THE RATES OF CHEMICAL REACTIONS

Introduction
Chemical kinetics is the branch of physical chemistry concerned with the rates of
chemical reactions. Chemical kinetics deals with how rapidly reactants are consumed and
products are formed. It is concerned with how reaction rates respond to changes in the conditions
or presence of a catalyst, and the identification of the steps by which a reaction takes place. It is
important to study the rates of reactions because it enables chemists to predict how quickly the
reaction mixture approaches equilibrium. That is, rate might depend on variables that can be
controlled. For example, the pressure, the temperature can be able to optimize by the appropriate
choice of conditions. Another reason is that, the study of reaction rates leads to an understanding
of the mechanism of a reaction, that is, its analysis into a sequence of elementary steps. By
analysing the rate of a biochemical reaction, how an enzyme acts could be discovered. This is
called enzyme kinetics and it is defined as the study of the effect of enzymes on the rates of
reactions. This shows how these proteins work.

Empirical chemical kinetics

The first stage in the study of the rate and mechanism of a reaction is to determine the
overall stoichiometry of the reaction and to identify any side reactions. The next step is to
determine how the concentrations of the reactants and products change with time after the
reaction has been initiated. The method used to monitor the concentrations of reactants and
products and their variation with time depends on the substances involved and the rapidity with
which their concentrations change.

The definition of rates of reaction

The rate of a reaction is defined as the rate of change of the concentration of a designated
species. The rates at which reactants are consumed and products are formed change in the course
of a reaction. Once the reaction is initiated, reactants decrease and products are formed with
time. Therefore, it is necessary to consider the instantaneous rate of the reaction, that is, its rate
at a specific instant.
 dξ
v= rate of reaction
dt
1 dn J 1 d [J ]
v= v=
ν J dt ν J dt
homogeneous

The graph shows instantaneous rate of consumption of reactant. This is a graph that
shows the slope of a graph of its molar concentration plotted against time. The slope is evaluated
at the instant of interest. The steeper the slope, the greater the rate of consumption of the
reactant. The the reaction rate is reported in molL -1s-1. In general, the various reactants in a given
reaction are consumed at different rates and the various products are formed at different rates.

Rate laws and rate constants

The rate of reaction is often found to be proportional to the molar concentrations of the
reactants raised to a simple power. A rate law is an equation that expresses the rate of reaction in
terms of the molar concentrations of the species in the overall reaction. An experimentally
determined equation is called the ‘rate law’ of the reaction. The reaction:
 pA + qB → nC + mD
Rate of reaction = k[A]p [B]q
Where k is the rate constant

The rate constant is independent of the concentration of the species taking part in the
reaction but depends on the temperature. The units of k are always such as to convert the product
of concentrations into a rate expressed as a change of concentration divided by time. Once the
rate law and the rate constant of the reaction are known, the rate of the reaction for any given
composition of the reaction mixture can be predicted. That is, molL-1s-1
The rate law can be used to predict the concentrations of the reactants and products at
any time after the start of the reaction. A rate law is also an important guide to the reaction
mechanism. Any proposed mechanism must be consistent with the observed rate law. Two
methods are used to determine the rate law. These are the isolation method and the initial rate
method.

Reaction order
Reactions are classified according to their kinetics (rate laws). The classification is based
on their order of the reaction. This is the power to which the concentrations of a species is raised
in the rate law. The order of the reaction can be first-order, second-order or even a half order.
The order of the reaction is determined experimentally and rate law cannot in general be inferred
from the chemical equation for the reaction.

Methods to Determining Reaction Order

For chemical reactions that require only one elementary step, the values of x and y are
equal to the stoichiometric coefficients of each reactant. For chemical reactions that require more
than one elementary step, this is not always the case. However, there are many simple ways of
determining the order of a reaction. One very popular method is known as the differential
method also known as the initial rates method.
The recombination of I atoms in the gas phase in the presence of argon was investigated
and the order of the reaction was determined by the method of initial rates. For the reaction
A+B→P
 Experiment [A]/moldm-3 [B]/moldm-3 Initial rates/ moldm-3s-1
1 0.100 0.100 1.0 x 10-3
2 0.200 0.100 1.0 x 10-3
3 0.100 0.200 2.0 x 10-3

a. Write the rate law

b. Determine the overall order of the reaction
c. Determine the rate constant

solution
In order to determine the reaction order with respect to A, one must note in which experiment A
is changing; that is, between experiments 1 and 2. Write a rate law equation based on the
chemical reaction above. This is the rate law:
Rate = K[A]n [B]m
Factors Affecting Reaction Rates
According to their nature, some reactions occur very quickly, while others are very slow.
However, certain changes in the reacting conditions can have an effect on the rate of a given
chemical reaction. Collision theory can be utilized to explain these rate effects.

Collision theory of chemical reactions

According to the collision theory, “the molecules of reactants are assumed to be hard
spheres and the reactions are assumed to occur only when these molecules collide with each
other”. A reaction occurs when reactant molecules collide with each other. The more collisions
per unit time, the faster the reaction rate. he colliding molecules must possess a minimum
amount of total energy, called the activation energy (Ea). The term was given by Arrhenius. It is
the minimum amount of energy that the reactants must possess in order to form a product during
a chemical reaction. All the molecules that have energy greater than or equal to activation energy
will collide to form products. Collisions with total energy less than the threshold energy are
ineffective and simply result in the molecules bouncing back. Furthermore, the colliding
molecules must be oriented in a specific way such that the atoms involved in bond breaking and
bond formation come into direct contact.
Concentration
An increase in the concentration of one or more reacting substances results in an increase
in the rate of reaction. When more particles are present in a given amount of space, a greater
number of collisions will naturally occur between those particles. Since the rate of a reaction is
dependent on the number of collisions occurring between reactants, the rate increases as
the concentration increases.

Pressure
When the pressure of a gas is increased, its particles are forced closer together,
decreasing the amount of empty space between the particles. Therefore, an increase in
the pressure of a gas is also an increase in the concentration of the gas. For gaseous reactions, an
increase in pressure increases the rate of reaction due to a greater number of collisions between
reacting particles.

Surface Area
A large log placed in a fire will burn relatively slowly. If the same mass of wood were
added to the fire in the form of small twigs, the twigs would burn much more quickly. This is
because the twigs provide a greater surface area than the log does. An increase in the surface area
of a reactant increases the rate of a reaction. Surface area is larger when a given amount of a
solid is present as smaller particles. A powdered reactant has a greater surface area than the same
reactant as a solid chunk. In order to increase the surface area of a substance, it may be ground
into smaller particles or dissolved into a liquid. In solution, the dissolved particles are separated
from each other and will react more quickly with other reactants.

Temperature
Raising the temperature of a chemical reaction usually results in a higher rate of reaction.
When the reactant particles are heated, they move faster and faster. This results in a greater
frequency of collisions. A more important effect of the temperature increase is that the collisions
occur with a greater force, and are thus more likely to surmount the activation energy barrier and
go on to form products. Increasing the temperature of a reaction increases the number of
effective collisions between reacting particles, so the reaction rate increases.
Catalysis
A catalyst, a species that increases the reaction rate but is not itself consumed in a
reaction, acts by providing and alternative reaction path with a lower activation energy.
Activation energy is the minimum amount of energy required for a chemical reaction to proceed
in the forward direction. A catalyst that is in the same phase as the reactants is called a
homogeneous catalyst. A catalyst that is in a different phase is called a heterogeneous catalyst.
Many industrial processes make use of heterogeneous catalysts, which include platinum,
rhodium, zeolites, and various metal oxides, but increasingly attention is turning to homogeneous
catalysts, partly because they are easier to cool.
Nature produced catalysts long before chemists. Natural catalysts are the protein
molecules called enzymes. The enzyme provides a reaction pathway with a low activation energy
and accelerates the reaction for which it has evolved.
 THE ORGANIZATION OF THE ELEMENTS

Mendeleev’s Periodic Table

During the 1800s, when most of the elements were being discovered, many chemists tried to
classify the elements according to their similarities. In 1829, Johann Dobereiner noted chemical
similarities in several groups of three elements and placed these elements into what he called
triads. His groupings included the triads of
 chlorine, bromine, and iodine,
 sulphur, selenium, and tellurium,
 calcium, strontium, and barium, and
 lithium, sodium, and potassium.
In all of the triads, the atomic weight of the second element was almost exactly the average of
the atomic weights of the first and third element. In 1864, John Newlands saw a connection
between the chemical properties of elements and their atomic masses. He stated that if the
known elements, beginning with lithium are arranged in order of increasing mass, the eighth
element will have properties similar to the first, the ninth similar to the second, the tenth
similar to the third, and so on. Newlands called his relationship the law of octaves, comparing
the elements to the notes in a musical scale. Newlands tried to force all the known elements to
fit into his octaves but many of the heavier elements, when discovered, did not fit into his
patterns.

Mendeleev’s Table According to Chemical Behaviour

By 1869, a total of 63 elements had been discovered. As the number of known elements grew,
scientists began to recognize patterns in the way chemicals reacted and began to devise ways to
classify the elements. Dmitri Mendeleev, a Siberian-born Russian chemist, was the first scientist
to make a periodic table much like the one we use today.

Mendeleev’s table listed the elements in order of increasing atomic mass. Then he placed
elements underneath other elements with similar chemical behaviour. For example, lithium is a
shiny metal, soft enough to be cut with a spoon. It reacts readily with oxygen and reacts violently
with water. Water, it produces hydrogen gas and lithium hydroxide. As we proceed through the
elements with increasing mass, we will come to the element sodium. Sodium is a shiny metal,
soft enough to be cut with a spoon. It reacts readily with oxygen and reacts violently with water.
When it reacts with water, it produces hydrogen gas and sodium hydroxide.

One would note that the description of the chemical behaviour of sodium is very similar to the
chemical description of lithium. When Mendeleev found an element whose chemistry was very
similar to a previous element, he placed it below the similar element. Mendeleev avoided
Newlands’ mistake of trying to force elements into groups where their chemistry did not match,
but still ran into a few problems as he constructed his table. Periodically, the atomic mass of
elements would not be in the right order to put them in the correct group. For example, look at
iodine and tellurium on your periodic table. Tellurium is heavier than iodine, but he put it before
iodine in his table, because iodine has properties most similar to fluorine, chlorine, and bromine.

Additionally, tellurium has properties more similar to the group with oxygen in it. On his table,
he listed the element and its place according to its properties and put a question mark (?) next to
the symbol. The question mark indicated that he was unsure if the mass had been measured
correctly. Another problem Mendeleev encountered was that sometimes the next heaviest
element in his list did not fit the properties of the next available place on the table. He would skip
places on the table, leaving holes, in order to put the element in a group with elements with
similar properties. For example, at the time the elements Gallium and Germanium had not yet
been discovered.

After zinc, arsenic was the next heaviest element he knew about, but arsenic had properties most
similar to nitrogen and phosphorus, not boron. He left two holes in his table for what he claimed
were undiscovered elements. Note the dashes (-) with a mass listed after it in his original table.
These indicate places in which he predicted elements would later be discovered to fit and his
predicted mass for these elements.

Mendeleev went further with his missing elements by predicting the properties of elements in
those spaces. In 1871 Mendeleev predicted the existence of a yet-undiscovered element he called
eka-aluminium (because its location was directly under aluminum’s on the table). The table
below compares the qualities of the element predicted by Mendeleev with actual characteristics
of Gallium (discovered in 1875). Mendeleev made similar predictions for an element to fit in the
place next to silicon. Germanium, isolated in 1882, provided the best confirmation of the theory
up to that time, due to its contrasting more clearly with its neighbouring elements than the two
previously confirmed predictions of Mendeleev do with theirs.

He understood the patterns that appeared between elements within a family, as well as patterns
according to increasing mass, that he was able to fill in the missing pieces of the patterns. The
ability to make accurate predictions is was put Mendeleev’s table apart from other organization
systems that were made at the same time and is what led to scientists accepting his table and
periodic law.

Changes to our Modern Periodic Table

The periodic table we use today is similar to the one developed by Mendeleev, but is not exactly
the same. There are some important distinctions: Mendeleev’s table did not include any of the
noble gases, which were discovered later. These were added by Sir William Ramsay as Group 0,
without any disturbance to the basic concept of the periodic table. (These elements were later
moved to form group 18 or 8A.) Other elements were also discovered and put into their places on
the periodic table.

As previously noted, Mendeleev organized elements in order of increasing atomic mass, with
some problems in the order of masses. In 1914 Henry Moseley found a relationship between an
element's X-ray wavelength and its atomic number, and therefore organized the table by nuclear
charge (or atomic number) rather than atomic weight. Thus, Moseley placed argon (atomic
number 18) before potassium (atomic number 19) based on their X-ray wavelengths, despite the
fact that argon has a greater atomic weight (39.9) than potassium (39.1). The new order agrees
with the chemical properties of these elements, since argon is a noble gas and potassium an alkali
metal.

Similarly, Moseley placed cobalt before nickel, and was able to explain that tellurium should be
placed before iodine, not because of an error in measuring the mass of the elements (as
Mendeleev suggested), but because tellurium had a lower atomic number than iodine. Moseley's
research also showed that there were gaps in his table at atomic numbers 43 and 61 which are
now known to be Technetium and Promethium, respectively, both radioactive and not naturally
occurring. Following in the footsteps of Dmitri Mendeleev, Henry Moseley also predicted new
elements.

You already saw that the elements in vertical columns are related to each other by their electron
configuration, but remember that Mendeleev did not know anything about electron
configuration. He placed the elements in their positions according to their chemical behaviour.
Thus, the vertical columns in Mendeleev’s table were composed of elements with similar
chemistry. These vertical columns were called groups or families of elements.

Metals, Nonmetals, and Metalloids

In the periodic table, the elements are arranged according to similarities in their properties. The
elements are listed in order of increasing atomic number as you read from left to right across a
period and from top to bottom down along a group. There is a progression from metals to non-
metals across each row of elements in the periodic table. The diagonal line at the right side of the
table separates the elements into two groups: the metals and the non-metals.
 The modern periodic table

1. Metals: The elements that are on the left of this line tend to be metals, while those to the
right tend to be non-metals (with the exception of hydrogen which is a non-metal). The
elements that are directly on the diagonal line are metalloids, with some exceptions.
Aluminium touches the line, but is considered a metal. Metallic character generally
increases from top to bottom down a group, and right to left across a period, meaning that
francium (Fr) has the most metallic character of all of the discovered elements.

Most of the chemical elements are metals. Most metals have the common properties of
being shiny, very dense, and having high melting points. Metals tend to be ductile (can be
drawn out into thin wires) and malleable (can be hammered into thin sheets). Metals are
good conductors of heat and electricity. All metals are solids at room temperature except
for mercury. In chemical reactions, metals easily lose electrons to form positive ions.
Examples of metals are silver, gold, and zinc.
 2. Nonmetals are generally brittle, dull, have low melting points, and they are generally poor
conductors of head heat and electricity. In chemical reactions, they tend to gain electrons to
form negative ions. Examples of non-metals are hydrogen, carbon, and nitrogen.

3. Metalloids have properties of both metals and nonmetals. Metalloids can be shiny or dull.
Electricity and heat can travel through metalloids, although not as easily as they can
through metals. They are also called semimetals. They are typically semi-conductors,
which means that they are elements that conduct electricity better than insulators, but not
as well as conductors. They are valuable in the computer chip industry. Examples of
metalloids are silicon and boron.

Valence Electrons
The electrons in the outermost shell are the valence electrons these are the electrons on an atom
that can be gained or lost in a chemical reaction. Since filled d or f subshells are seldom
disturbed in a chemical reaction, the valence electrons include those electrons in the outermost s
and p sublevels. Gallium has the following electron configuration.
Ga: [Ar] 4s2 3d10 4p1
The electrons in the fourth energy level are further from the nucleus than the electrons in the
third energy level. The 4s and 4p electrons can be lost in a chemical reaction, but not the
electrons in the filled 3d subshell. Gallium therefore has three valence electrons: the two in 4s
and one in 4p.

Determining Valence Electrons

The number of valence electrons for an atom can be seen in the electron configuration. The
electron configuration for magnesium is 1s2 2s2 2p6 3s2. The outer energy level for this atom is
n=3 and it has two electrons in this energy level. Therefore, magnesium has two valence
electrons.

The electron configuration for sulphur is 1s2 2s2 2p6 3s2 3p4. The outer energy level in this
atom is n=3 and it holds six electrons, so sulphur has six valence electrons. The electron
configuration for gallium is 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p1. The outer energy level for this
atom is n=4 and it contains three electrons. You must recognize that even though the 3d sub-
level is mixed in among the 4s and 4p sub-levels, 3d is NOT in the outer energy level and
therefore, the electrons in the 3d sub-level are NOT valence electrons.

Gallium has three electrons in the outer energy level and therefore, it has three valence electrons.
The identification of valence electrons is vital because the chemical behaviour of an element is
determined primarily by the arrangement of the electrons in the valence shell. This pattern can be
summarized very easily, by merely counting the s and p blocks of the periodic table to find the
total number of valence electrons. One system of numbering the groups on the periodic table
numbers the s and p block groups from 1A to 8A. The number indicates the number of valence
electrons.

Groups and Periods of the Periodic Table

The chemical behaviour of atoms is controlled by their electron configuration. Since the families
of elements were organized by their chemical behaviour, it is predictable that the individual
members of each chemical family will have similar electron configurations.

1. Groups of the Periodic Table

Remember that Mendeleev arranged the periodic table so that elements with the most
similar properties were placed in the same group. A group is a vertical column of the
periodic table. All of the 1A elements have one valence electron. This is what causes these
elements to react in the same ways as the other members of the family. The elements in 1A
are all very reactive and form compounds in the same ratios with similar properties with
other elements. Because of their similarities in their chemical properties, Mendeleev put
these elements into the same group. Group 1A is also known as the alkali metals.

Although most metals tend to be very hard, these metals are actually soft and can be easily
cut. Group 2A is also called the alkaline earth metals. Once again, because of their
similarities in electron configurations, these elements have similar properties to each other.
The same pattern is true of other groups on the periodic table. Remember, Mendeleev
 arranged the table so that elements with the most similar properties were in the same group
on the periodic table.
It is important to recognize a couple of other important groups on the periodic table by
their group name. Group 7A (or 17) elements are also called halogens. This group contains
very reactive nonmetals elements.

The noble gases are in group 8A. These elements also have similar properties to each other,
the most significant property being that they are extremely unreactive rarely forming
compounds. We will learn the reason for this later, when we discuss how compounds form.
The elements in this group are also gases at room temperature. An alternate numbering
system numbers all of the s, p, and d block elements from 1- 18.

In this numbering system, group 1A is group 1; group 2A is group 2; the halogens (7A) are
group 17; and the noble gases (8A) are group 18. You will come across periodic table with
both numbering systems. It is important to recognize which numbering system is being
used and to be able to find the number of valence electrons in the main block elements
regardless of which numbering systems is being used.

2. Periods of the Periodic Table

If one can locate an element on the Periodic Table, one can use the element’s position to
figure out the energy level of the element’s valence electrons. A period is a horizontal row
of elements on the periodic table. For example, the elements sodium (Na) and magnesium
(Mg) are both in period 3. The elements astatine (At) and radon (Rn) are both in period 6.

3. Periodic Trends
To be periodic means to “have repeating cycles” or repeating patterns. In the periodic table,
there are a number of physical properties that are “trend-like”. This means is that as you
move down a group or across a period, you will see the properties changing in a general
direction. The periodic table is a powerful tool that provides a way for chemists to organize
the chemical elements. The word “periodic” means happening or recurring at regular
intervals.
The periodic law states that the properties of the elements recur periodically as their atomic
numbers increase. The electron configurations of the atoms vary periodically with their
atomic number. Because the physical and chemical properties of elements depend on their
electron configurations, many of the physical and chemical properties of the elements tend
to repeat in a pattern. The actual repeating trends that are observed have to do with three
factors. These factors are:
 The number of protons in the nucleus (called the nuclear charge).
 The number of energy levels holding electrons (and the number of electrons in the
outer energy level).
 The number of electrons held between the nucleus and its outermost electrons (called
the shielding effect). This affects the attraction between the valence electrons and the
protons in the nucleus.

i. Trends in Atomic Radius

The atomic radius is a way of measuring the size of an atom. Although this is
difficult to directly measure, we are, in essence, looking at the distance from
the nucleus to the outermost electrons. Let’s look at the atomic radii or the size
of the atom from the top of a family or group to the bottom. Take, for example,
the Group 1 metals. Each atom in this family (and all other main group
families) has the same number of electrons in the outer energy level as all the
other atoms of that family. Each row (period) in the periodic table represents
another added energy level.

When we first learned about principal energy levels, we learned that each new
energy level was larger than the one before. Energy level 2 is larger than
energy level 1, energy level 3 is larger than energy level 2, and so on.
Therefore, as we move down the periodic table from period to period, each
successive period represents the addition of a larger energy level.
You can imagine that with the increase in the number of energy levels, the size
of the atom must increase. The increase in the number of energy levels in the
electron cloud takes up more space. Therefore, the trend within a group or
family on the periodic table is that the atomic size increases with increased
number of energy levels.

In order to determine the trend for the periods, we need to look at the number
of protons (nuclear charge), the number of energy levels, and the shielding
effect. For a row in the periodic table, the atomic number still increases (as it
did for the groups) and thus the number of protons would increase. When we
examine the energy levels for period 2, we find that the outermost energy level
does not change as we increase the number of electrons.

In period 2, each additional electron goes into the second energy level. So the
number of energy levels does not go up. As we move from left to right across a
period, the number of electrons in the outer energy level increases but it is the
same outer energy level. Looking at the elements in period 2, the number of
protons increases from lithium with three protons, to fluorine with nine
protons.

Therefore, the nuclear charge increases across a period. Meanwhile, the

number of energy levels occupied by electrons remains the same. The numbers
of electrons in the outermost energy level increases from left to right across a
period, but how will this affect the radius? With an increase in nuclear charge,
there is an increase in the pull between the protons and the outer level, pulling
the outer electrons toward the nucleus. The net result is that the atomic size
decreases going across the row.

Considering all the information about atomic size, you will recognize that the
largest atom on the periodic table is all the way to the left and all the way to the
bottom, francium (with the atomic number 87), and the smallest atom is all the
way to the right and all the way to the top, helium (with the atomic number 2).
 The fact that the atoms get larger as you move downward in a family is
probably exactly what you expected before you even read this section, but the
fact that the atoms get smaller as you move to the right across a period is most
likely a big surprise. Make sure you understand this trend and the reasons for it.

Example:
Which of the following has a greater radius?
a. As or Sb
b. Ca or K
c. Polonium or Sulfur

Solution:
a. Sb because it is below As in Group 15.
b. K because it is further to the left on the periodic table.
c. Polonium because it is below Sulfur in Group 16.

ii. Periodic Trends in Ionization Energy

Lithium has an electron configuration of 1s 2 2s1. Lithium has one electron in its
outermost energy level. In order to remove this electron, energy must be added.
Li(g) + energy Li+(g) + e-
With the addition of energy, a lithium ion can be formed from the lithium atom
by losing one electron. This energy is known as the ionization energy.
The ionization energy is the energy required to remove the most loosely held
electron from a gaseous atom. The higher the value of the ionization energy,
the harder it is to remove that electron. Consider the ionization energies for the
elements in group 1A of the periodic table, the alkali metals. Comparing the
electron configurations of lithium to potassium, we know that the electron to be
removed is further away from the nucleus, as the energy level of the valence
electron increase. Because potassium’s valence electron is further from the
nucleus, there is less attraction between this electron and the protons and it
requires less energy to remove this electron.
 As you move down a family (or group) on the periodic table, the ionization
energy decreases. We can see a trend when we look at the ionization energies
for the elements in period 2. When we look closely at the data presented in the
table above, we can see that as we move across the period from left to right, in
general, the ionization energy increases. As we move across the period, the
atoms become smaller which causes the nucleus to have greater attraction for
the valence electrons. Therefore, as you move from left to right in a period on
the periodic table, the ionization energy increases.

Example:
Which of the following has a greater ionization energy?
(a) As or Sb
(b) Ca or K
(c) Polonium or Sulfur

Solution:
(a) As because it is above Sb in Group 15.
(b) Ca because it is further to the right on the periodic table.
(c) S because it is above Po in Group 16.

iii. Periodic Trends in Electronegativity

Around 1935, the American chemist Linus Pauling developed a scale to
describe the attraction an element has for electrons in a chemical bond. This is
the electronegativity. The electronegativity of an atom is the ability of an atom
to attract or pull electrons to itself when it is involved in a covalent bond. An
atom of a molecule which tends to attract more electrons to itself is described
as a more electronegative atom. The main factor that influences the value of
electronegativity is the atomic radius of the atom. Electronegativity has no unit.
The values of electronegativity are higher for elements that more strongly
attract electrons. On this Pauling scale fluorine, with an electronegativity of 4.0
is the most electronegative element, and cesium and francium, with
electronegativities of 0.7, are the least electronegative.

The electronegativity of atoms increases as you move from left to right across a
period in the periodic table. This is because as you go from left to right across a
period, the atoms of each element have the same number of energy levels.
However, the nucleus charge increases, so the attraction that the atoms have for
the valence electrons increases.

The electronegativity of atoms decreases as you move from top to bottom

down a group in the periodic table. This is because as you go from top to
bottom down a group, the atoms of each element have an increasing number of
energy levels. Atoms with low ionization energies have low electronegativities
because their nuclei do not have a strong attraction for electrons. Atoms with
high ionization energies have high electronegativities because the nucleus has a
strong attraction for electrons.
 TRANSITION METALS
Introduction
Series of elements in the periodic table in which the d and f subshells are gradually filled are
called the transition elements. There are about 50 transition elements, and they have widely
varying and fascinating properties. To present even one interesting feature of each transition
element is beyond the scope this book. We will therefore limit our discussion to the transition
elements that have incompletely filled d subshells and to their most commonly encountered
property—the tendency to form complex ions.

Properties of the Transition Metals

Transition metals typically have incompletely filled d subshells or readily give rise to ions with
incompletely filled d subshells (Figure 1). (The Group 2B metals—Zn, Cd, and Hg—do not have
this characteristic electron configuration and so, although they are sometimes called transition
metals, they really do not belong in this category.) This attribute is responsible for several
notable properties, including distinctive coloring, formation of paramagnetic compounds,
catalytic activity, and especially a great tendency to form complex ions. In this section we will
focus on the first-row elements from scandium to copper, the most common transition metals.

As we read across any period from left to right, atomic numbers increase, electrons are added to
the outer shell, and the nuclear charge increases by the addition of protons. In the third-period
elements—sodium to argon—the outer electrons weakly shield one another from the extra
nuclear charge. Consequently, atomic radii decrease rapidly from sodium to argon, and the
electronegativities and ionization energies increase steadily.

For the transition metals, the trends are different. Looking at Table 1 we see that the nuclear
charge, of course, increases from scandium to copper, but electrons are being added to the inner
3d subshell. These 3d electrons shield the 4s electrons from the increasing nuclear charge
somewhat more effectively than outer-shell electrons can shield one another, so the atomic radii
decrease less rapidly. For the same reason, electronegativities and ionization energies increase
only slightly from scandium across to copper compared with the increases from sodium to argon.
Although the transition metals are less electropositive (or more electronegative) than the alkali
and alkaline earth metals, their standard reduction potentials suggest that all of them except
copper should react with strong acids such as hydrochloric acid to produce hydrogen gas.
However, most transition metals are inert toward acids or react slowly with them because of a
protective layer of oxide. A case in point is chromium: Despite a rather negative standard
reduction potential, it is quite inert

The transition metals (blue squares). Note that although the Group 2B elements (Zn, Cd, Hg) are
described as transition metals by some chemists, neither the metals nor their ions possess
incompletely filled d subshells.

Table 1 shows the electron configuration and other properties of the first row transition metals

Chemically because of the formation on its surfaces of chromium(III) oxide, Cr 2O3.

Consequently, chromium is commonly used as a protective and noncorrosive plating on other
metals. On automobile bumpers and trim, chromium plating serves a decorative as well as a
functional purpose.

General physical properties

Most of the transition metals have a close-packed structure in which each atom has a
coordination number of +2. Furthermore, these elements have relatively small atomic radii. The
combined effect of closest packing and small atomic size results in strong metallic bonds.
Therefore, transition metals have higher densities, higher melting points and boiling points, and
higher heat of fusion and vaporization than group 1A, 2A and 2B metals.

The physical properties element from K to Zn.

Electron configurations
The electron configurations of the first-row transition metals were discussed in electronic
configuration. Calcium has the electron configuration [Ar]4s2. From scandium across to copper,
electrons are added to the 3d orbitals. Thus, the outer electron configuration of scandium is
4s23d1, that of titanium is 4s23d2, and so on. The two exceptions are chromium and copper, whose
outer electron configurations are 4s13d5 and 4s13d10, respectively. These irregularities are the
result of the extra stability associated with half-filled and completely filled 3d subshells. When
the first-row transition metals form cations, electrons are removed first from the 4s orbitals and
then from the 3d orbitals. (This is the opposite of the order in which orbitals are filled in atoms.)
For example, the outer electron configuration of Fe2+ is 3d6, not 4s23d4.

Coordination compounds
Transition metals have a distinct tendency to form complex ions. A coordination compound
typically consists of a complex ion and counter ion. [Note that some coordination compounds
such as Fe(CO)5 do not contain complex ions.] Nineteenth-century chemists were puzzled by a
certain class of reactions that seemed to violate valence theory. For example, the valences of the
elements in cobalt(III) chloride and in ammonia seem to be completely satisfied, and yet these
two substances react to form a stable compound having the formula CoCl3.6NH3.

To explain this behaviour, Werner postulated that most elements exhibit two types of valence:
primary valence and secondary valence. In modern terminology, primary .valence corresponds to
the oxidation number and secondary valence to the coordination number of the element. In
CoCl3.6NH3, according to Werner, cobalt has a primary valence of 3 and a secondary valence of
6. Today we use the formula [Co(NH3)6]Cl3 to indicate that the ammonia molecules and the
cobalt atom form a complex ion; the chloride ions are not part of the complex but are held to it
by ionic forces. Most, but not all, of the metals in coordination compounds are transition metals.
The molecules or ions that surround the metal in a complex ion are called ligands.

The atom in a ligand that is bound directly to the metal atom is known as the donor atom. For
example, nitrogen is the donor atom in the [Cu(NH 3)4]2+ complex ion. The coordination number
in coordination compounds is defined as the number of donor atoms surrounding the central
metal atom in a complex ion. For example, the coordination number of Ag+ in [Ag(NH 3)2]+ is 2,
that of Cu2+ in [Cu(NH3)4]2+ is 4, and that of Fe 3+ in [Fe(CN)6]3+ is 6. The most common
coordination numbers are 4 and 6, but coordination numbers such as 2 and 5 are also known.

Depending on the number of donor atoms present, ligands are classified as monodentate,
bidentate, or polydentate. H2O and NH3 are monodentate ligands with only one donor atom each.
One bidentate ligand is ethylenediamine (sometimes abbreviated “en”):

The two nitrogen atoms can coordinate with a metal atom, as shown below:
Structure of a metal-ethylenediamine complex cation, such as [Co(en) 3]2+. Each ethylenediamine
molecule provides two N donor atoms and is therefore a bidentate ligand. Bidentate and
polydentate ligands are also called chelating agents because of their ability to hold the metal
atom like a claw (from the Greek chele, meaning “claw”). One example is
ethylenediaminetetraacetate ion (EDTA), a polydentate ligand used to treat metal poisoning
(Figure 22.8). Six donor atoms enable EDTA to form a very stable complex ion with lead. In this
form, it is removed from the blood and tissues and excreted from the body. EDTA is also used to
clean up spills of radioactive metals.

Oxidation states of metals in coordination compounds

Another important property of coordination compounds is the oxidation number of the central
metal atom. The net charge of a complex ion is the sum of the charges on the central metal atom
and its surrounding ligands. In the [PtCl 6]2- ion, for example, each chloride ion has an oxidation
number of -1, so the oxidation number of Pt must be +4. If the ligands do not bear net charges,
the oxidation number of the metal is equal to the charge of the complex ion. Thus, in
[Cu(NH3)4]2+ each NH3 is neutral, so the oxidation number of Cu is +2.

Transition metals exhibit variable oxidation states in their compounds. The figure below shows
the oxidation states from scandium to copper. Note that the common oxidation States for each
element include +2, +3, or both. The +3 oxidation states are more stable at the beginning of the
series, whereas toward the end the +2 oxidation states are more stable. The reason for this trend
can be understood by examining the ionization energy plots in diagram, below. In general, the
ionization energies increase gradually from left to right.

However, the third ionization energy (when an electron is removed from the 3d orbital) increases
more rapidly than the first and second ionization energies. Because it takes more energy to
remove the third electron from the metals near the end of the row than from those near the
beginning, the metals near the end tend to form M 2+ ions rather than M3+ ions. The highest
oxidation state for a transition metal is +7, for manganese (4s23d5). For elements to the right of
Mn (Fe to Cu), oxidation numbers are lower. Transition metals usually exhibit their highest
oxidation states in compounds with very electronegative elements such as oxygen and fluorine—
for example, V2O5, CrO3, and Mn2O7.

Oxidation states of the first-row transition metals. The most stable oxidation numbers are shown in
color. The zero oxidation state is encountered in some compounds, such as Ni(CO) 4 and Fe(CO)5.

The trend of ionization energy.

Trial Question
Specify the oxidation number of the central metal atom in each of the following compounds:
 a. [Ru(NH3)5(H2O)]Cl2,
b. [Cr(NH3)6](NO3)3,
c. [Fe(CO)5], and
d. K4[Fe(CN)6].

Hint:
The oxidation number of the metal atom is equal to its charge. First we examine the anion or the
cation that electrically balances the complex ion. This step gives us the net charge of the complex
ion. Next, from the nature of the ligands (charged or neutral species) we can deduce the net
charge of the metal and hence its oxidation number.

Solution
a. Both NH3 and H2O are neutral species. Because each chloride ion carries a -1 charge, and
there are two Cl2 ions, the oxidation number of Ru must be +2.
b. Each nitrate ion has a charge of -1; therefore, the cation must be [Cr(NH 3)6]3+. NH3 is
neutral, so the oxidation number of Cr is +3.
c. Because the CO species are neutral, the oxidation number of Fe is zero.
d. Each potassium ion has a charge of +1; therefore, the anion is [Fe(CN) 6]4-. Next, we know
that each cyanide group bears a charge of -1, so Fe must have an oxidation number of +2.

Chemistry of Iron and Copper

we are briefly going to survey the chemistry of two of these elements—iron and copper—paying
particular attention to their occurrence, preparation, uses, and important compounds.

Iron
After aluminum, iron is the most abundant metal in Earth’s crust (6.2 percent by mass). It is
found in many ores; some of the important ones are hematite, Fe2O3; siderite, FeCO3; and
magnetite, Fe3O4 Pure iron is a gray metal and is not particularly hard. It is an essential element
in living systems. Iron reacts with hydrochloric acid to give hydrogen gas:

Fe(s) + 2H+ (aq) → Fe2+(aq) + H2(g)

Concentrated sulfuric acid oxidizes the metal to Fe 3+, but concentrated nitric acid renders the
metal “passive” by forming a thin layer of Fe3O4 over the surface. One of the best-known
reactions of iron is rust formation. The two oxidation states of iron are 12 and 13. Iron(II)
compounds include FeO (black), FeSO 4•7H2O (green), FeCl2 (yellow), and FeS (black). In the
presence of oxygen,
Fe21 ions in solution are readily oxidized to Fe31 ions. Iron(III) oxide is reddish brown, and
iron(III) chloride is brownish black.

Copper
Copper, a rare element (6.8 x 10-3 percent of Earth’s crust by mass), is found in nature in the
uncombined state as well as in ores such as chalcopyrite, CuFeS 2. The reddish-brown metal is
obtained by roasting the ore to give Cu2S and then metallic copper:

After silver, which is too expensive for large-scale use, copper has the highest electrical
conductivity. It is also a good thermal conductor. Copper is used in alloys, electrical cables,
plumbing (pipes), and coins. Copper reacts only with hot concentrated sulfuric acid and nitric
acid. Its two important oxidation states are +1 and 12. The +1 state is less stable and
disproportionate in solution:

All compounds of Cu(I) are diamagnetic and colorless except for Cu 2O, which is red. The Cu(II)
compounds are all paramagnetic and colored. The hydrated Cu 2+ ion is blue. Some important
Cu(II) compounds are CuO (black), CuSO4 • 5H2O (blue), and CuS (black).

Naming Coordination Compounds

Now that we have discussed the various types of ligands and the oxidation numbers of metals,
our next step is to learn what to call these coordination compounds. The rules for naming
coordination compounds are as follows:
1. The cation is named before the anion, as in other ionic compounds. The rule holds
regardless of whether the complex ion bears a net positive or a negative charge. For
example, in K3[Fe(CN)6] and [Co(NH3)4Cl2]Cl compound, we name the K+ and
[Co(NH3)4Cl2]+ cations first, respectively.
2. Within a complex ion the ligands are named first, in alphabetical order, and the metal ion
is named last.
3. The names of anionic ligands end with the letter o, whereas a neutral ligand is usually
called by the name of the molecule. The exceptions are H 2O (aqua), CO (carbonyl), and
NH3 (ammine). The table below lists some common ligands.

NAMES OF COMMON LIGANDS IN COORDINATION COMPOUNDS

Name of Ligand in
Ligand Ion Coordination Compound
Bromide Br- Bromo
Chloride Cl- Chloro
Cyanide CN- Cyano
Hydroxide OH- Hydroxo
Oxide O2- Oxo
Carbonate CO32- Carbonato
Nitrite NO2- Nitro
Oxalate C2O42- Oxalate
Ammonia NH3 Ammine
Carbon monoxide CO Carbonyl
Water H2O Aqua
Ethylenediamine Ethylenediamine
Ethylenediaminetetraacetate Ethylenediaminetetraacetato

4. When several ligands of a particular kind are present, we use the Greek prefixes di-, tri-,
tetra-, penta-, and hexa- to name them. Thus, the ligands in the cation [Co(NH 3)4Cl2]+ are
“tetraamminedichloro.” (Note that prefixes are ignored when alphabetizing ligands.) If
the ligand itself contains a Greek prefix, we use the prefixes bis (2), tris (3), and tetrakis
(4) to indicate the number of ligands present. For example, the ligand ethylenediamine
 already contains di; therefore, if two such ligands are present the name is
bis(ethylenediamine).
5. The oxidation number of the metal is written in Roman numerals following the name of
the metal. For example, the Roman numeral III is used to indicate the +3 oxidation state
of chromium in [Cr(NH3)4Cl2]+, which is called tetraamminedichlorochromium(III) ion.
6. If the complex is an anion, its name ends in -ate. For example, in K 4[Fe(CN)6] the anion
[Fe(CN)6]4- is called hexacyanoferrate(II) ion. Note that the Roman numeral II indicates
the oxidation state of iron. Table below gives the names of anions containing metal
atoms.

NAMES OF ANIONS CONTAINING METAL ATOMS

Metal Name of metal in anionic complex
Aluminium Aluminate
Chromium Chromate
Cobalt Cobaltate
Copper Cuprate
Gold Aurate
Iron Ferrate
Lead Plumbate
Manganese Manganate
Molybdenum Molybdate
Nickel Nickelate
Silver Argentate
Tin Stannate
Tungsten Tungstate
Zinc Zincate

Trial Questions
Write the systematic names of the following coordination compounds:
a. Ni(CO)4,
b. NaAuF4,
 c. K3[Fe(CN)6],
d. [Cr(en)3]Cl3.

Solution
a. The CO ligands are neutral species and therefore the Ni atom bears no net charge. The
compound is called tetracarbonylnickel(0) , or more commonly, nickel tetracarbonyl.
b. The sodium cation has a positive charge; therefore, the complex anion has a negative
charge (AuF4-). Each fluoride ion has a negative charge so the oxidation number of gold
must be +3 (to give a net negative charge). The compound is called sodium
tetrafluoroaurate(III) .
c. The complex ion is the anion and it bears three negative charges because each potassium
ion bears a +1 charge. Looking at [Fe(CN)6]3-, we see that the oxidation number of Fe
must be +3 because each cyanide ion bears a -1 charge (-6 total). The compound is
potassium hexacyanoferrate(III). This compound is commonly called potassium
ferricyanide.
d. As we noted earlier, en is the abbreviation for the ligand ethylenediamine. Because there
are three chloride ions each with a -1 charge, the cation is [Cr(en)3] 3+. The en ligands are
neutral so the oxidation number of Cr must be +3. Because there are three en groups
present and the name of the ligand already contains di (rule 4), the compound is called
tris(ethylenediamine)chromium(III) chloride .

Magnetic Properties
Many transition metal compounds are paramagnetic due to the presence of unpaired electrons.
Magnetic moment of each such electron is associated with its spin angular momentum and
orbital angular momentum. For the compounds of the first transition series, the orbital angular
momentum quantum number is effectively quenched and hence is of no significance. For these
the magnetic moment is determined by the number of electrons and is calculated by using ‘spin-
only’ formula, i.e., µ s = √n(n+2) where n is the number of unpaired electrons and µs is the
magnetic moment in Bohr magneton (BM). A single 1s electron has a magnetic moment of 1.73
BM (1 BM = 9.2732 × 10-24 A m2).
The magnetic moment increases with increasing number of unpaired electrons. Thus, the
observed magnetic moment value gives a useful information about the number of unpaired
electrons present in the species. The magnetic moments calculated from the ‘spin-only’ formula
and those determined experimentally for some first row transition metal ions are given in the
table below.

Colour
Many transition metal ions are coloured due to d-d transitions. The energy absorbed in excitation
of an electron from a lower energy d orbital to a higher energy d orbital corresponds to the
frequency which generally lies in the visible region. The colour observed corresponds to the
complementary colour of the light absorbed. The frequency of light absorbed is determined by
the nature of ligand. A substance appears black if it absorbs all the visible light that strikes it. If it
absorbs no visible light, it is white or colourless. An object appears green if it absorbs all light
but reflects the green component. An object also looks green if it reflects all colours except red,
the complementary colour of green.

What has been said of reflected light also applies to transmitted light (that is, the light that passes
through the medium, for example, a solution). Consider the hydrated cupric ion, [Cu(H 2O)6]2+,
which absorbs light in the orange region of the spectrum so that a solution of CuSO 4 appears blue
to us. When the energy of a photon is equal to the difference between the ground state and an
excited state, absorption occurs as the photon strikes the atom (or ion or compound), and an
electron is promoted to a higher level. This knowledge enables us to calculate the energy change
involved in the electron transition. The energy of a photon is given by
E = hv
where h represents Planck’s constant (6.63 x 10-34 J.s) and v is the frequency of the radiation.

Alloy formation
The transition metals readily form alloys with each other because of similar radii. The alloys so
formed are hard and have often high melting points. The best known are ferrous alloys;
vanadium, chromium, molybdenum, tungsten and manganese are used for the production of
variety of steels and stainless steel. Industrially important alloys of transition metals with non-
transition metals are brass (copper-zinc), bronze (copper-tin) and so on.

Metallurgy
The extraction of silver and gold by the formation of cyanide complexes and the purification of
nickel by converting the metal to the gaseous compound Ni(CO) 4 are typical examples of the use
of coordination compounds in metallurgical processes.

Therapeutic chelating agents

Earlier we mentioned that the chelating agent EDTA is used in the treatment of lead poisoning.
Certain platinum-containing compounds can effectively inhibit the growth of cancerous cells.

Chemical analysis
Although EDTA has a great affinity for a large number of metal ions (especially 2+ and 3+ ions),
other chelates are more selective in binding. For example, dimethylglyoxime, forms an insoluble
brick-red solid with Ni2+ and an insoluble bright-yellow solid with Pd2+. These characteristic
colors are used in qualitative analysis to identify nickel and palladium. Further, the quantities of
ions present can be determined by gravimetric analysis as follows: To a solution containing Ni 2+
ions, say, we add an excess of dimethylglyoxime reagent, and a brick-red precipitate forms. The
precipitate is then filtered, dried, and weighed. Knowing the formula of the complex, we can
readily calculate the amount of nickel present in the original solution.
Detergents
The cleansing action of soap in hard water is hampered by the reaction of the Ca 2+ ions in the
water with the soap molecules to form insoluble salts or curds. In the late 1940s the detergent
industry introduced a “builder,” usually sodium tripolyphosphate, to circumvent this problem.
The tripolyphosphate ion is an effective chelating agent that forms stable, soluble complexes
with Ca2+ ions. Sodium tripolyphosphate revolutionized the detergent industry. However, because
phosphates are plant nutrients, waste waters containing phosphates discharged into rivers and
lakes cause algae to grow, resulting in oxygen depletion. Under these conditions most or all
aquatic life eventually succumbs. This process is called eutrophication. Consequently, many
states have banned phosphate detergents since the 1970s, and manufacturers have reformulated
their products to eliminate phosphates.