-aerobic and
anaerobic.
Aerobic microorganisms grow in an atmosphere containing
oxygen, while anaerobic species grow in an environment devoid of
atmospheric oxygen.
The activity of these microorganisms can cause corrosion by:
1. Producing a corrosive environment.
2. Altering the resistance of the surface film.
3. Having an effect on the rate of anodic or cathodic reaction.
4. Creating electrolytic concentration cells on the metal surface.
5. Altering the environment composition.

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Sulphate-reducing bacteria (anaerobic) easily reduce inorganic


sulphates to sulphides such as calcium sulphide or hydrogen sulphide.
When these compounds come into contact with iron (such as
underground iron pipes), conversion of the iron to iron sulphide occur.
Since these bacteria thrive under such conditions, the reaction will
continue until the pipe fails. Damage can be reduced by chlorination or
the addition of certain bactericides.
Stress corrosion cracking:
Stress corrosion cracking is the result of accelerated corrosion,
which is caused by either residual internal stress in the metal or an
external applied stress.
Residual internal stresses can occur as a result of cold forming, un
equal cooling from high temperature, and by internal structure
arrangement involving volume change. These stresses can be relieved by
proper annealing after fabrication. Applied stresses can result from faulty
design, vibrations, excessive flexing, and expansion and contraction due
to thermal changes.
Practically all alloys are subject to stress corrosion cracking in
certain specific environment. Examples are:
1. Caustic embrittlement of carbon steel when temperature exceed
49C (120F) or the caustic concentration exceeds 30%.
2. Cracking of cold-formed brass in the presence of ammonia.
3. Cracking of austenitic stainless steels in the presence of chlorides
[(Cl-) > 2 ppm], T > 50C.
4. Cracking of Monel in hydroflurosilic acid.
5. Carbon steel in hot nitrate solution.
6. Cracking of nickel in fused caustic soda.
7. Cracking of titanium alloys in methanol/hydrochloric acid mixture.
8. Cracking of carbon steel in carbonate/bicarbonate mixtures.

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Corrosion fatigue:
When a metal is subjected to cyclic or repeated stress conditions,
the protective oxide films present rupture at a rate greater than new films
can be formed.
This condition results in the formation of anodic areas at the point
of the film rupture. This, in turn causes the formation of pits, which serve
as a stress concentration point for the origin of the cracks, leading to
ultimate failure.
This phenomenon results in the reduction of the ability of the metal
to resist cyclic or repeated stresses. Corrosion of the metal surface lowers
the fatigue resistance, and stressing of the surfaces will tend to accelerate
corrosion.
Typical example:
Structural steel in seawater (e.g. Oil production platforms).
Erosion corrosion:
Occurs when high velocity fluid flow disrupts passive films or
prevents their formation. Damage to passive film may be due to the
erosive effect of the fluid and/or entrained solid or gases.
Fluid is then corrosive towards the un-protected metal. Turbulent
flow in pipe work may initiate erosion corrosion. Flow disturbance
produced at bends and tees, in pumps and valves, or by orifice plates and
badly made welds, can cause problems.
Typical example:
1. Damage at elbows in gas production tubing.
2. Damage to copper pipework at high velocities (> 2 m/sec) on
seawater systems.
3. Damage to copper-based heat exchanger tubes at inlet end.
4. Vessel wall damage near badly directed inlet tube.

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Cavitation corrosion:
This is more correctly termed cavitation erosion. It is caused by the
formation of bubbles and their collapse on the metal surface, causing
mechanical erosion of the surface, which in turn destroys the protective
oxide film.
This results in more rapid corrosion attack as a result of the
destruction of the protective film. This phenomenon is experienced
around propellers, rudders, struts, the water-cooled side of diesel engines,
and the rotors of pumps.
Since the bubbles are formed when a vacuum condition exists, and
they collapse when pressure exists, a redesign of the operation or the use
of more resistant alloy can correct this condition.
Fretting corrosion:
Fretting corrosion is defined as damage occurring at the interface
of two surfaces in contact, one or both of which are metals, subject to
slight relative slip.
Fretting corrosion is responsible for the failure of both heads,
contacts of electrical relay, connecting rods, and various parts of vibrating
machinery. This type of corrosion can be prevented and/or greatly
reduced by the following methods.
1. Use of lubricants.
2. Use of a soft metal with a hard metal.
3. Use of gasketing materials like (Teflon).
4. Design of contacting surfaces to avoid slip.
7. 5. Corrosion control:
By design:
Good design can permit the effective use of cheaper materials. Bad
design may render good materials selection wholly ineffective.

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Expensive corrosion resistance materials may fail prematurely as a


result of a bad design.
Good corrosion engineering design:
1. Avoids crevices.
2. Avoids deposits.
3. Permits free drainage.
4. Creates access for maintenance.
5. Avoids impingement or wear.
6. Control galvanic couples.
7. Avoids condensation of aggressive fluids.
By coatings:
Protective coatings and linings serve to control corrosion by
providing one of the following.
1. An inert or highly corrosion resistant barrier between the metal and
the environment.
e.g. Vitreous enamel coating, nickel alloy cladding, chromium.
2. A sacrificial barriers between the metal and the environment
e.g. Zinc (galvanized, flame sprayed, etc.), cadmium coating,
aluminum (flame spray, hot dip.)
3. A high resistance electric path between anodic and cathodic
reaction sites
e.g. Most polymeric coatings, paints, rubbers, plastics.
4. A reservoir of corrosion inhibitor adjacent to the metal surface.
e.g. primer paints with anticorrosive pigments.

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5. Cathodic protection.
e.g. Zinc rich paints.
Cathodic protection:
Cathodic protection can be achieved by the use of either an
impressed electric current or a sacrificial anode.
Although it cannot be used above the water line (out the area of the
electrolyte), it can be effectively used to eliminate corrosion fatigue,
Intergranular corrosion, and stress corrosion cracking, dezincification of
brass, or pitting of steels in seawater or steel in soil.

Fig. 7.3
Cathodic protection

Cathodic protection is accomplished when an external current is


supplied to the corroding metal on the surfaces of which local action cells
operate, Fig. 7.3, illustrate this principle.
Alternatively, it is possible to select an anode of a more active
metal in the galvanic series than the metal to be protected, and thus
eliminate the need for an external source of DC current. This combination
of metals will establish a galvanic cell with the current direction exactly
the same as if an external current had been impressed.

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Most sacrificial anodes are of magnesium construction. These are


typically used to protect hot water tanks, buried pipelines, and structures
below ground.
Corrosion inhibitors:
The addition of small amounts of chemical compounds to a
corrodent, which are able to reduce the corrosion of the exposed metal, is
a preventive measure known as inhibition.
Inhibitors will reduce the rate of either anodic oxidation or cathodic
reduction. On this basis it is possible to have anodic, cathodic, and mixed
inhibitors.
Inhibitors can also be classified according to their chemical nature
(organic or inorganic substances), their characteristics (oxidizing or non
oxidizing compounds) or their technical field of application (pickling,
descaling, acid cleaning, cooling water systems, etc.).
It is possible to use inhibitors at different pH values, from acid to
near neutral to alkaline. The corrosion attack of aqueous acid solutions on
metals and alloys is usually very severe.
This attack can be inhibited by the addition of a large number of
organic compounds such as triple-bond hydrocarbons, acetylenic
alcohols, sulfoxides, sulfides and mercaptans, aliphatic, aromatic, or
heterocyclic compounds containing nitrogen, and many other families of
simple organic compounds.
It is postulated that the inhibitors are absorbed on to metal surface
either by physical (electro static) adsorption or chemisorptions. Physical
adsorption is the result of electrostatic attractive forces between the
organic ions and the electrically charged metal surface.
Chemisorptions is the transfer of, or sharing of, the inhibitors
molecules charge to the metal surface, forming a coordinate type of bond.
The use of inhibitors can create problems as well as retard corrosion.
If the incorrect inhibitor is used, corrosion or hydrogen penetration
into the metal can be accelerated. Therefore care must be taken in the
selection of an inhibitor for use in acid solutions.

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Inhibitors, which are efficient in controlling corrosion in acid


solution, have little or no effect in near-neutral solution. In many cases
inorganic compounds are used in these instances as inhibitors.
Inorganic anions such as polysulphates, silicates, borates, and
phosphates are typically used. Oxidizing inhibitors such as chromates or
nitrites are also used.
A third group of inhibitors are used in alkaline solutions. All metals
whose hydroxides are amorphic, and those metals whose protective
oxides are destroyed in the presence of alkalis are subject to caustic
attack.
Inhibitors for this class of solution consist of organic substances
such as tannins, gelatin, spooning thiourea, substituted phenols and
naphthols, beta-diketons, and quinalizarine.
The primary use of inhibitors is to prevent or reduce general
corrosion. However, this is not the important form of corrosion.
Approximately 65 to 75% of all chemical plant failures are due to stress
corrosion cracking, corrosion fatigue, pitting or erosion corrosion, and
only 35% are the result of general corrosion.
The use of inhibitors plays an important part in the control of
corrosion for those areas where general corrosion is the problem. The use
of inhibitors to control corrosion requires continued attention to be sure
that the inhibitors are being constantly added and the proper
concentrations are being maintained.
A primary advantage for the use of inhibitors is when existing
equipment is to be used for a new application. This may be the most
economical approach, rather than changing the materials of construction.

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18. 8. WATER TREATMENT


8. 1. Introduction:
Water is essential to the development of industry. Enormous
quantities are required for cooling of product and equipment, for process
need, for boiler feed and for drinking water.
In order to be used in industry, water must be free from impurities;
these impurities are a source of a potential trouble to industry through
deposition of the impurities in water lines, boiler tubes and on products
which are connected by it. Impurities found in fresh water supplies may
be broadly classified as dissolved and suspended solids and dissolved
gases.
Industry spends millions annually for water treatment equipment
and chemical to remove, reduce or otherwise alter the impurities, which
are inherent in its use.
Drinking water should be free from apparent turbidity, color and
odor and any objectional taste.
8. 2. Selection of water treatment processes:
Water treatment selection is a complex task involving the
consideration of various factors. The choice of water treatment scheme
depends on:
1.
2.
3.
4.
5.

Water supply source quality.


Designed finished water quality.
Reliability of process equipment.
Operational requirements and personal capabilities.
Flexibility in dealing with changing water quality and equipment
malfunction.
6. Available space for construction of treatment facilities.
7. Waste disposal constraints.
8. Capital and operating costs.
Water treatment unit processes are interrelated such that modifications
in one unit process may affect other unit process and the overall treatment
objective.

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Water treatment processes can be grouped according to their general


functions in the water treatment scheme.
8. 3. Water treatment unit processes:
a. Air stripping and aeration:
These processes are used in water treatment of dissolved gases
such as CO2, H2S and other taste and odor causing compounds and
volatile organic compounds (VOC). Aeration is also used to add oxidized
iron and manganese, and to prevent formation of reducing environments
that exacerbate taste and odor problems.
Several methods of contacting air with water to strip dissolved
gases are available. Spray nozzles, function type aerators, cascading trays
aerators, packed-tower stripping are used widely in water treatment field.

Fig: 8.1
Percentage CO2 available for removal

Fig: 8.2
Percentage NH3 available for removal

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Fig: 8.3
Percentage H2S available for removal

Fig: 8.4
Forced draft aerator

b. Clarification:
Suspended matter in raw water-supplies is removed by various
methods to provide a water suitable for domestic purposes and most
industries requirement. Removal is generally accomplished by
coagulation; flocculation and sedimentation, often referred to us
conventional clarification.
Coagulation is the process to promote aggregation of small
particles into large particles. Flocculation is the process of bringing
together the coagulated particles to form a large agglomeration or
flocculation.

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Sedimentation refers to the physical removal from suspension or settling


that occurs once the particles have been coagulated and flocculated.

Fig: 8.5
Up flow sludge blanket clarifier

Fig: 8.6
Solid-contact clarifier

c. Filtration:

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Coagulation and sedimentation of a surface supply produce water


of suitable quality for most industrial uses. When water is to be used for
drinking, boiler make-up or special process cooling purposes, additional
particulate matter usually must be removed, water can be filtered by
passing it through a bed of porous medium, such as sand, anthracite or
combination of both.
Filtration does not remove dissolved solids, but may be used
together with softening process that does reduce concentration can reduce
the turbidity of water which has been pretreated with either inorganic or
synthetic organic coagulates.

Fig: 8.6
Vertical-type pressure sand filter

d. Precipitation softening processes:


Precipitation softening processes are used to reduce raw water
hardness, alkalinity, silica and other constituents to prepare water for
direct use as cooling tower make-up as a first stage treatment followed by
ion exchange for boiler make up or process use.
The treatment is accomplished by the use of lime or lime and soda
ash or lime and sodium aluminate.

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These chemicals react with the hardness and natural alkalinity in


the water to form insoluble compounds, which precipitate and are
removed from water by sedimentation and usually, filtration. Water with
moderate to high hardness and alkalinity concentrations (150 to 500 ppm
as CaCO3) are treated in this fashion.
In almost every raw water supply, hardness is present as calcium or
magnesium bicarbonate, either referred to as carbonate hardness or
temporary hardness.
However, hardness may also present as sulphate or chloride salts,
referred as a non-temporary hardness, this may be reduced in
concentration simply by heating:
+ heat

Ca (HCO3)2

CaCO3 + H2O + CO2

The reduction of non-carbonate hardness requires chemical


addition, the addition of lime, lime and soda ash, or lime and sodium
aluminate to raw water promotes the precipitation reactions, so that
softening may take place under controlled conditions.

Fig: 8.7
Sludge-contactor softener

Cold lime softening:

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Precipitation softening accomplished at ambient temperature is referred


as cold lime softening.
Hydrate lime Ca (OH)2 is added to the raw water being treated and
the following reactions occur:
CO2 + Ca (OH)2
Ca (HCO3)2 + Ca (OH)2
Mg (HCO3)2 + 2Ca (OH)2

CaCO3 + H2O
2CaCO3 + 2H2O
Mg (OH)2 +2CaCO3 + 2H2O

By maintaining the proper chemical control on lime feed, the


calcium hardness may be reduced to 35 to 50 ppm. Magnesium reduction
is a function of the amount of (OH ) alkalinity excess maintained.
Non-carbonate calcium hardness, if present is not affected by
treatment with lime alone, the magnesium will be reduced to 70 ppm, but
the calcium will increase to the extent of the magnesium reduction due to
the following reactions:
MgSO4 + Ca (OH)2

Mg (OH)2 + CaSO4

MgCl2 + Ca (OH)2

Mg (OH)2 + CaCl2

To improve magnesium reduction, which also improves silica


reduction in cold process softening, sodium aluminate may be used. The
sodium aluminate provides the hydroxyl ion (OH ) needed for improved
magnesium reduction without increasing calcium hardness in the treated
water.
In addition the hydrolysis of sodium aluminate results in the
formation of aluminum hydroxide, which aids in flocculation formation.
The reaction is:
Na2Al2O4 + 4H2O

2Al (OH)3 + 2NaOH

SO4
Mg

Na2SO4
+ 2NaOH

Cl2

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Mg(OH)2 +
2NaCl

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Fig: 8.8
Calcium reduction
vs.
Carbonate alkalinity.

Fig: 8.9
Magnesium reduction
vs.
Causticity

Warm lime softening:


This softening process is carried out at temperature in the range of
120 to 140F. Reaction rates are improved by the increase in temperature.
In any warm lime or warm lime soda ash process, temperature control is
very critical because temperature variations are 3 to 5F per hour can
cause carry over.
Hot process softening:
This process is usually carried out at temperature of 227 to 240F.
A pressure vessel is required.
At the operating temperature, hot process softening reactions go
essentially to completion. The same reactions as described before are
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involved in this treatment method. The use of lime and soda ash permits
hardness reduction down to 0.5 grain per gallon, or about 8 ppm as
calcium carbonate.
Magnesium is reduced to 2 to 5 ppm because of the greater
insolubility of magnesium hydroxide at the elevated temperature.

Fig: 8.10
Down flow design of hot-process softener.

Silica reduction:
Hot process softening also permits a very good silica reduction.
Silica reduction is accomplished by sorption of silica on the magnesium
hydroxide precipitate. If there is insufficient magnesium present in the
raw water to reduce silica to the desired value, magnesium compounds
such as MgO, MgSO4, MgCO3, . . . etc, may be used.
Silica reduction by cold or warm processes is not nearly as good as
with hot process.

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Other contaminates reduction:


Iron and manganese, if present, will be reduced to about 0.05 and
0.01 ppm respectively by these processes, if as in usual, filters are
included in the system, raw water organics will also reduced.

Fig: 8.11
Approximate magnesium oxide
Requirements for silica removal
In a hot process softener

e. Ion exchange:
All natural water contains in varying concentrations, dissolved salts
that dissociate in water to form charged particles called ions. The
negatively charged ions are called anions; the positively charged ions are
called cations.
Calcium, magnesium and sodium cation, along with bicarbonate,
sulfate and chloride anions are present in most raw water supplies.
Ion exchangers are materials that exchange one ion for another,
hold it temporarily and release it to a regenerante solution. A proper
regenerant can replace undesirable ions. For example the commonly used
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sodium zeolite softener replaces scale forming calcium and magnesium


ions with sodium ions.

Fig: 8.12
Sodium zeolite softener

Classification of ion exchange resins:


Ion exchange resins consist of a hydrocarbon network to which
ionizable functional groups are attached. The network may be formed
from various organic materials. The ionizable group attached to the bead
structure determines the functional capability of the resin. Present
industrial water treatment resins may be classified as one of the following
main basic type:
1. Strong cation (S.C).
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2. Weak cation (W.C).


3. Strong base anion (S.B).
4. Weak base anion (W.B).

Fig: 8.13
Strong base anion resins.

Fig: 8.14
Schematic of hydrate strong-acid
Cation exchanger

The strong cation and the strong base anion resins can convert
neutral salts into their corresponding acids and base respectively.
This ability called salt splitting, results in different treated water
quality than that obtained by treatment with WC or WB resins. SC resins
derive their exchange activity from sulphonic acid functional groups

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(HSO3-) when operated on the hydrogen cycle they will remove nearly
all-raw water cations according to these reactions.
Ca
2HCO3
Mg SO4
+ 2ZSO3H
2Na 2Cl

2ZSO3

Ca
2HCO3
Mg + H2SO4
2Na
2HCl

Where Z represent complex resin matrix. Because these reactions


are reversible, when the resin capacity has been exhausted, it can be
recovered through regeneration with mineral acids.
SC exchangers function is well at all pH ranges and split neutral salts into
their corresponding acids. These resins have found a wide range of
applications, being used for the sodium cycle for softening and on the
hydrogen cycle for softening and decationization.
Weak cation (WC) exchange resins have carboxylic group (- COOH) as
the exchange sites. When operated on the hydrogen cycle, WC resins can
remove cations associated with alkalinity according to:
Ca
Mg (HCO3)2 + 2ZCOOH
2Na

2ZCOO

Ca
Mg + H2CO3
2Na

These reactions are also reversible and permit acid regeneration to


return the exhausted resin to the hydrogen form.
Because WC exchangers do not function efficiently at pH levels
below 5.0, they cannot split neutral salts effectively. The main asset of
WC resins is their high regenerative efficiency, which not only reduces
the amount of acid required for regeneration, but also minimizes waste
disposal problems.
WC resins are used primarily for softening and dealkalization,
frequently in conjunction with a strongly acidic polishing resin.
Strong anion exchanger resins that derive their functionality from
the quaternary ammonium exchange sites are commercially available and
are commonly referred to as Type I and Type II
Type I sites have three methyl groups:
CH3
|

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R N CH3
|
CH3
An ethanol group replaces one of the methyl groups in type II resin.
CH3
+
|
R N CH2CH2OH
|
CH3
The principal difference between the two resins operationally, is
that type I has a greater chemical stability and type II has a slightly
greater regeneration efficiency, and capacity.
In the hydroxide from SB resin will remove all commonly
encountered inorganic acid according to these reactions:
H2SO4
2HCl
2H2SiO3
2H2CO3

+ 2ZOH

SO4
2Z 2Cl
2HSiO3
2HCO3

+ 2H2O

Like the cation resin reactions, the anion exchange reactions are
also reversible, regeneration with a strong alkali, such as caustic soda,
will return the resins to the hydroxide form.
Weak anion resins derive their functionality from primary (R NH 2),
Secondary (R NHR) and tertiary (R N R2) amine groups
WB resin absorb such free mineral acids such hydrochloric acid,
sulphuric acid and nitric acid, the reaction may represent as:
H2SO4
2HCl
2HNO3

+ 2ZOH

SO4
2Z 2Cl
NO3

+ 2H2O

WB resins are essentially mineral acids neutralizers. Because the


above reactions are also reversible, WB resins can be regenerated by
applying caustic soda, soda ash or ammonia.

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Regeneration efficiency of WB resin is substantially greater than


for strong base resin. While WB resins readily adsorb free mineral acids,
these resins will not remove such weakly Ionized acids.
Weakly basic resins are used in demineralizer systems in
conjunction with strongly basic resins to reduce regenerant costs, to
scavenge organic thereby protecting the more susceptible strongly basic
resins.

Fig: 8.15
Calcium sulfate-fouled resin

Fig: 8.16
Iron-fouled resin

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Fig: 8.17
Organic-fouled resin

Demineralization:
Demineralization, as applied to water treatment, is the removal of
essentially all inorganic salts by ion exchange. In this process, hydrogen
cation exchange converts dissolved salts to their corresponding acids, and
basic anion exchange removes these acids.
The only other commercial process, which produces water of
comparable purity, is distillation. Because demineralization of most fresh
water supplies is substantially less expensive than distillation, it is widely
used.
Principles of demineralization:
The demineralizer system consists of one or more ion exchange
resin columns, which is includes a strong cation unit and a strong anion
unit.
The cation resin exchanges hydrogen for raw water cation as
shown by these reactions:
Ca
Mg
2Na

SO4
2Cl
2HCO3
2NO3

+ 2HZ

2Z

Ca
Mg
2Na

H2SO4
+ 2HCl
2H2CO3
2HNO3

The anion resin exchanges hydroxyl anions for the highly ionized
anions as shown by these reactions:
H2SO4
2HCl
+ 2ZOH
2HNO3

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SO4
2Z 2Cl
2NO3

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Because the anion used a demineralizer resin is strongly basic, it


will also remove weakly ionized carbonic and silicic acids, according to
these reactions.
H2CO3
H2SiO3

+ ZOH

HCO3
Z HSiO3

+ H2O

The above reactions indicate complete removal of cations and


anions from the water, but in reality these are equilibrium reactions, and
even with very efficient column operations, leakage will occur.
The leakage will vary according to the system used and for any
given system, according to the raw water mineral and demineralizer
reagent level (the amount of acid and caustic soda used for regeneration).
To minimize cation leakage, the exchanger may be regenerated up-flow
and operated down-flow in the service cycle. This insures that the water
will pass through the most highly regenerated resin just before leaving the
unit.
The cation resin is regenerated with acid.
2ZSO3

Ca
Mg
2Na

+ 2HCl

2ZSO3H

Ca
Mg
2Na 2Cl

The anion exchange resin is regenerated with an alkaline material.


Caustic soda is the most common regenerant; Caustic soda usually
applied as 4% solution regenerant the resin in accordance with these
reactions.
SO4
2Cl
2Z 2NO
3
2HCO3
2HSiO3

+ 2NaOH

Na2SO4
2NaCl
2ZOH + 2NaNO
3
2NaHCO3
2NaHSiO3

Caustic Soda is that preferred regenerant wherever silica must be


removed. Weak base anion exchange resins may be regenerated with
caustic soda, ammonia or soda ash.

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Fig: 8.18
Mixed bed ion exchange unit, showing internal distribution

Equipment:
The demineralization system will vary according to the
requirements of the application. Fig. 8.19 shows nine basic demineralizer
systems and lists areas of application, typical treated water quality and the
relative advantages/disadvantages of each.
The cation and anion exchange columns for demineralization are
similar for hydrogen zeolite softening. The only difference is the use of
anion resin in the anion exchange column.
The piping, valves and fittings are made of lined or acid resistant
material, when required the decarbonator or vacuum degasifier is
identical in design to the unit used in split-stream softening.
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The mixed-bed demineralizer is also similar to the hydrogen zeolite


softener except that the resin bed is a mixture of cation and anion
exchange resins. In addition, sight glass windows and an interface
regenerant collector are typically part of the design. One of the sight glass
window is located for observing the resin level in the unit, since of the
loss of even small quantities of resin may cause poor performance.
The lower sight glass window is positioned to allow detection of
the line of separation between the cation and anion resins when the unit is
prepared for regeneration (see Fig. 8.19).
The efficient regeneration requires a clear and distinct line of
separation. If the resins are not completed separated, the anion resin that
remains in the bottom of the unit will be regenerated with H 2SO4, which
converts it to the sulphate form. Any cation resin in the upper portion of
the column will be regenerated with caustic soda and converted to the
sodium or exhausted form.
Therefore the operating capacity and treated water quality will both
suffer if complete resin separation is not achieved prior to regeneration.
The interface regenerant collector as its name implies, is positioned
at the interface between the cation and anion resins to collect spent
regenerant.
If the unit does not contain the correct amount of cation resin, the
regenerant collector will not be positioned properly with respect to the
resin interface. The result will be similar to the effect of inadequate
separation of the resins (a portion of the cation or anion resin will be
treated with the wrong regenerant solution).
The mixed-bed demineralizer is equipped for air injection in to the
bottom of the unit to re-mix the separated resins following regeneration.
Both the quality of the treated water and the capacity of the unit
may be affected if the resin is not thoroughly and uniformly mixed.

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Fig: 8.19
Dematerialize systems.

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