AP Chemistry Atomic Structure/Periodicity

Unit 1
Atomic Structure &
Properties
1.1 Moles and Molar Mass

Formula mass: the mass of one mole of a compound, atom, or ion.

Find the formula mass of each of the following:

sodium chloride arsenic trichloride potassium sulfate ammonium phosphate

Measuring Matter: There are three ways to measure matter: by counting representative particles (typically
molecules or formula units), by mass (in grams), or by volume (in liters for gases). The method used is usually
chosen by the ease of each method and the information needed. Once a measurement has been made, it is
possible to convert between the units for the other methods.

1 mole of a compound = fm (in g) compound

1 mole of an element = 6.022 x 1023 atoms of that element
1 mole of a compound = 6.022 x 1023 representative particles (molecules or formula units)

The mole is the link between grams and the number of representative particles.

Draw the mole map below:

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For neutral compounds, the representative particle is either the molecule (covalent) or the formula unit (ionic).
However, to simplify matters we will just use the term molecule for both.

EXAMPLES (One Step Conversions): Remember to show all work using dimensional analysis and to keep
significant figures in mind.
1. How many moles are in 18.0 grams of sugar (C6H12O6)?

2. What is the formula mass of 4.50 moles of barium sulfide?

3. How many molecules are in 28.6 mole of nitrogen gas?

4. How many moles are in 3.90 x 1028 molecules of methane (CH4)?

5. How many atoms of oxygen are in 2.5 moles of oxygen gas? (Diatomic alarms should be ringing in your head)

EXAMPLES (Two-Step and Three-Step Conversions): Remember to show all work using dimensional analysis
and to keep significant figures in mind.

6. How many molecules are in 198.5 grams of sodium chloride?

7. How many molecules are in 937 g of calcium acetate?

8. How many grams are in 3.21 x 1024 molecules of potassium hydroxide?

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9. How many atoms of aluminum are in 2.00 moles of aluminum fluoride?

10. How many atoms of chlorine are in 654.5 grams of calcium chloride?

11. How many moles of carbon are in 1.00 x 1020 molecules of propane, C3H8?

12. How many grams of magnesium are in 5.55 x 1026 molecules of magnesium sulfide?

Complete the following table

M, Molar m, Mass of n, Moles of N, Number of atoms,

Formula Mass (mol/g) sample (g) sample (mol) molecules, or formula units

H2SO4 98.0 0.825

Cr2O3 9.63 x 1023

unknown 56.8 0.476

Mo 62.8

Do scratch work below:

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AP Chemistry Atomic Structure/Periodicity

1.2 Mass Spectroscopy of Elements

mass spectrometer – a device for measuring the mass of atoms or molecules

average atomic mass

percent abundance

mass spectrometer to determine isotopic composition

load in a pure sample of natural neon or other substance. The areas of the “peaks” or heights of the bars indicate
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the relative abundances of 10 Ne , 1021Ne , and 10 Ne

13. When a sample of natural copper is vaporized and injected into a mass spectrometer, the results shown in the
figure are obtained. Use these data to compute the average mass of natural copper. (The mass values for 63Cu
and 65Cu are 62.93 amu and 64.93 amu, respectively.)

14. Two isotopes of chlorine exist in nature. 75.77% of chlorine is 35Cl with a mass of 34.96885 amu. What is
the mass of the other isotope of chlorine?

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Particulates!

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AP Chemistry Atomic Structure/Periodicity

1.3 Elemental Composition of Pure Substances

Law of definite proportion: a given compound always contains exactly the same proportion of elements by
mass.
When two elements form a series of compounds, the ratios of the masses of the second element that combine with
1 g of the first element can always be reduced to small whole numbers.

Percent Composition

15. Determine the percent composition of each element in Ni3(PO4)2.

Empirical and Molecular Formulas

16. Determine the empirical and molecular formulas for a compound that gives the following percentages on
analysis:

71.65% Cl 24.27% C 4.07% H. The molar mass is known to be 98.96 g/mol.

17. Determine the empirical formula for a compound which is 26.6 % potassium, 35.4 % chromium and 38.1 %
oxygen. The compound has a molecular weight of 294.2 g/mol. What is the molecular formula?

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1.4 Composition of Mixtures

Separation of Mixtures

18. For each of the separation techniques listed below, describe each and how it is used to separate the
components of a mixture.

a. Decantation

b. Filtration

c. Evaporation

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d. Distillation

e. (Paper) Chromatography - method that use a system with two phases (states) of matter: the stationary
phase is a solid, and the mobile phase is either a liquid or a gas.

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AP Chemistry Atomic Structure/Periodicity

Each diagram (A - P) show a sample of substances as viewed at the atomic level.

19. Characterize the contents of the container in terms of each of the following categories:

Category I: Homogeneous mixture, heterogeneous mixture or pure substance

Category II.: Element(s), compound(s) or both
Category III: Solid, liquid, gas or combination of phases

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AP Chemistry Atomic Structure/Periodicity

Combustion Analysis

20. A 0.00300 g sample of napthalene, a compound containing only carbon and hydrogen, was burned in excess
oxygen to give 0.0103 g of CO2. Determine the empirical formula of napthalene. The formula weight of
napthalene is 128 u, determine the molecular formula.

1.5 Atomic Structure and Electron Configuration

Breaking down the Periodic Table of Elements - Levels, sublevels, and orbital types

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Sublevel # Orbitals # Electrons

Energy Level # Sublevels # Orbitals Maximum # Electrons

In summary, for any energy level (n), there can be at most:

_______ sublevels _______ orbitals _______ electrons

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Electron Configuration

21. Write electron configuration for the following atoms:

H He

Li B

O Ne

Na P

Ca V

Valence electrons - the electrons present in the highest occupied energy level. These electrons are important
because they are the electron involved in chemical reactions and basically define the chemical properties of the
element.
22. List the number of valence electrons in the above elements.

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Electron configurations of ions: elements gain or lose electrons to form ions. Ions are atoms or groups of atoms
that carry a net charge. Atoms will gain or lose electrons to become more chemically stable.

• If an atom loses electrons, there will be more protons than electrons and the ion will have a positive
charge and is called a cation.
• If an atom gains electrons, there will be more electrons than protons and the ion will have a negative
charge and be called an anion.

23. Write the electron configuration for the following ions:

F-1

Sr+2

Isoelectronic –

*transition metal ions - remember that the valence electrons are the electrons involved in reactions. In transition
metals, the valence electrons are the electrons that are lost, not the highest energy electrons.

24. Write the electron configuration for Fe+2:

Exceptions to writing electron configurations: It is important to remember that these exceptions apply ONLY to
transition elements. For certain reasons, there is special stableness associated with both half-filled orbitals and
filled orbitals. This means that the electron configurations of all the elements in the columns containing the
elements copper and chromium do not fill as expected.

25. Write electron configurations for the following atoms:

Cu:
as expected:

actual:

Cr:
as expected:

actual:

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AP Chemistry Atomic Structure/Periodicity

Orbital Spin Diagrams

• A notation that shows how many e-‘s an atom has in each of its occupied electron orbitals.

26. Draw orbital spin diagrams for the following atoms.

N: Mn:

Diamagnetic vs Paramagnetic:

An element is said to be diamagnetic if there are NO unpaired electrons.

An element is said to be paramagnetic if unpaired electrons are present.

27. Which of the following elements are diamagnetic and which are paramagnetic?

Mg Cd

Fe P

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Electrons in Excited States

• Electrons in their lowest energy electron configuration in an atom are said to be in the ground
state. When electrons are in the ground state they usually obey the three rules governing
electron configurations (don’t forget the exceptions we covered earlier).
• Aufbau Principle – electrons enter orbitals of lowest energy first
• Hund’s Rule – electrons enter orbitals of equal energy one at a time with parallel spins
• Pauli Exclusion Principle – no 2 e-‘s in the same atom can have the same four quantum #’s.
• When electrons in the ground state absorb energy they change their configuration to an excited
state. This means that either the Aufbau principle or Hund’s rule is violated. However, the
Pauli Exclusion Principle can NEVER be violated. Any violation of the Pauli Exclusion
Principle is impossible.
• For each of the following decide if the electrons are in a ground state, excited state, or
impossible state. If a violation of any rule occurs, state the name of the rule violated.

State Violation

↑↓ ↑ ↑ ↑

__________________ __________________

↑↓ ↑ ↓ ↑

__________________ __________________

↑↑ ↑ ↑ ↑

__________________ __________________

↑↓ ↑ ↑ ↑ ↓ ↑

__________________ __________________

↑↓ ↑↓ ↓↓ ↑↓

__________________ __________________

↑ ↑ ↑ ↑ ↑ ↑

__________________ __________________

↑ ↑↓ ↑↓ ↑↓

__________________ __________________

↑↓ ↑↓ ↑

__________________ __________________

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1.6 Photoelectron Spectroscopy

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1.7 Periodic Trends

• Atomic and Ionic Radius

• Electronegativity
• Ionization Energy
• Electron affinity

Atomic Radius
• In general, atomic radius increases going down a group. Orbital sizes increase on successive levels and
SHIELDING INCREASES!

The atomic and ionic radius can be described as a boundary beyond which the electron rarely strays. The “size” of
the atom or ion is affected by two things; the attraction the protons in the nucleus have towards the electron cloud
and the number of energy levels of electrons (n) in the cloud. Think effective nuclear charge and Coulomb’s Law.

As you move from Hydrogen to Lithium to Sodium to Potassium (i.e. down Group I or any group) what trend is
developing with the ATOMIC RADII?

Element H Li Na K
Atomic Radius 0.37 1.52 1.86 2.31

The atomic radius INCREASES as you move down a group in the periodic table? Why?

𝑞1 𝑞2
• Think back to Coulomb’s Law: 𝑈𝐸 ∝ 𝑑
As the distance (d) decreases, (when you add more shells), the
electrostatic potential energy of the electrons decreases. So, electrons are further from the positive nucleus
and are further shielded by the inner electrons from the nucleus. As this increases so does the size of the
atom.
In general, as we go across a period from left to right, the atomic radius decreases. Effective nuclear charge
increases, therefore valence electrons are drawn closer to the nucleus, decreasing the size of the atom

As you move from Lithium ACROSS PERIOD 2 to Fluorine what trend is developing with the ATOMIC RADII?

Element Li Be B C N O F
Atomic Radius 1.52 1.11 0.88 0.77 0.70 0.66 0.64

Generally, the atomic radius DECREASES as you move ACROSS a Period in the Periodic Table. Why?

• As explained earlier…It is all about the nucleus! All of the elements in Period 2 have their valence
electrons in the same energy shell – i.e. they are essentially the same distance from the nucleus. However,
Li has 3 protons, Be 4, B5, and so on up to F, which has 9.

• The higher the nuclear charge (the more effective the nuclear charge Zeff), the more tightly held the
electron, the more energy required to remove the electron within a given energy shell this the electrons are
pulled in closer – they are getting smaller!

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Ionic Radius
• Ions compared to their own neutral element

• Ions in the same family

• Ions that are isoelectronic

28. Rank the atomic sizes of the following elements from small to large: O, N, Ne

29. Rank the atomic sizes of the following elements from small to large: K, Ca, Rb

30. Rank the ionic sizes of the following particles from small to large: Na+1, Mg+2, S-2, Cl-1

31. Circle the larger particle in each of the following:

Fe or Fe+3 As or As-3 S-2 or S Mg+2 or Mg

32. Circle the larger particle in each of the following:

K+1 or Ca+2 Se-2 or Br-1 Br-1 or Cs+1 Be+2 or O-2

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Electronegativity
• Relative tendency of an atom to attract electrons to itself when it is bonded to another atom.

This can be thought of as the ability of atoms to attract a shared electron pair in a covalent bond. Think tug of
war! Again, use effective nuclear charge and Coulomb’s Law to guide your thinking!

As you move from Hydrogen to Lithium to Sodium to Potassium (i.e. down Group I or any group) the atoms
electronegativity is DECREASING. Why?

𝑞1 𝑞2
• Think back to Coulomb’s Law: 𝑈𝐸 ∝ 𝑑
As the distance (d) decreases, (when you add more shells), the
electrostatic potential energy of the electrons decreases. So, the ability of that atom’s nucleus to attract
electrons from another atom in a covalent bond DECREASES as well since the electrons being attracted
are further from the positive nucleus and are further shielded by the inner electrons from the nucleus.

As you move from Lithium ACROSS PERIOD 2 to Fluorine the electronegativity INCREASES. Why?

• As explained earlier…It is all about the nucleus! All of the elements in Period 2 have their valence
electrons in the same energy shell. However, Li has 3 protons, Be 4, B 5, and so on up to F, which has 9.

• The higher the nuclear charge (the more effective the nuclear charge Zeff), the more tightly held the
electron, the more attraction the nucleus will have on electrons in another atom in a covalent bond.

Which element is more electronegative?

33. K, As

34. N, Sb

35. Sr, Be

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Ionization Energy

• Energy required to remove an electron from a gaseous atom or ion.

As discussed in the PES section, the minimum energy needed to remove an electron from an atom or ion is
defined as ionization energy and the energy required to remove the least tightly held electron is the first
ionization energy.
X(g) → X+(g) + e–

Element H Li Na K
First Ionization Energy (MJ/mol) 1.31 0.52 0.50 0.42

The first ionization energy DECREASES as you move down a Group in the Periodic Table. Why?

𝑞1 𝑞2
• Think back to Coulomb’s Law: 𝑈𝐸 ∝ 𝑑
As the distance (d) decreases, (when you add more shells),
the electrons are further from the positive nucleus and are further shielded by the inner electrons) their
electrostatic potential energy decreases, this is takes less energy (or is easier) to remove the electron.

As you move from Lithium ACROSS PERIOD 2 to Fluorine what trend is developing with the FIRST
IONIZATION ENERGY?

Element Li Be B C N O F
First Ionization Energy 0.52 0.90 0.80 1.09 1.40 1.31 1.68

Generally, the first ionization energy INCREASES as you move ACROSS a Period in the Period Table. Why?

• The higher the nuclear charge (the more effective the nuclear charge Zeff), the more tightly held the
electron, the more energy required to remove the electron within a given energy shell.

Multiple Ionization Energies:

These are just removing additional electrons. It always takes energy to remove an electron, and each additional
electron takes even move energy.

For Be:
• IE1 = 899.5 kJ
• IE2 = 1760 kJ
• IE3 = 14850 kJ

• Notice that the energy to remove an electron skyrockets between the 2 and the 3rd.
• This is because the first two electrons removed are valence electrons, but the third removed is a core
electron.
• It is very hard to remove a core electron, and takes a lot of energy because they are closer to the
nucleus!!!

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The Values of First Ionization Energy for the Elements in the First Six Periods

Where are the exceptions to the ionization energy trend? Why?

First Exception in Ionization Energy

• Be to B (group II to IV)
What is happening here? Look at the PES for these 2 elements:

It takes less energy to remove the first electron in B that in Be

because the electron being removed from B is the first electron in
the “p” orbital where the electron removed from Be is in the “s”
orbital. The electrons in the “p” orbital penetrate the nucleus less
than those of the “s” orbital thus they are typically not as attracted
to the nucleus and require less energy to remove. You see this
“glitch in the trend” between all Group III and Group IV elements.

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• N to O (group V to VI)
What is happening here? Look at the PES for these 2 elements:

It take less energy to remove the least tightly held electron

in the O than in N because the electron being remove in O
is the first electron in the “p” orbital that is paired with
another electron (there are 3 “orbitals” so the 4th electron is
paired), whereas N’s 3 electrons are all unpaired. The added
electron – electron repulsion with the paired electron means
this electron will require less energy to remove it.

36. Which atom has the highest ionization energy? Why? Na or Cl

37. Which has the lowest ionization energy? Why? Li Cs

38. Which has the larger second ionization energy? Why? Li or Be

39. Arrange the elements oxygen, fluorine, and sulfur according to increasing:

Ionization energy Atomic size Electronegativity

40.

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Electron Affinity

• Energy change associated with the addition of an electron to a gaseous atom.

X(g) + e– → X–(g)

• In general as we go across a period from left to right, the electron affinities become more negative.
• In general electron affinity becomes more positive in going down a group.

41. Briefly explain each of the following statements.

The atomic radius of Mg is smaller is Ba.

The ionization of S is lower than P.

The energy required to remove the fourth electron in Al is significantly larger than the third electrons.

The energy change associated with gaining an electron, the electron affinity, is positive for some atoms and
negative for others.

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1.8 Valence Electrons and Ionic Compounds

42. What class(es) of element(s) typically unite to form compounds that contain ionic bonds?

43. If lithium and fluorine react, which has more attraction for an electron? Why?

Ionic Bonding and Lattice Energy

• Any compound that conducts an electric current when melted will be classified as ionic.
• Composed of elements with very large differences in electronegativity.
• Usually made up of a metal and a non metal OR metal and polyatomic.
• lattice energy – energy that is released when two ions of an ionic compound come together to form a
crystal.
• The change in energy that takes place when separated gaseous ions are packed together to form an ionic
solid.

Q Q 
Lattice energy = k  1 2 
 r 
k = proportionality constant
Q1 and Q2 = charges on the ions
r = shortest distance between the centers of the cations and anions

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