Notes: Atoms and Periodicity

Atoms:
The atom is the base or building block for all matter. The atom is the smallest particle which still retains all the physical and chemical properties of an element. So, if you hold a pure gold nugget, the smallest piece of this element that would still be considered gold would be one atom. The atom is composed of 3 fundamental particles: the proton, neutron and electron. The following table describes these particles: Particle Charge Location AMU p + nucleus 1 n n/a nucleus 1 e orbit 0 AMU - Atomic Mass Unit 1/12 the mass of a carbon-12 atom The general concept of an atom has been around for thousands of years. Around 440 BC, Leucippus of Greece originated the concept of the atom. Democritus (Leucippuss student), Aristotle and Epicurus added to this concept in the following centuries. The following points are key to their theories: = correct = incorrect

Greek Atomic Theory:

1. 2. 3. 4. 5. 6. 7. 8. All matter is composed of atoms, which are bits of matter too small to be seen. Atoms cannot be further split into smaller portions. There is a void, which is empty space between atoms. Atoms are completely solid. Atoms are homogeneous, with no internal structure. Atoms are different in their sizes. Atoms are different in their shapes. Atoms are different in their weights.

This is amazing in that we are talking about men who lived over 2400 years ago. At the time they lacked the ability to properly clean their water, and frankly they did not know what they needed to clean in the water, and here they are correctly theorizing on atomic structure. The microscope will not be invented until 1590 over a millennia away! The next solid advancement in atomic theory comes from a Pennsylvania Quaker, John Dalton. The following assumptions summarize Daltons theory.

Daltons Atomic Theory:

1. All matter is composed of extremely small particles called atoms. 2. Atoms of any given element are identical in; a. size b. mass c. properties 3. Atoms of different elements are different in; a. size

b. mass c. properties 4. Atoms cannot be subdivided, created, or destroyed. 5. In chemical reactions, atoms are combined, separated, or rearranged. 6. Atoms of different elements combine in simple whole number ratios to form chemical compounds. And sometimes will create more than one compound with differing ratios. The last point defines the law of Definite Proportions. This law states that a molecule always has the same ratio of atoms. For example water is ALWAYS H2O, only two hydrogens and one oxygen. Another example, carbon dioxide, is always CO 2, never C2O or C2O2; carbon dioxide will only ever be CO2. Many of these are rewriting the Greek theory, the new concepts are found in the final two points. The concept that atoms only combine in simple whole number ratios and that chemical reactions are simply rearrangements of atoms. These concepts were hard for the scientific community of the 1800s to accept. At the time Alchemy, was still holding firm, the search for the philosophers stone was ongoing. The stone was the substance that would allow elements to be converted to other elements through chemical means, as in the turning of lead to gold. At the time it was known that both lead and gold were pure substance, which could not be broken down into smaller parts. Daltons theory basically told the alchemist you will never be able to turn lead into gold. Chemical reactions will only rearrange the atoms that the lead atoms are combined with, it will never make gold. The Greek and Dalton theories gave rise to questions of the atoms structure. The five most important scientists involved in the discovery of the atomic structure are JJ Thomson, Ernest Rutherford, Niels Bohr, Werner Heisenberg and James Chadwick. Thomsons theory is called the Plum Pudding Model, after a certain British holiday dessert which I am very glad has never caught on in the USA. In this model the atom is a round object composed of a positive mass embedded with small negatively charged particles. Thomson named his small negatively charged particles corpuscles. The corpuscles, thankfully, were later named electrons.

He discovered and proved the existence of electrons with the use of the cathode ray tube, the forerunner of the tube use in televisions.

Ernest Rutherford modified this structure. His gold foil experiment is the key to the center of the atom. In his experiment Rutherford used the new discovery of radioactivity, a radioactive element is aimed at a piece of gold foil. The element shot alpha particles at a piece of gold foil. The foil was surround by a wall coated with a phosphorescent material. When the alpha particle impacted the walls a spark of light was emitted. What Rutherfords group of scientists found was that most of the alpha particles passed right through the foil. This is contrary to Thomsons model as the alpha particles are positively charged and would surely be deflected by a solid positive mass. The very interesting point was that the particles that did not pass through were deflected or scattered. Some veered only slightly off their path, fewer were scattered to a larger degree and few yet were actually deflected back the direction in which they came. Rutherford therefore concluded that the atom has a very small, densely packed, positively charged center. Another scientist Frederick Soddy proved that the positive center is actually composed of protons. Particles with and equal yet opposite charge to that of the electron, but 1839 times more massive.

Though the two charged particles had been found by 1902, it took another 33 years for the final particle to be discovered. The neutron, is as its name implies, neutrally charged, in other words, it is not charged. This lack of a charge prevented it from interacting with the many detection devices of the time. It would have been many more years before its discovery if scientists, James Chadwick in particular, had not been looking for the neutron. The push to find this third particle was due to the variations in the masses of elements from different areas of the world. It seemed that elements from different regions chemically behaved the same but the atoms in the elements had a different mass. All forms of chemical analysis came up empty. The difference was the neutron, the uncharged particle of mass equal to that of the proton. Daltons second assumption in his atomic theory is that all atoms of the same element are identical in size, mass, and other properties. While all atoms of the same element have the same chemical properties regardless of its number of neutrons, the size and mass portion of this assumption are incorrect. All atoms of the same element have the same number of protons, but the number of neutrons may vary. Atoms with the same number of protons but different numbers of neutrons are isotopes of each other. An interesting note is that most isotopes of a given element are radioactive, only one or two are stable, non-radioactive.

The final two scientists involved in the development of the atomic structure are Niels Bohr and Werner Heisenberg. Like Rutherford, these two did not discover one of the particles but instead they described where these particles are to be found. Both Bohr and Heisenberg described where the electron resides in the atom. Bohr developed his model in 1913, his model is the one that most of us envision when thinking about the atom; it follows a planetary model. Rutherfords nucleus acts like the sun to which the tiny planetary electrons orbit. The electrons are place around the nucleus in symmetrically larger orbits or shells as they were called. Each shell holds a specific number of electrons. Bohrs model is a good one, and is very intuitive; the problem was that it did not describe all the data that was being rapidly collected. Bohrs colleague Heisenberg developed our current atomic model based on the newly found science Quantum Mechanics. To date this model has described much of the collected data, but not all. It is only a model and cannot be proven. The quantum mechanics model uses high-level calculus and wave functions to predicted the regions the electrons will occupy, these regions are called atomic orbital. These positions do not follow Bohrs concentric orbital model, they are more complicated.

Bohr Model

Heisenberg Model

An interesting couple of notes on Niels Bohr: Upon flee persecution from the Nazis he was force to leave his Nobel Prize in his Copenhagen laboratory. But knowing the Nazis would comb every inch of the complex he dissolved his gold medal in aqua regia, a mixture of hydrochloric and nitric acids and placed it on a shelf in his stockroom. After the Germans surrendered, he returned to his laboratory, precipitated his gold and had it recast by the Nobel Society. Bohr showed the remarkable ability to recognize a breakthrough in science, even when the breakthrough countered a theory of his own. Not only did he refrain from burying the new idea, he fostered it, championing the idea to the world on behalf of his fellow scientist, this is how Heisenbergs and many other brilliant scientists ideas found widespread acceptance.

As stated more than 2000 years ago, atoms are very small. So small we still do not have the technology to photograph one. Size-wise an atom is in the 10 -10 meter range. Actually, in 1925, Werner Heisenberg, the author of the currently accepted model for the atom stated that a photography of atomic sized particles is impossible. It is termed Heisenbergs uncertainty principal. The premise is that the atom is so small, that the light used to photograph the atom is strong enough to move the atom, so now the atom is no longer where it was and is no longer in the picture. All atoms are neutrally charged, meaning they are composed of equal numbers of protons and electrons and, with the exception of hydrogen, a certain number of neutrons. Since the neutrons have no charge, the atoms neutrality is unaffected by number of neutrons. Looking at the above table you will see that the electron has no mass, 0 AMU. This is not completely true, but its mass, as stated before, is around 2000 times less than that of a proton or neutron. So, when discussing an atoms mass a count of the protons and neutrons is all that is needed. An atom with 4 protons and 5 neutrons has an atomic mass of 9 AMU. The atomic number of an atom is simply its number of protons. For example all carbon atoms have 6 protons. If you add another proton you no longer have carbon you now have nitrogen. If you were given the following table but it only contained the black numbers and symbols you should be able to fill in the boxes with the red numbers and symbols.

symbol atomic # neutrons electrons atomic mass Na 11 12 11 23 P 15 20 15 35 U 92 146 92 238 Ti 22 25 22 47

Diatomics and Allotropes:

Most of the elements on the periodic table are found as individual atoms in their elemental state. But a few are found linked to themselves. A diatomic is an element that is found paired with itself. There are seven diatomics found in nature on the surface of the Earth. H 2, N2, O2, F2, Cl2, Br2 and I2. With the exception of hydrogen, they are all found together and they are all nonmetals. Yes, oxygen will form a three atom triatomic, but only in the very upper atmosphere at very low pressures. The name for these elements found in different combination with themselves is allotrope. So, you would say that O2 and O3 are allotropes of each other. Sulfur forms an interesting S 8 allotrope. Carbon has three noteworthy allotropes, graphite (found in your pencils), diamonds (hopefully found on your finger) and the Buckyball (shaped like Epcot Center or a soccer ball).

graphite

diamond

Buckyball

Periodic Table and Periodicity:

This table holds so much information. It is easily the most important tool of a chemist. Some sit and stare at it like art, similar to those 3D drawings when after staring for a while an image pops out at you, an idea may emerge from the table. This is not a random collage of strange names, there is meaning to its arrangement. Periodicity, as defined by Websters is the quality, state, or fact of being regularly recurrent or having periods. As this concept applies to the periodic table, at regular intervals you will find elements with similar chemical properties if the elements are placed in order of ascending atomic number. So, periodically the elements in the periodic table have similar physical and chemical properties. In 1896, the Russian chemist Dmitri Mendeleev, usually regarded as father of the periodic table, pinned cards of all the elements on a board and tried to arrange them in a pattern. Legend claims he sat back in his chair and stared at the board of elements. He eventually drifted off to sleep and when he awoke, comprehended the importance of the periodicity and finalized the first basic periodic table. The most amazing facet of his table was its holes. He recognized that even though the elements are arranged in order of increasing mass (later by atomic number) for all of the elements in a certain column to have the same properties he would need to skip a column in the table to better place that element in it own family. He actually predicted that eventually scientists would find new elements to fit in those holes. And he was right! Earlier I stated that Mendeleev is usually regarded as the father of the periodic table. I say usually because Julius Meyer, a German chemist, actually published a similar table at the same time. So, if you find yourself in the company of German chemists they might remind you that Mendeleev was not the first and that the great chemist Meyer, had at the same time, came to the same conclusions. The columns, vertical, are called Groups or Families, and react similarly from top to bottom. The rows, horizontal, are called periods. Elements next to each other may react similarly, but from side to side they are VERY different. As you move across a period, the number of protons in each element is increased by one. What does react similarly mean? Take Na and K. Both react with water, both are in a 1:1 ratio with group 7 elements, they even taste similar. They each have one outer electron. The number of outer electrons causes the elements to react similar. Elements with one outer electron react the same, elements with 7 outer electrons react the same. This is the origin of the periodicity! Mendeleev really had no idea why, he had no knowledge of electrons. When they were discovered he did not believe in their existence and so he did not think they were responsible for his periodicity. But he was incorrect; the periodicity is due to the elements having the same number of outer electrons, called valence electrons. We now must discuss the arrangement of electrons about the atom in more detail, on a more quantum mechanical level. Dont get overwhelmed by all the terminology that follows, it all comes back to the structure of the periodic table.

Dmitri Mendeleevs first hand written and typed drafts of the periodic table.

Dmitri Mendeleev

Energy Levels:
Electrons are found outside the nucleus of the atom. Their locations are highly organized. J.J. Thomson theorized the electron was stuck to the surface of the atom, Niels Bohrs postulated a solar system like model and finally Werner Heisenberg used quantum mechanics, calculus and wave functions to describe the electrons whereabouts. Regrettably, very few people can follow the math that explains Heisenbergs theory. But the results can be followed. Some of Bohrs model is still useful for visualizing the electrons locations. The electrons location will be described in terms of a Principal Energy Level, a Sublevel, an orbital and a Spin characteristic. Each spinning electron is found in an orbital. Orbitals makeup a sublevel and the sublevels complete the principal energy level. There are seven principal energy levels. One for each row on the periodic table. Each successive level is able to hold another sublevel. The 1 st primary energy level contains only 1 sublevel, the second primary energy level contains 2 sublevels. This trend continues to the 7 th primary energy level, which contains 7 sublevels. The sublevels are named by a single letter. The first sublevel is the s, followed by p, d, f, g, h & i. The first four sublevels are the most important. There are seven sublevels. Each successive level is able to hold two more orbitals. The 1st sublevel, s, can hold 1 orbital. the 2nd sublevel, p, can hold 3 orbitals. This trend continued in the following table: Energy Level Sublevels per level 1 s 2 sp 3 spd 4 spdf 5 spdfg 6 spdfgh 7 spdfghi Each sublevel is able to hold a specific number of orbitals. And each orbital can hold only two electrons. The total number of electrons that a sublevel can hold is listed in the below table. Sublevel s p d f Orbitals per Sublevel 1 3 5 7 Electrons per Sublevel 2 6 10 14

You may be asking yourself why the g, h, and I sublevels are not listed here. That is a very good question and there is a very good answer. No element exists which has so many electrons that the g, h or i sublevels will ever be filled.

The periodic table will tell you how many electrons will fit into each sublevel. The shape of the table is based on the arrangement of the electrons. The below table is color coded in blocks. The greenish area is the s-block, the red area is the p-block, the yellow area is the d-block and the blue area is the f-block. This will tell you how many electrons will fit into a sublevel. The s-block is 2 column wide, the s-block will hold 2 electrons as it contains 1 orbital. The p-block is 6 column wide, the p-block will hold 6 electrons as it contains 3 orbital. The d-block is 10 column wide, the d-block will hold 10 electrons as it contains 5 orbital. The f -block is 14 column wide, the f -block will hold 14 electrons as it contains 7 orbital. Remember, each orbital can hold 2 electrons.

The table may be show in the following manner. You normally see it in the above manner because it is more condensed and will fit on a page more easily.

Orbital Shapes:
This is what the wave function orbitals look like in calculus.

Electron Configurations:
The notation to identify the location of each electron within an atom is the electron configuration. Each electron has a specific spot or orbit where it will be found. The orbits or orbitals are shown in the above diagrams. The format is to give the number of the energy level, followed by the sublevel letter and then the number of electrons in that sublevel written as a superscripted number next to the sublevel letter. Here are two examples:

hydroge n 1s1

carbon 1s22s22p2

The electron configuration accounts for all electrons in the atom. The hydrogen atom has one electron and that electron is found in the first energy level; it is found in the s sublevel and the subscript shows the one electron in that sublevel. The carbon atom contains 6 electrons. The first two electrons are in the first energy level and in the s sublevel. The first energy level can only hold one sublevel and the s sublevel can only hold one orbital so it can only house the 2 electrons. So we must add our next two electrons to the second energy level. The first two electrons are placed in the s sublevel. Again, since s sublevels can only hold one orbital, it can only hold 2 electrons and we must move on to the next sublevel in the second energy level. The second energy level can hold two sublevel, s and p. The last two electrons can fit in the p sublevel as the p sublevel can hold 3 orbitals. The electron configurations of the noble gasses act as a stepping point to the next energy level. These configurations provide a break point when writing long configurations. Since every element past a noble gas will have the same configuration up to that noble gas, it is used as an abbreviation. See the following examples. Full Configuration Noble Gas Configuration

S: 1s22s22p63s23p4 S: [Ne] 3s23p4

Na: 1s22s22p63s1 Na: [Ne] 3s1

Be: 1s22s2 Be: [He]2s2

Order of Filling Sublevels:

Unfortunately, electrons do not fill all of the sublevels contained in a given energy level before they begin to fill the sublevels in the next, higher energy level. The following diagram lays out the order in which the sublevels are filled.

Energy Level Diagrams:

These diagrams depict which energy levels and sublevels the electrons are found. In these diagrams the lines indicate orbitals and the arrows indicate electrons. The energy level diagrams for H and C atoms are as follows:

Two things may strike you as you look at the carbon atoms energy level diagram. First, why are the arrows alternating in direction? The Pauli Exclusion Principal states that electrons have spin and electrons in the same orbital must have opposite spin. The reason for this is that electrons are negatively charged, so they repel each other. But, when a charged particle spins it produces a magnetic field. In the picture below the electrons are spinning in opposite directions producing opposite magnetic fields and the norths and souths are attracted to each other. So, even though the negative charges are forcing the electrons apart, at least their magnetic fields are pulling them together.

The second point of interest in carbons energy level diagram is the question as to why the top two electrons not in the same orbital? Hunds Rule states that electrons fill empty orbitals in the same sublevel before combining electrons in the same orbital; because they are both negatively charged, they want to stay as far away from each other as possible.

Groups of the Periodic Table:

IUPAC Group numbers 1 2 13 14 15 16 17 18 US Group numbers 1A 2A 3A 4A 5A 6A 7A 8A Activity very reactive reactive semi-reactive mildly reactive semi reactive reactive very reactive non-reactive Names alkali metals alkali earths halogens noble gasses Charges Formed +1 +2 +3 +4 or - 4 -3 -2 -1 none Valence Electron Configuration s1 s2 s2 p1 s2 p2 s2 p3 s2 p4 s2 p5 s2 p6

The d - block is called the transition metals. These elements are strange in that when they react they use different numbers of their electrons depending on the other reactant(s) and environmental conditions. The f - block is called the lanthanide and actinide series. Most are very rare and so they are also named rare earths or rare earth metals or inner transition metals. The elements in the actinide series, past uranium are all man made, these elements are called transuranium. Classes of Elements: Looking at the below diagram you will see a red stair-step line. This is the periodic tables dividing line. On the left side of the line you will find the metal (with the acceptation of hydrogen). On the right side of the line you will find the non-metals. Those elements touching this stair-step line are considered metalloids. Metalloids have properties of both metals and non-metals.

The properties of these three classes of elements, both chemical and physical, vary greatly.

Metals physical properties include: being a solid at STP, standard temperature and pressure, (except for mercury) and having high electrical and thermal conductivity, luster, malleability and ductility. Substances which exhibit luster characteristics reflect light well. Malleable substances can be flattened into sheets. Ductility refers to a substances ability to be pulled into a wire. Another interesting point about metals is their ability to form a homogeneous mixture, an alloy, with other metals. The properties of the alloy are different than those of the component metals. An alloy is normally stronger, more heat resistant and more resistant to corrosion. Steel is the most common alloy. When undergoing a spontaneous chemical reaction metals lose electrons to non-metals forming ionic compounds. The physical properties of non-metals are less uniform than those of metals. At STP, many non-metals are gasses (oxygen, neon...), a few are solids (sulfur, iodine...) and one is a liquid (bromine). Non-metals are poor thermal and electrical conductors. The solid non-metals are powders or are brittle, they cannot be formed into any structurally sound shape. When chemically reacting with metals, non-metals tend to gain electrons to form anions, but non-metals share electrons when forming compounds with other non-metals to create covalent compounds. Relative Atomic Size: An atom is approximately 10-10m in diameter. But each elements atoms are a slightly different size. Using the periodic table as a guide, as you move down a group (column), the atom becomes larger. But as you move across a period (row), the atoms become smaller. Ionization Energy: When an atoms charges are not balanced, it has more electrons than protons or less electrons than protons; therefore, the atom becomes a charged species and is now an ion. The amount of energy needed to remove an electron from an atom is termed ionization energy. The periodic table is used as a guide to relative ionization energies of atoms. As you move down a group less energy is required to remove an electron. Conversely, as you move across the periods more energy is needed to remove an electron. Helium is the most difficult atom from which to remove an electron. Francium releases its valence electron most easily.

Electronegativity: Chemical reactions occur as atoms attempt to fill energy levels. Some atoms fill energy levels by adding electrons while others give up their electrons. An atoms electronegativity is a measure of that atoms affinity for electrons. Again, the periodic table can be used as a guide. The relative electronegativity of atoms decreases as you move down a group, the electronegativity of the atoms decreases. On the other hand, as you travel across a period the electronegativity increases. These rules exclude the noble gasses as they already have filled energy levels and do not react chemically unless forced by extreme environmental conditions. The most electronegative element is fluorine and the least is francium. Fluorine can be thought of as the bully of the periodic table. It has the ability to take an electron from all other types of atoms, again with the exception of the noble gasses. In the bully analogy I relate noble gasses to the parents of the elements, a they cannot be bullied. Awesome Web Site: http://www.colorado.edu/physics/2000/periodic_table

Lewis Dot Structures:

A Lewis Dot Diagram is a simple way to show how many electrons will be involved in a chemical reaction. These electrons are named the atoms valence electrons as they are in the outer level of the atom and are most accessible for a reaction to occur. Lewis recognized that atoms gained or lost electrons in an effort to complete or fill this valence level. The electrons inside of this valence level are not available for reacting. The electrons in the valence level are those added after the last noble gas configuration. Lewis used dots around the atoms symbols to show that atoms number of valence electrons. Example 1: Sodium has 1 valence electron, the electron configurations is 1s22s22p63s1 The blue portion of the electron configuration is the noble gas configuration of neon. The one electron added after neon, shown in red, is found in the 3s1 sub-level

Na
Example 2: Fluorine has 7 valence electrons, the electron configuration is 1s22s22p5

If we look at the periodic table the group tells us the number of valence electrons. But, this only applies to the s and p blocks. It does not apply to the transition metals or d-block. All group 1A elements have 1 valence electron, therefore 1 dot All group 2A elements have 2 valence electron, therefore 2 dot All group 3A elements have 3 valence electron, therefore 3 dot All group 4A elements have 4 valence electron, therefore 4 dot All group 5A elements have 5 valence electron, therefore 5 dot All group 6A elements have 6 valence electron, therefore 6 dot All group 7A elements have 7 valence electron, therefore 7 dot All group 8A elements have 8 valence electron, therefore 8 dot The term octet has come out of this line of thought. There are 8 groups in the above list. When atoms react with other atoms they appear to be collecting or losing electrons to arrive at 8 total valence electrons or an octet. Look at the above two examples. If sodium is to lose 1 electron, it will have 8 valence electrons, found in the 2s 22p6 orbitals. If fluorine gains 1 valence electron, it will have 8 valence electrons found in the 2s 22p6 orbitals.