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RY
We have measured two extensive properties (mass and volume) of the same
sample of matter. This allows us to define a new quantity, the quotient m/V
which defines another property of water which we call the density. Unlike the
mass and the volume, which by themselves refer only to individual samples
of water, the density (mass per unit volume) is a property of all samples of
pure water at the same temperature. Density is an example of an intensive
property of matter.
Intensive properties are extremely important, because every possible
kind of matter possesses a unique set of intensive properties that
distinguishes it from every other kind of matter. Some intensive properties
can be determined by simple observations: color (absorption spectrum),
melting point, density, solubility, acidic or alkaline nature, and density are
common examples. Even more fundamental, but less directly observable, is
chemical composition.
The more intensive properties we know, the more precisely we can
characterize a sample of matter. Intensive properties are extremely
important, because every possible kind of matter possesses a unique set of
intensive properties that distinguishes it from every other kind of matter. In
other words, intensive properties serve to characterize matter. Many
of the intensive properties depend on such variables as the temperature and
pressure, but the ways in which these properties change with such variables
can themselves be regarded as intensive properties.
Problem Example:
Classify each of the following as an extensive or intensive property.
1. The volume of beer in a mug
2. The percentage of alcohol in
the beer
3. The number of calories of
energy you derive from
eating a banana
4. The number of calories of
energy made available to
your body when you
consume 10.0 g of sugar
5. The mass of iron present in
your blood
6. The mass of iron present in 5
mL of your blood
7. The electrical resistance of a
piece of 22-gauge copper
wire.
8. The electrical resistance of a
1-km length of 22-gauge
copper wire
9. The pressure of air in a
bicycle tire
Notice, in the bottom line of boxes above, that "mixtures" and "pure
substances" can fall into either the homogeneous or heterogeneous
categories.
Since this latter schema covers virtually all matter that we encounter in the
world, it is important that you thoroughly understand the meaning of each
part of it. We will begin by looking at the distinction represented in the top
line of the diagram.
The phase
boundaries in an oilvinegar salad
dressing are easy to
see...
direction of travel is slightly bent, and a portion of the light gets reflected
back; it is these reflected and distorted light
rays emerging from that reveal the chunks
of ice floating in the liquid.
If, instead of visible chunks of material, the
second phase is broken into tiny particles, the light rays usually bounce off
the surfaces of many of these particles in random directions before they
emerge from the medium and are detected by the eye. This phenomenon,
known as scattering, gives multiphase systems of this kind a cloudy
appearance, rendering them translucent instead of transparent. Two very
common examples are ordinary fog, in which water droplets are suspended
in the air, and milk, which consists of butterfat globules suspended in an
aqueous solution.
Getting back to our classification,
we can say that
Homogeneous
matter
consists of a single phase
throughout
its
volume;
heterogeneous
matter
contains two or more phases.
Dichotomies
("either-or"
classifications) often tend to break down when closely examined, and the
distinction between homogeneous and heterogeneous matter is a good
example; this is really a matter of degree, since at the microscopic level all
matter is made up of atoms or molecules separated by empty space! For
most practical purposes, we consider matter as homogeneous when any
discontinuities it contains are too small to affect its visual appearance.
How large must a molecule or an agglomeration of molecules be before
it begins to exhibit properties of a being a separate phase? Such particles
span the gap between the micro and macro worlds, and have been known as
colloids since they began to be studied around 1900. But with the
development of nanotechnology in the 1990s, this distinction has become
even more fuzzy.
2.5
The air around us, most of the liquids and solids we encounter, and all
too much of the water we drink consists not of pure substances, but of
mixtures. You probably have a general idea of what a mixture is, and how it
differs from a pure substance; what is the scientific criterion for making this
distinction?
the
2.7.1
CARBOHYDRATES
2.7.2
LIPIDS
Certain fatty acids have one or more double bonds in their molecules.
Fats that include these molecules are unsaturated fats. Other fatty acids
have no double bonds. Fats that include these fatty acids are saturated fats.
In most human health situations, the consumption of unsaturated fats is
preferred to the consumption of saturated fats.
Fats stored in cells usually form clear oil droplets called globules
because fats do not dissolve in water. Plants often store fats in their seeds,
and animals store fats in large, clear globules in the cells of adipose tissue.
The fats in adipose tissue contain much concentrated energy. Hence, they
serve as a reserve energy supply to the organism. The enzyme lipase breaks
down fats into fatty acids and glycerol in the human digestive system.
A fat molecule is constructed by combining a
glycerol molecule with three fatty acid molecules.
(Two saturated fatty acids and one unsaturated
fatty acid are shown for comparison.) The
constructed molecule is at the bottom.
2.7.3PROTEINS
Proteins, among the most complex of all
organic compounds, are composed of amino
acids (see Figure 2-4), which contain carbon,
hydrogen, oxygen, and nitrogen atoms. Certain amino acids also have sulfur
atoms, phosphorus, or other trace elements such as iron or copper.
The structure and chemistry of amino acids. When two amino acids
are joined in a dipeptide, the OH of one amino acid is removed, and the H
of the second is removed. So, water is removed. A dipeptide bond (right)
forms to join the amino acids together.
2.8.1
Distillation
A mixture of two volatile liquids is partly boiled away; the first portions
of the condensed vapor will be enriched in the component having the lower
boiling point.
Note that if all the liquid were boiled away, the distillate would be
identical with the original liquid. But if, say, half of the liquid is distilled, the
distillate would contain a larger fraction of the more volatile component.
If the distillate is then re-distilled, it can be further enriched in the lowboiling liquid. By repeating this process many times (aided by the
fractionating column above the boiling vessel), a high degree of separation
can be achieved.
2.7.2
Fractional crystallization
Note that because the various components of granite are not removed
as they crystallize out, they remain embedded in the solidified material.
2.7.3
Liquid-liquid extraction
in
2.7.4
Solid-liquid extraction
2.7.5Chromatography
PHYSICAL PROPERTIES
(25C)
CHEMICAL PROPERTIES
forms an oxide Na2O and a hydride NaH
2. All collisions between gas particles are perfectly elastic (meaning that
the kinetic energy of the system is conserved).
3. The volume of the gas molecules in a gas is negligible.
4. Gases have no intermolecular attractive or repulsive forces.
5. The average kinetic energy of the gas is directly proportional to its
Kelvin temperature and is the same for all gases at a specified
temperature.
Only four measurable properties are used to describe a gas: its quantity,
temperature, volume, and pressure. The quantity (amount) of the gas is
usually expressed in moles (n). The temperature, T, of gases must always be
converted to the Kelvin temperature scale (the absolute temperature scale).
The volume, V, of a gas is usually given in liters. Finally, the pressure, P, of a
gas is usually expressed in atmospheres. Gases are often discussed in terms
of standard temperature and pressure (STP), which means 273K (or
0C) and 1 atm.
Example
Which of the following statements is not true of ideal gases?
1. The volume occupied by gas particles is only significant at very low
pressures.
2. Gas molecules occupy an insignificant volume compared to the volume
of the container that holds them.
3. The particles of a gas move in random straight line paths until a
collision occurs.
4. The collisions that occur between gas particles are considered elastic.
5. At a given temperature, all gas molecules within a sample possess the
same average kinetic energy.
Explanation
In this example, choice 1 is incorrect. Choices 2, 3, 4, and 5 all describe
an ideal gas. Choice 1 makes an incorrect assumption: it begins with a true
statement about volume not being very significant but then turns around and
gives the incorrect scenarioif the pressure is low, then gas particles
undergo very few collisions, so the volume is insignificant. The volume only
becomes significant if gas particles collide often, increasing the chances that
intermolecular forces will hold them together.
Measuring the Pressure of a Gas
Gas pressure is a gauge of the number and force of collisions between
gas particles and the walls of the container that holds them. The SI unit for
pressure is the pascal (Pa), but other pressure terms include atmospheres
(atms), millimeters of mercury (mmHg), and torr. The following is a list
of all of the standard pressure in every unit for pressure. Memorize these for
the exam so you can convert units where necessary:
760 mmHg
760 torr
1.00 atm
101,325 Pa
101.325 kPa
The piece of lab equipment specifically designed to measure the
pressure of gases is known as the barometer. A barometer uses the height
of a column of mercury to measure gas pressure in millimeters of mercury or
torr (1 mmHg = 1 torr). The mercury is pushed up the tube from the dish
until the pressure at the bottom of the tube (due to the mass of the mercury)
is balanced by the atmospheric pressure.
When using a barometer, you calculate gas pressure with the following
equation:
Gas pressure = atmospheric pressure - h (height of the mercury)
The open-tube manometer is another device that can be used to
measure pressure. The open-tube manometer is used to measure the
pressure of a gas in a container.
A graph of Boyle's
original data
This relationship between pressure and volume was first noted by two
new scientists, Richard Towneley and Henry Power. Robert Boyle confirmed
their discovery through experiments and published the results. According to
Robert Gunther and other authorities, it was Boyle's assistant, Robert Hooke,
who built the experimental apparatus. Boyle's law is based on experiments
with air, which he considered to be a fluid of particles at rest in between
small invisible springs. At that time, air was still seen as one of the four
elements, but Boyle disagreed. Boyle's interest was probably to understand
Example
A sample of gas at 15C and 1 atm has a volume of 2.50 L. What
volume will this gas occupy at 30C and 1 atm?
Explanation
The pressure remains the same, while the volume and temperature change
this is the hallmark of a Charless law question.
So,
the same for the lightest gas (hydrogen) as for a heavy gas such as carbon
dioxide or bromine.
The law can be stated mathematically
.
where:
V is the volume of the gas.
n is the amount of substance of the gas.
k is a proportionality constant.
The most important consequence of Avogadro's law is that the ideal gas
constant has the same value for all gases. This means that the constant
where:
p is the pressure of the gas
T is the temperature of the gas
has the same value for all gases, independent of the size or mass of the gas
molecules.
One mole of an ideal gas occupies 22.4 liters (dm) at STP, and
occupies 24.45 litres at SATP (Standard Ambient Temperature and Pressure =
273K and 1 atm or 101.325 kPa). This volume is often referred to as the
molar volume of an ideal gas. Real gases may deviate from this value.
Or to put it another way "the principle that equal volumes of all gases
at the same temperature and pressure contain the same number of
molecules. Thus, the molar volume of all ideal gases at 0 C and a pressure
of 1 atm. is 22.4 liters"
Avogadro's number is one of the fundamental constants of chemistry. It
permits calculation of the amount of pure substance (mole), the basis of
stoichiometric relationships. It also makes possible determination of how
much heavier a simple molecule of one gas is than that of another, as a
result the relative molecular weights of gases can be ascertained by
comparing the weights of equal volumes.
PV = nRT
where
P = pressure (atm), V = volume (L),
n = number of moles (mol),
R = 0.08206 L atm/mol K, and
T = temperature (K).
Now try an example using the ideal gas law equation.
Example
A 16.0 g sample of methane gas, CH4, the gas used in chemistry lab, has a
volume of 5.0 L at 27C. Calculate the pressure.
Explanation
Looking at all the information given, you have a mass, a volume, and a temperature, and
you need to find the pressure of the system. As always, start by checking your units. You must
first convert 16.0 g of CH4 into moles: 16.0 g CH4
1 mol CH4/16.0 g CH4 = 1 mol of methane.
The volume is in the correct units, but you must convert the temperature into Kelvins: 27 + 273 =
300K. Now youre ready to plug these numbers into the ideal gas law equation:
PV = nRT
(P) (5.0 L) = (1.0 mol) (0.0821 L
atm/mol
Among the experiments that led John Dalton to propose the atomic
theory were his studies of mixtures of gases. In 1803 Dalton summarized his
observations as follows: For a mixture of gases in a container, the total
pressure exerted is the sum of the pressures that each gas would exert if it
were alone. This statement, known as Daltons law of partial pressures,
can be expressed as follows:
Ptotal = P1 + P2 + . . . Pn
where the subscripts refer to the individual gases (gas 1, gas 2, and so on).
The symbols
P1, P2, P3, and so on represent each partial pressure, the pressure that a
particular gas
would exert if it were alone in the container.
Assuming that each gas behaves ideally, the partial pressure of each
gas can be calculated from the ideal gas law:
Where:
ek is the average translation kinetic energy,
R is the gas constant,
NA is Avogadro's number, and
T is temperature in Kelvins.
Since R and NA are constants, this means that the Kelvin temperature
(T) of a gas is directly proportional to the average kinetic energy of its
molecules. This means that at a given temperature, different gases (for
example He or O2) will the same average kinetic energy.
Graham's Law
Gas molecules move constantly and randomly throughout the volume
of the container they occupy. When examining the gas molecules
individually, we see that not all of the molecules of a particular gas at a
given temperature move at exactly the same speed. This means that each
molecule of a gas have slightly different kinetic energy. To calculate the
with
The root mean square speed, urms, can be determined from the
temperature and molar mass of a gas.
with
T temperature (Kelvin)
When examining the root mean square speed equation, we can see that
the changes in temperature (T) and molar mass (M) affect the speed of the
gas molecules. The speed of the molecules in a gas is proportional to the
temperature and is inversely proportional to molar mass of the gas. In other
words, as the temperature of a sample of gas is increased, the molecules
speed up and the root mean square molecular speed increases as a result.
Graham's Law states that the rate of effusion of two different gases at the
same conditions are inversely proportional to the square roots of their molar
masses as given by the following equation:
Example:
Calculate the root mean square speed, urms , in m/s of helium at 30oC.
Solution:
Start by converting the molar mass for helium from g/mol to kg/mol.
Now, using the equation for urms substitute in the proper values for each
variable and perform the calculation.
Stone
Fur
In the late 1700s and early 1800s, scientists began noticing that when
certain substances, like hydrogen and oxygen, were combined to produce a
new substance, like water, the reactants (hydrogen and oxygen) always
reacted in the same proportions by mass. In other words, if 1 gram of
hydrogen reacted with 8 grams of oxygen, then 2 grams of hydrogen would
react with 16 grams of oxygen, and 3 grams of hydrogen would react with 24
grams of oxygen. Strangely, the observation that hydrogen and oxygen
always reacted in the same proportions by mass wasnt special. In fact, it
turned out that the reactants in every chemical reaction reacted in the same
proportions by mass. This observation is summarized in the law of definite
proportions. Take, for example, nitrogen and hydrogen, which react to
produce ammonia. In chemical reactions, 1 gram of hydrogen will react with
4.7 grams of nitrogen, and 2 grams of hydrogen will react with 9.4 grams of
nitrogen. Can you guess how much nitrogen would react with 3 grams of
hydrogen? Scientists studied reaction after reaction, but every time the
result was the same. The reactants always reacted in the same proportions.
At the same time that scientists were finding this pattern out, a man named
John Dalton was experimenting with several reactions in which the reactant
elements formed more than one type of product, depending on the
experimental conditions he used. One common reaction that he studied was
the reaction between carbon and oxygen. When carbon and oxygen react,
they produce two different substances well call these substances A and
B. It turned out that, given the same amount of carbon, forming B always
required exactly twice as much oxygen as forming A. In other words, if you
can make A with 3 grams of carbon and 4 grams of oxygen, B can be made
with the same 3 grams of carbon, but with 8 grams oxygen. Dalton asked
himself why does B require 2 times as much oxygen as A? Why not 1.21
times as much oxygen, or 0.95 times as much oxygen? Why a whole number
like 2? The situation became even stranger when Dalton tried similar
experiments with different substances.
For example, when he reacted nitrogen and oxygen, Dalton discovered
that he could make three different substances well call them C, D, and
E. As it turned out, for the same amount of nitrogen, D always required
twice as much oxygen as C. Similarly, E always required exactly four times as
much oxygen as C. Once again, Dalton noticed that small whole numbers
J.J. Thomson
conducted
experiments that
suggested that
Daltons atomic
theory wasnt
telling the entire
story.
The figure shows a basic diagram of a cathode ray tube like the one J. J.
Thomson would have used. A cathode ray tube is a small glass tube with a
would have to contain a whole lot of electrons. But theres another, even
bigger problem: electrons
are negatively charged.
Therefore, if atoms were
made
entirely
out
of
electrons, atoms would be
negatively
charged
themselves
and
that
would mean all matter was
negatively charged as well.
Of course, matter isnt
Thomsons plum pudding model was much
negatively charged. In fact,
like a chocolate chip cookie. Notice how
most matter is what we call
the chocolate chips are the negatively
neutral it has no charge at
charged electrons, while the positive
all. If matter is composed of
charge is spread throughout the entire
atoms, and atoms are
batter.
composed
of
negative
electrons, how can matter
be neutral? The only possible explanation is that atoms consist of more than
just electrons. Atoms must also contain some type of positively charged
material that balances the negative charge on the electrons. Negative and
positive charges of equal size cancel each other out, just like negative and
positive numbers of equal size. What do you get if you add +1 and -1? You
get 0, or nothing. Thats true of numbers, and thats also true of charges. If
an atom contains an electron with a -1 charge, but also some form of
material with a +1 charge, overall the atom must have a (+1) + (-1) = 0
charge in other words, the atom must be neutral, or have no charge at all.
Based on the fact that atoms are neutral, and based on J. J. Thomsons
discovery that atoms contain negative subatomic particles called
electrons, scientists assumed that atoms must also contain a positive
substance. It turned out that this positive substance was another kind of
subatomic particle, known as the proton. Although scientists knew that
atoms had to contain positive material, protons werent actually discovered,
or understood, until quite a bit later. When Thomson discovered the negative
electron, he realized that atoms had to contain positive material as well
otherwise they wouldnt be neutral overall. As a result, Thomson formulated
whats known as the plum pudding model for the atom. According to the
plum pudding model, the negative electrons were like pieces of fruit and
the positive material was like the batter or the pudding. This made a lot of
sense given Thomsons experiments and observations. Thomson had been
able to isolate electrons using a cathode ray tube; however he had never
managed to isolate positive particles. As a result, Thomson theorized that
the positive material in the atom must form something like the batter in a
plum pudding, while the negative electrons must be scattered through this
batter. (If youve never seen or tasted a plum pudding, you can think of a
chocolate chip cookie instead. In that case, the positive material in the atom
would be the batter in the chocolate chip cookie, while the negative
electrons would be scattered through the batter like chocolate chips.)
Notice how easy it would be to pick the pieces of fruit out of a plum
pudding. On the other hand, it would be a lot harder to pick the batter out of
the plum pudding, because the batter is everywhere. If an atom were similar
to a plum pudding in which the electrons are scattered throughout the
batter of positive material, then youd expect it would be easy to
pick out the electrons, but a lot harder to pick out the positive material.
J.J. Thomson had measured the charge to mass ratio of the electron,
but had been unable to accurately measure the charge on the electron. With
his oil drop experiment, Robert Millikan was able to accurately measure the
charge of the electron. When combined with the charge to mass ratio, he
was able to calculate the mass of the electron. What Millikan did was to put a
harge on tiny droplets of oil and measured their rate of descent. By varying
the charge on different drops, he noticed that the electric charges on the
drops were all multiples of 1.6x10-19C, the charge on a single electron.
Keypoints
The atom's electron cloud does not influence alpha particle scattering.
The atom itself is about one trillion (10^12) the size of the nucleus.
That's like putting a marble in the center of a football field.
Atomic shells
do not necessarily
fill up with
electrons
in
consecutive
order.
The
electrons of the first 18
elements
in
the periodic table are added
in a regular manner, each shell being filled to a designated limit before a
new shell is started. Beginning with the 19th element, the outermost electron
starts a new shell before the previous shell is completely filled. A regularity is
still maintained, however, as electrons fill successive shells in a repetitious
back-and-forth pattern. The result is the regular repetition of chemical
properties for atoms of increasing atomic weight that corresponds to the
arrangement of the elements in the periodic table.
It is convenient to visualize the electrons moving about the nucleus of
an atom much as if they were planets moving about the sun. This view is
much more precise than that held by contemporary physicists, however. It is
now known that it is impossible to pinpoint the precise position of an electron
in the atom's space without disturbing its predicted location at some future
time. This uncertainty is resolved by attributing to the atom a cloudlike form,
in which the electron's position is defined in terms of the probability of
finding it at some distance from the nucleus. This rather fuzzy schematic
conception of the atom may be reconciled with the solar-system model by
noting that in the tiny space of the atom the electron, which makes many
billions of orbits around the nucleus in a single second, is everywhere at
once. The cloud view thus gives a form to the atom that is not supplied by a
solar-system model.
In the years since Thomson and Rutherford, a great deal has been
learned about atomic structure. Because much of this material will be
covered in detail in later chapters, only an introduction will be given here.
The simplest view of the atom is that it consists of a
tiny nucleus (with a diameter of about 10_13 cm) and electrons that move
about the nucleus at an average distance of about 10_8 cm from it.
As we will see later, the chemistry of an atom mainly results from its
electrons. For this reason, chemists can be satisfied with a relatively crude
nuclear model. The nucleus is assumed to contain protons, which have a
positive charge equal in magnitude to the electrons negative charge, and
neutrons, which have virtually the same mass as a proton but no charge.
The masses and charges of the electron, proton, and neutron are shown in
Table.
Two striking things about the nucleus are its small size compared with
the overall size of the atom and its extremely high density. The tiny nucleus
accounts for almost all the atoms mass. Its great density is dramatically
demonstrated by the fact that a piece of nuclear material about the size of a
pea would have a mass of 250 million tons!
Atoms are the basic units of matter and the defining structure of
elements. Atoms are made up of three particles: protons, neutrons and
electrons.
Protons and neutrons are heavier than electrons and reside in the
center of the atom, which is called the nucleus. Electrons are extremely
lightweight and exist in a cloud orbiting the nucleus. The electron cloud has a
radius 10,000 times greater than the nucleus.
Protons and neutrons have approximately the same mass. However,
one proton weighs more than 1,800 electrons. Atoms always have an equal
number of protons and electrons, and the number of protons and neutrons is
usually the same as well. Adding a proton to an atom makes a new element,
while adding a neutron makes an isotope, or heavier version, of that atom.
4.7.1
Nucleus
The nucleus was discovered in 1911, but its parts were not identified
until 1932. Virtually all the mass of the atom resides in the nucleus. The
nucleus is held together by the "strong force," one of the four basic forces in
nature. This force between the protons and neutrons overcomes the
repulsive electrical force that would, according to the rules of electricity,
push the protons apart otherwise.
4.7.2
Protons
4.7.3
Electrons
4.7.4
Neutrons
4.7.5
Isotopes
Ivanovich
similar
essentially
classify
Meyer
gave
a
of
Dr. Seaborg and his colleagues are also responsible for the identification of
more than 100 isotopes of elements.
5.4.1Atomic Radius
We can never determine the atomic radius of an atom because there is
never a zero probability of finding an electron, and thus never a distinct
boundary to the atom. All that we can measure is the distance between two
nuclei (internuclear distance). A covalent radius is one-half the distance
between the nuclei of two identical atoms. An ionic radius is one-half the
distance between the nuclei of two ions in an ionic bond. The distance must
be apportioned for the smaller cation and larger anion. A metallic radius is
one-half the distance between the nuclei of two adjacent atoms in a
crystalline structure. The noble gases are left out of the trends in atomic radii
because there is great debate over the experimental values of their atomic
radii. The SI units for measuring atomic radii are the nanometer (nm) and the
picometer (pm). 1 nm = 1 X 10-9 m; 1 pm = 1 X 10-12 m.
Figure 3:
Metallic Radii
10 inner electrons (S) would screen out the positive charge of ten protons.
Therefore there would be and effective nuclear charge of 17-10 or +7. The
effective nuclear charge shows that the nucleus is pulling the outer electrons
with a +7 charge and therefore the outer electrons are pulled closer to the
nucleus and the atomic radii is smaller. In summary, the greater the nuclear
charge, the greater pull the nucleus has on the outer electrons and the
smaller the atomic radii. In contrast, the smaller nuclear charge, the lesser
pull the nucleus has on the outer electrons, and the larger atomic radii.
Additionally, as the atomic number increases, the effective nuclear charge
also increases. Figure 3 depicts the effect that the effective nuclear charge
has on atomic radii.
Now we are ready to describe the atomic radius trend in the periodic
table. The atomic number increases moving left to right across a period and
subsequently so does the effective nuclear charge. Therefore, moving left to
right across a period the nucleus has a greater pull on the outer electrons
and the atomic radii decreases. Moving down a group in the periodic table,
the number of filled electron shells increases. In a group, the valence
electrons keep the same effective nuclear charge, but now the orbitals are
farther from the nucleus. Therefore, the nucleus has less of a pull on the
outer electrons and the atomic radii are larger.
We can now use these concept to explain the atomic radius differences
of cations and anions. A cation is an atom that has lost one of its outer
electrons. Cations have a smaller radius than the atom that they were
formed from. With the loss of an electron, the positive nuclear charge out
powers the negative charge that the electrons exert. Therefore, the positive
nucleus pulls the electrons tighter and the radius is smaller. An anion is an
atom that has gained an outer electron. Anions have a greater radius than
the atom that they were formed from. The gain of an electron does not alter
the nuclear charge, but the addition of an electron causes a decrease in the
effective nuclear charge. Therefore, the electrons are held more loosely and
the atomic radius is increased.
1st
496
738
577
786
1060
999.6
1256
1520
2nd
4562
1451
1817
1577
1903
2251
2297
2666
3rd
4th
5th
6th
7th
7733
2745
3232
2912
3361
3822
3931
11580
4356
4957
4564
5158
5771
16090
6274
7013
6542
7238
21270
8496
9362
8781
27110
11020
12000
These are the ionization energies for the period three elements. Notice
how Na after in the second I.E, Mg in the third I.E., Al in the fourth I.E., and so
on, all have a huge increase in energy compared to the proceeding one. This
The ionization energy is only a general rule. There are some instances
when this trend does not prove to be correct. These can typically be
explained by their electron configuration. For example, Magnesium has
higher ionization energy than Aluminum. Magnesium has an electron
configuration of [Ne]3s2. Magnesium has a high ionization energy because it
has a filled 3s orbital and it requires a higher amount of energy to take an
electron from the filled orbital.
5.4.3Electron Affinity
Electron affinity (E.A.) is the energy change that occurs when an
electron is added to a gaseous atom. Electron affinity can further be defined
as the enthalpy change that results from the addition of an electron to a
gaseous atom. It can be either positive or negative value. The greater the
negative value, the more stable the anion is.
X(g) + e- ---> X- + Energy (Exothermic) The electron affinity is positive
X(g) + e- + Energy ---> X- (Endothermic) The electron affinity is
negative
5.4.4Electronegativity
5.4.5Metallic Character
The metallic character is used to define the chemical properties that metallic elements
present. Generally, metals tend to lose electrons to form cations. Nonmetals tend to gain
electrons to form anions. They also have a high oxidation potential therefore they are easily
oxidized and are strong reducing agents. Metals also form basic oxides; the more basic the oxide,
the higher the metallic character.
As you move across the table from left to right, the metallic character decreases, because
the elements easily accept electrons to fill their valance shells. Therefore, these elements take on
the nonmetallic character of forming anions. As you move up the table, the metallic character
decreases, due to the greater pull that the nucleus has on the outer electrons. This greater pull
makes it harder for the atoms to lose electrons and form cations.
5.4.6
Other
Trends
Melting
Points:
According
to General
Chemistry
by Petrucci,
trends
in
melting
points and
molecular
mass
of
binary
carbonhalogen compounds and hydrogen halides are due to intermolecular forces. Melting destroys the
arrangement of atoms in a solid; therefore the amount of heat necessary for melting to occur
depends on the strength of attraction between the atoms. This strength of attraction increases as
the number of electrons increase. Increase in electrons increases bonding.
Example: Melting point of HF should be approximately -145 C based off melting points
of HCl, HBr, and HI, but the observed value is -83.6 (Petrucci)
Heat and electricity conductibility vary regularly across a period. Melting points may
increase gradually or reach a peak within a group then reverse direction.
The Periodic Table of Elements categorizes like elements together. Dmitri Mendeleev, a
Russian scientist, was the first to create a widely accepted arrangement of the elements in 1869.
Mendeleev believed that when the elements are arranged in order of increasing atomic mass,
certain sets of properties recur periodically. Although most modern periodic tables are arranged
in eighteen groups (columns) of elements, Mendeleev's original periodic table had the elements
organized into eight groups and twelve periods (rows).
On the periodic table, elements that have similar properties are in the same groups
(vertical). From left to right, the atomic number (z) of the elements increases from one period to
the next (horizontal). The groups are numbered at the top of each column and the periods on the
left next to each row. The main group elements are groups 1,2 and 13 through 18. These groups
contain the most naturally abundant elements, and are the most important for life. The elements
shaded in light pink in the table above are known as transition metals. The two rows of elements
starting at z=58, are sometimes called inner transition metals and have that have been extracted
and placed at the bottom of the table, because they would make the table too wide if kept
continuous. The 14 elements following lanthanum (z=57) are called lanthanides, and the 14
following actinium (z=89) are called actinides.
Elements in the periodic table can be placed into two broad categories, metals and
nonmetals. Most metals are good conductors of heat and electricity, are malleable and ductile,
and are moderate to high melting points. In general, nonmetals are nonconductors of heat and
electricity, are nonmalleable solids, and many are gases at room temperature. Just as shown in
the table above, metals and nonmetals on the periodic table are often separated by a stairstep
diagonal line, and several elements near this line are often called metalloids (Si, Ge, As, Sb, Te,
and At). Metalloids are elements that look like metals and in some ways behave like metals but
also have some nonmetallic properties. The group to the farthest right of the table, shaded
orange, is known as the noble gases. Noble gases are treated as a special group of nonmetals.
The shapes of the first five atomic orbitals: 1s, 2s, 2p x, 2py, and 2pz.
The colors show the wave function phase. These are graphs of (x,y,z)
functions which depend on the coordinates of one electron. To see the
elongated shape of (x,y,z)2 functions that show probability density more
directly, see the graphs of d-orbitals below.
An atomic orbital is a mathematical function that describes the wavelike behavior of either one electron or a pair of electrons in an atom.[1] This
function can be used to calculate the probability of finding any electron of an
atom in any specific region around the atom's nucleus. The term may also
refer to the physical region or space where the electron can be calculated to
be present, as defined by the particular mathematical form of the orbital.[2]
Each orbital in an atom is characterized by a unique set of values of
the three quantum numbers n, , and m, which respectively correspond to
the electron's energy, angular momentum, and an angular momentum
vector component (the magnetic quantum number). Any orbital can be
occupied by a maximum of two electrons, each with its own spin quantum
number. The simple names s orbital, p orbital, d orbital and f orbital
refer to orbitals with angular momentum quantum number = 0, 1, 2 and 3
respectively. These names, together with the value of n, are used to describe
the electron configurations of atoms. They are derived from the description
by early spectroscopists of certain series of alkali metal spectroscopic lines
as sharp, principal, diffuse, and fundamental. Orbitals for > 3 continue
alphabetically, omitting j (g, h, i, k, ...).
Atomic orbitals are the basic building blocks of the atomic orbital
model (alternatively known as the electron cloud or wave mechanics
5.9 METALLOIDS
As mentioned in the introduction, metalloids are located along the
staircase separating the metals from the nonmetals on the periodic table.
Boron, silicon, germanium, arsenic, antimony, and tellurium all have metal
and nonmetal properties. For example, Silicon has a metallic luster but is
brittle and is an inefficient conductor of electricity like a nonmetal. As the
5.10 HALOGENS
Halogens are comprised of the five nonmetal elements Flourine,
Chlorine, Bromine, Iodine, and Astatine. They are located on group 17 of the
periodic table and have a charge of -1. The term "halogen" means "saltformer" and compounds that contain one of the halogens are salts. The
physical properties of halogens vary significantly as they can exist as solids,
liquids, and gases at room temperature. However in general, halogens are
very reactive, especially with the alkali metals and earth metals of groups 1
and 2 with which they form ionic compounds.
As shown, the 1s subshell can hold only two electrons and when
filled the electrons have opposite spins.
Example
If we look at the correct electron configuration of Nitrogen (Z = 7),
a very important element in the biology of plants: 1s2 2s2 2p3
We can clearly see that p orbitals are half filled as there are three
electrons and three p orbitals. This is because Hund's Rule states
that the three electrons in the 2p subshell will fill all the empty
orbitals first before filling orbitals with electrons in them. If we
Oxygen has one more electron than Nitrogen and as the orbitals
are all half filled the electron must pair up.
Exceptions
Although the Aufbau rule accurately predicts the electron configuration
of most elements, there are notable exceptions among the transition metals
and heavier elements. The reason these exceptions occur is that some
elements are more stable with fewer electrons in some subshells and more
electrons in others. A list of the exceptions to the Aufbau process is given
below.
Table 1: Exceptions to Electron Configuration Trends
Period 4:
Chromium: Z:24 [Ar] 3d54s1
Period 5:
Niobium: Z:41 [Kr] 5s1 4d4
Period 6:
Period 7:
Platinum: Z:78 [Xe] 6s1 4f14 5d9 Uranium: Z:92 [Rn] 7s2 5f3 6d1
Gold: Z:79 [Xe] 6s1 4f14 5d10
atomic number, Z. The rules above allow one to write the electron
configurations for all the elements in the periodic table.
Three methods are used to write electron configurations:
1. orbital diagrams
2. spdf notation
3. noble gas notation
Each method has its own purpose and each has its own drawbacks.
Note that in the orbital diagram, the two opposing spins of the electron can
be visualized. This is why it is sometimes useful to think about electron
configuration in terms of the diagram. However, because it is the most
time consuming method, it is more common to write or see electron
configurations in spdf notation and noble gas notation. Another example is
the electron configuration of iridium:
Example: Yttrium
Start with the straightforward problem of finding the electron configuration
of the element yttrium. As always, refer to the periodic table. The element
yttrium (symbolized Y) is a transition metal, found in the fifth period and in
Group 3. In total it has thirty-nine electrons. Its electron configuration is as
follows:
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d1
This is a much simpler and more efficient way to portray electron
configuration of an atom. A logical way of thinking about it is that all that is
required is to fill orbitals across a period and through orbital blocks. The
number of elements in each block is the same as in the energy level it
corresponds. For example, there are 2 elements in the s-block, and 10
elements in the d-block. Moving across, simply count how many elements
fall in each block. Yttrium is the first element in the fourth period dblock; thus there is one electron in that energy level. To check the answer,
verify that the subscripts add up to the atomic number. In this case,
2+2+6+2+6+2+10+6+2+1= 39 and Z=39, so the answer is correct.
A slightly more complicated example is the electron configuration of
bismuth (symbolized Bi, with Z = 83). The periodic table gives the following
electron configuration:
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p65s2 4d10 5p6 6s2 4f14 5d10 6p3
The reason why this electron configuration seems more complex is that
the f-block, the Lanthanide series, is involved. Most students who first learn
electron configurations often have trouble with configurations that must pass
through the f-block because they often overlook this break in the table and
skip that energy level. Its important to remember that when passing the 5d
and 6d energy levels that one must pass through the f-block lanthanoid and
actinoid series. Keeping this in mind, this "complex" problem is greatly
simplified.
Another method (but less commonly used) of writing the spdf notation
is the expanded notation format. This is the same concept as before, except
that each individual orbital is represented with a subscript. The p, d, and f
orbitals have different sublevels. The p orbitals are px, py, and pz, and if
represented on the 2p energy with full orbitals would look like: 2p x2 2py2 2pz2.
The expanded notation for neon (Ne, Z=10) is written as follows:
1s2 2s2 2px2 2py2 2pz2
The individual orbitals are represented, but the spins on the electrons
are not; opposite spins are assumed. When representing the configuration of
an atom with half filled orbitals, indicate the two half filled orbitals. The
expanded notation for carbon is written as follows:
1s2 2s2 2px1 2py1
Because this form of the spdf notation is not typically used, it is not as
important to dwell on this detail as it is to understand how to use the general
spdf notation.
Example: Vanadium
What is the electronic configuration of vanadium (V, Z=23)?
SOLUTION
Vanadium is the transition metal in the fourth period and the fifth group.
The noble gas preceding it is argon (Ar, Z=18), and knowing that vanadium
has filled those orbitals before it, argon is used as the reference noble gas.
The noble gas in the configuration is denoted E, in brackets: [E]. To find the
valance electrons that follow, subtract the atomic numbers: 23 - 18 = 5.
Instead of 23 electrons to distribute in orbitals, there are 5. Now there
is enough information to write the electron configuration:
Vanadium, V: [Ar] 4s2 3d3
6CHEMICAL BONDS
6.1 ENERGY AND BONDING
Lets start by imagining that there are two hydrogen atoms
approaching one another. As they move closer together, there are three
forces that act on the atoms at the same time. These forces are shown in
figure and are described below:
1. repulsive force between the electrons of the atoms, since like charges
repel
2. attractive force between the nucleus of one atom and the electrons of
another
3. repulsive force between the two positively-charged nuclei
In the example of the two hydrogen atoms, where the resultant force
between them is attraction, the energy of the system is zero when the atoms
are far apart (point A), because there is no interaction between the atoms.
When the atoms are closer together, attractive forces dominate and the
atoms are pulled towards each other. As this happens, the potential energy
of the system decreases because energy would now need to be supplied to
the system in order to move the atoms apart. However, as the atoms move
closer together (i.e. left along the horizontal axis of the graph), repulsive
forces start to dominate and this causes the potential energy of the system
to rise again. At some point, the attractive and repulsive effects are
balanced, and the energy of the system is at its minimum (point X). It is at
this point, when the energy is at a minimum, that bonding takes place.
The distance marked P is the bond length, i.e. the distance between the
nuclei of the atoms when they bond. Q represents the bond energy i.e. the
amount of energy that must be added to the system to break the bonds that
have formed. Bond strength means how strongly one atom attracts and is
held to another. The strength of a bond is related to the bond length, the size
of the bonded atoms and the number of bonds between the atoms. In
general, the shorter the bond length, the stronger the bond between the
atoms, and the smaller the atoms involved, the stronger the bond. The
greater the number of bonds between atoms, the greater will be the bond
strength.
Ionic Bonds
transfer or
extreme
electrons
a
in the
6.6.1
LEWIS THEORY
Between 1916 and 1919, Gilbert Newton Lewis, Walther Kossel, and Irving
Langmuir came up with a theory to explain chemical bonding. This theory
would be later called Lewis Theory and it is based on the following
principles:
1. Valence electrons, or the electrons in the outermost electron shell,
have an essential role in chemical bonding.
2. Ionic bonds are formed between atoms when electrons are
transferred from one atom to another. Ionic bond is a bond between
nonmetals and metals.
3. Covalent bonds are formed between atoms when pairs of electrons
are shared between atoms. A covalent bond is between two nonmetals.
4. Electrons are transferred/shared so that each atom may reach a more
stable electron configuration i.e. the noble gas configuration which
contains 8 valence electrons. This is called octet rule.
6.6.2
This Lewis symbol shows that carbon has four valence electrons in its
outer orbital and these four electrons play a major role in bonding of carbon
molecules.
Lewis symbols differ slightly for ions. When forming a Lewis symbol for
an ion, the chemical symbol is surrounded by dots that are used to represent
valence electrons, and the whole structure is placed in square brackets with
superscript representing the charge of the ion. An example of a Lewis symbol
for the cation and anion of Carbon is shown below:
Cation of Carbon
Anion of Carbon
Roman Numerals
A Roman numeral in parentheses, followed by the name of the
element, is used for elements that can form more than one positive
ion. This is usually seen with metals. You can use a chart to see the
possible valences for the elements.
Fe2+ Iron (II)
Fe3+ Iron (III)
Cu+ Copper (I)
Cu2+ Copper (II)
-ide
The -ide ending is added to the name of a monoatomic ion of an
element.
H- Hydride
F- Fluoride
O2- Oxide
S2- Sulfide
N3- Nitride
P3- Phosphide
hypo- and perIn the case where there is a series of four oxyanions, the hypo- and
per- prefixes are used in conjunction with the -ite and -ate suffixes.
The hypo- and per- prefixes indicate less oxygen and more oxygen,
respectively.
ClO- Hypochlorite
ClO2- Chlorite
ClO3- Chlorate
ClO4- Perchlorate
induced dipole interactions may exist. The image below illustrates a network
of induced dipole-induced dipole interactions.