Chem 101 Chapter 08 LEC

Chemistry: A Molecular Approach, 1st Ed.
Nivaldo Tro
Chapter 8 Periodic Properties of the Elements

Roy Kennedy Massachusetts Bay Community College Wellesley Hills, MA
2007, Prentice Hall
Mendeleev
order elements by atomic mass saw a repeating pattern of properties Periodic Law When the elements are arranged in
order of increasing atomic mass, certain sets of properties recur periodically put elements with similar properties in the same column used pattern to predict properties of undiscovered elements where atomic mass order did not fit other properties, he re-ordered by other properties
Te & I
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Periodic Pattern
nm H2O a/b
H2
m Li2O m/nm BeOnm B2O3 nm CO2 nm N2O5 nm O2 nm Li b Be a/b B a C a N a O F 7 LiH 9 BeH2 11 ( BH3)n 12 CH4 14 NH3 16 H2O 19 HF
m Na2O m MgO m Al2O3 nm/m SiO2nm P4O10nm SO3 nm Cl2O7 Na b Mg b Al a/b Si a P a S a Cl a 23 NaH24 MgH2 27 (AlH3) 28 SiH4 31 PH3 32 H2S 35.5 HCl
m = metal, nm = nonmetal, m/nm = metalloid a = acidic oxide, b = basic oxide, a/b = amphoteric oxide
Mendeleev's Predictions
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What vs. Why

Mendeleevs Periodic Law allows us to predict
what the properties of an element will be based on its position on the table it doesnt explain why the pattern exists Quantum Mechanics is a theory that explains why the periodic trends in the properties exist
Electron Spin
experiments by Stern and Gerlach showed a beam
of silver atoms is split in two by a magnetic field the experiment reveals that the electrons spin on their axis as they spin, they generate a magnetic field
spinning charged particles generate a magnetic field
if there is an even number of electrons, about half

the atoms will have a net magnetic field pointing North and the other half will have a net magnetic field pointing South
Electron Spin Experiment
Spin Quantum Number, ms

spin quantum number describes how the
electron spins on its axis
clockwise or counterclockwise spin up or spin down
spins must cancel in an orbital

paired
ms can have values of

no two electrons in an atom may have the same set of
Pauli Exclusion Principle
4 quantum numbers therefore no orbital may have more than 2 electrons, and they must have with opposite spins knowing the number orbitals in a sublevel allows us to determine the maximum number of electrons in the sublevel
s sublevel has 1 orbital, therefore it can hold 2 electrons p sublevel has 3 orbitals, therefore it can hold 6 electrons d sublevel has 5 orbitals, therefore it can hold 10 electrons f sublevel has 7 orbitals, therefore it can hold 14 electrons
Allowed Quantum Numbers

Number of Significance Values 1, 2, 3, ... distance from nucleus Azimuthal, l 0, 1, 2, ..., n-1 n shape of orbital Magnetic, ml -l,...,0,...+l 2l + 1 orientation of orbital Spin, ms -, + 2 direction of electron spin
Quantum Number Principal, n
Values
Quantum Numbers of Heliums Electrons

helium has two electrons both electrons are in the first energy level both electrons are in the s orbital of the first energy level since they are in the same orbital, they must have opposite spins
n
first electron second electron
l 0 0
ml 0 0
ms + -
11
1 1
Electron Configurations
the ground state of the electron is the lowest
energy orbital it can occupy the distribution of electrons into the various orbitals in an atom in its ground state is called its electron configuration the number designates the principal energy level the letter designates the sublevel and type of orbital the superscript designates the number of electrons in that sublevel He = 1s2
12
Orbital Diagrams
we often represent an orbital as a square and the
electrons in that orbital as arrows
the direction of the arrow represents the spin of the electron
unoccupied orbital
orbital with 1 electron
orbital with 2 electrons

13
Sublevel Splitting in Multielectron Atoms

the sublevels in each principal energy level of
or other single electron systems
Hydrogen all have the same energy we call orbitals with the same energy degenerate are split
for multielectron atoms, the energies of the sublevels

the lower the value of the l quantum number, the less
energy the sublevel has
s (l = 0) < p (l = 1) < d (l = 2) < f (l = 3)
caused by electron-electron repulsion
Penetrating and Shielding

the radial distribution function shows that
the 2s orbital penetrates more deeply into the 1s orbital than does the 2p the weaker penetration of the 2p sublevel means that electrons in the 2p sublevel experience more repulsive force, they are more shielded from the attractive force of the nucleus the deeper penetration of the 2s electrons means electrons in the 2s sublevel experience a greater attractive force to the nucleus and are not shielded as effectively the result is that the electrons in the 2s sublevel are lower in energy than the electrons in the 2p
Penetration & Shielding
16
7s 6s
6p 5p 4p
6 d 5d 4d 3d
5f
4f
5s
Energy 4s 3s
3p Notice the following:
2s
1s
1. because of penetration, sublevels within an energy level are not degenerate 2. penetration of the 4th and higher energy 2p levels is so strong that their s sublevel is lower in energy than the d sublevel of the previous energy level 3. the energy difference between levels becomes smaller for higher energy levels
Order of Subshell Filling in Ground State Electron Configurations

start by drawing a diagram putting each energy shell on a row and listing the subshells, (s, p, d, f), for that shell in order of energy, (left-to-right)
next, draw arrows through the diagonals, looping back to the next diagonal each time
1s 2s 3s 4s 5s 6s 7s
18
2p 3p 4p 5p 6p 3d 4d 5d 6d 4f 5f
Filling the Orbitals with Electrons

energy shells fill from lowest energy to high subshells fill from lowest energy to high orbitals that are in the same subshell have the same
energy no more than 2 electrons per orbital

Pauli Exclusion Principle s p d f Aufbau Principle
when filling orbitals that have the same energy, place

one electron in each before completing pairs
Hunds Rule
Example 8.1 Write the Ground State Electron Configuration and Orbital Diagram and of Magnesium.
1. Determine the atomic number of the element

from the Periodic Table
This gives the number of protons and electrons in the atom Mg Z = 12, so Mg has 12 protons and 12 electrons
20
2. Draw 9 boxes to represent the first 3 energy

levels s and p orbitals
a) since there are only 12 electrons, 9 should be plenty
1s
2s
2p
3s
3p
21
3. Add one electron to each box in a set, then

pair the electrons before going to the next set until you use all the electrons
When pair, put in opposite arrows
1s 2s 2p 3s 3p
22
4. Use the diagram to write the electron

configuration
Write the number of electrons in each set as a superscript next to the name of the orbital set 1s22s22p63s2 = [Ne]3s2
1s 2s 2p 3s 3p
23
Valence Electrons
the electrons in all the subshells with the
highest principal energy shell are called the valence electrons electrons in lower energy shells are called core electrons chemists have observed that one of the most important factors in the way an atom behaves, both chemically and physically, is the number of valence electrons
Kr = 36 electrons
Electron Configuration of Atoms in their Ground State

1s22s22p63s23p64s23d104p6
there are 28 core electrons and 8 valence electrons
Rb = 37 electrons
1s22s22p63s23p64s23d104p65s1 [Kr]5s1 for the 5s1 electron in Rb the set of quantum numbers is n = 5, l = 0, ml = 0, ms = + for an electron in the 2p sublevel, the set of quantum numbers is n = 2, l = 1, ml = -1 or (0,+1), and ms = - or (+)
25
Electron Configurations
26
Electron Configuration & the Periodic Table

the Group number corresponds to the number of
valence electrons the length of each block is the maximum number of electrons the sublevel can hold the Period number corresponds to the principal energy level of the valence electrons
27
28
s1
1 2 3 4 5 6 7 s2 p 1 p 2 p 3 p 4 p 5 s2 p6
d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
f2 f3 f4 f5 f6 f7 f8 f9 f10 f11 f12 f13 f14 f14d1
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Electron Configuration from the Periodic Table

1A 8A 2A
3s2
1 2 3 4 5 6 7
3A 4A 5A 6A 7A
Ne P
3p3
P = [Ne]3s23p3 P has 5 valence electrons

for the d block metals, the principal energy level is one less than
valence shell
one less than the Period number sometimes s electron promoted to d sublevel
Transition Elements
Zn Z = 30, Period 4, Group 2B [Ar]4s23d10
4s
3d
for the f block metals, the principal energy level is two

less than valence shell
two less than the Period number they really belong to sometimes d electron in configuration Eu Z = 63, Period 6 6s 4f [Xe]6s24f 7
31
Electron Configuration from the Periodic Table

1A 8A 2A
3d10 4s2
1 2 3 4 5 6 7
3A 4A 5A 6A 7A
Ar As
4p3
As = [Ar]4s23d104p3 As has 5 valence electrons

Practice Use the Periodic Table to write the short electron configuration and orbital diagram for each of the following
Na (at. no. 11)

Te (at. no. 52) Tc (at. no. 43)
Practice Use the Periodic Table to write the short electron configuration and orbital diagram for each of the following
Na (at. no. 11) [Ne]3s1

3s
Te (at. no. 52) [Kr]5s24d105p4

5s 4d 5p
Tc (at. no. 43) [Kr]5s24d5

5s
4d
34
Properties & Electron Configuration

elements in the same
column have similar chemical and physical properties because they have the same number of valence electrons in the same kinds of orbitals
Electron Configuration & Element Properties

the number of valence electrons largely determines the behavior
of an element
chemical and some physical
since the number of valence electrons follows a Periodic pattern,
the properties of the elements should also be periodic quantum mechanical calculations show that 8 valence electrons should result in a very unreactive atom, an atom that is very stable and the noble gases, that have 8 valence electrons are all very stable and unreactive conversely, elements that have either one more or one less electron should be very reactive and the halogens are the most reactive nonmetals and alkali metals the most reactive metals
as a group
36
Electron Configuration & Ion Charge

we have seen that many metals and nonmetals
form one ion, and that the charge on that ion is predictable based on its position on the Periodic Table
Group 1A = +1, Group 2A = +2, Group 7A = -1, Group 6A = -2, etc.
these atoms form ions that will result in an

electron configuration that is the same as the nearest noble gas
38
Electron Configuration of Anions in their Ground State

anions are formed when atoms gain enough
electrons to have 8 valence electrons
filling the s and p sublevels of the valence shell
the sulfur atom has 6 valence electrons

S atom = 1s22s22p63s23p4
in order to have 8 valence electrons, it must gain

2 more
S2- anion = 1s22s22p63s23p6
Electron Configuration of Cations in their Ground State

cations are formed when an atom loses all its
valence electrons
resulting in a new lower energy level valence shell however the process is always endothermic
the magnesium atom has 2 valence electrons

Mg atom = 1s22s22p63s2
when it forms a cation, it loses its valence electrons

Mg2+ cation = 1s22s22p6
Trend in Atomic Radius Main Group

Different methods for measuring the radius of an
atom, and they give slightly different trends
van der Waals radius = nonbonding covalent radius = bonding radius atomic radius is an average radius of an atom based on measuring large numbers of elements and compounds
Atomic Radius Increases down group

valence shell farther from nucleus effective nuclear charge fairly close
Atomic Radius Decreases across period (left to right)

adding electrons to same valence shell effective nuclear charge increases valence shell held closer
41
Effective Nuclear Charge

in a multi-electron system, electrons are simultaneously
attracted to the nucleus and repelled by each other outer electrons are shielded from full strength of nucleus screening effect effective nuclear charge is net positive charge that is attracting a particular electron Z is nuclear charge, S is electrons in lower energy levels
electrons in same energy level contribute to screening, but very little effective nuclear charge on sublevels trend, s > p > d > f
Zeffective = Z - S
42
Screening & Effective Nuclear Charge
43
Trends in Atomic Radius Transition Metals

increase in size down the Group atomic radii of transition metals roughly the
same size across the d block
must less difference than across main group elements valence shell ns2, not the d electrons effective nuclear charge on the ns2 electrons approximately the same
45
46
Example 8.5 Choose the Larger Atom in Each Pair

1) 2) 3) 4) N or F F, N is further left C or Ge Ge, Ge is further down N or Al, Al Al is further down & left Al or Ge? opposing trends
47
cations form when the atom loses electrons
Electron Configuration of Cations in their Ground State
from the valence shell for transition metals electrons, may be removed from the sublevel closest to the valence shell
Al atom = Al+3 ion = Fe atom = Fe+2 ion = Fe+3 ion = Cu atom = Cu+1 ion = 1s22s22p63s23p1 1s22s22p6 1s22s22p63s23p64s23d6 1s22s22p63s23p63d6 1s22s22p63s23p63d5 1s22s22p63s23p64s13d10 1s22s22p63s23p63d10
48
electron configurations that result in unpaired electrons

will be attracted to a magnetic field
Magnetic Properties of Transition Metal Atoms & Ions
mean that the atom or ion will have a net magnetic field this is called paramagnetism
electron configurations that result in all paired electrons

mean that the atom or ion will have no magnetic field this is called diamagnetism
slightly repelled by a magnetic field
both Zn atoms and Zn2+ ions are diamagnetic, showing

that the two 4s electrons are lost before the 3d
Zn atoms [Ar]4s23d10 Zn2+ ions [Ar]4s03d10
Example 8.6 Write the Electron Configuration and Determine whether the Fe atom and Fe3+ ion are Paramagnetic or Diamagnetic
Fe Z = 26 previous noble gas = Ar

18 electrons
23d5 6 Fe3+ atom ion = [Ar]4s0 unpaired electrons paramagnetic
4s
3d
50
Trends in Ionic Radius

Ions in same group have same charge Ion size increases down the group
higher valence shell, larger
Cations smaller than neutral atom; Anions bigger
than neutral atom Cations smaller than anions

except Rb+1 & Cs+1 bigger or same size as F-1 and O-2
Larger positive charge = smaller cation

for isoelectronic species isoelectronic = same electron configuration
Larger negative charge = larger anion

for isoelectronic series
1A
-1
Periodic Pattern - Ionic Radius ()

2A 3A +3 4A -4 5A 6A
-2
+1 7A
+1
+2
-3
-1
-1 -1
Li 0.68 Be 0.31 B 0.23 C +1 +2 +3 -4 Na 0.97 Mg 0.66 Al 0.51 Si +1 +1 +1 +2 +2 K 1.33 Ca 0.99 0.62 +3 Ga +1 -4 Ge
N 1.71 O 1.40 F 1.33 -3 -2 -2
P 2.12 S
-3
1.84 Cl 1.81
As 2.22 Se 1.98 Br 1.96
0.81 +3 0.71 +4 Rb 1.47 Sr 1.13 In +1 Sn +2 +2 0.95 +3 0.84 +4 Cs 1.69 Ba 1.35 Tl +1 Pb +2
-2
Sb Te 2.21
-1
I 2.20
Bi
53
54
Ionization Energy
minimum energy needed to remove an electron
from an atom
gas state endothermic process valence electron easiest to remove M(g) + IE1 M1+(g) + 1 eM+1(g) + IE2 M2+(g) + 1 efirst ionization energy = energy to remove electron from neutral atom; 2nd IE = energy to remove from +1 ion; etc.
General Trends in 1st Ionization Energy larger the effective nuclear charge on the
electron, the more energy it takes to remove it the farther the most probable distance the electron is from the nucleus, the less energy it takes to remove it 1st IE decreases down the group
valence electron farther from nucleus
1st IE generally increases across the period

effective nuclear charge increases
57
58
Example 8.8 Choose the Atom in Each Pair with the Higher First Ionization Energy
1) 2) 3) 4) Al or S S, Al is further left As or Sb Sb, Sb is further down N or Si Si, Si is further down & left O or Cl? opposing trends
59
Irregularities in the Trend

Ionization Energy generally increases from left
to right across a Period except from 2A to 3A, 5A to 6A
Be 1s B 1s 2s 2s 2p N 1s 1s 2s 2s 2p 2p
2p
O
Which Which is is easier easier to to remove remove an an electron electron from from B N or or Be? O? Why? Why?
60
Irregularities in the First Ionization Energy Trends

Be Be+ 1s 2s 2p 1s 2s 2p To ionize Be you must break up a full sublevel, cost extra energy
B+ 1s 2s 2p 1s 2s 2p When you ionize B you get a full sublevel, costs less energy B
Irregularities in the First Ionization Energy Trends

N+ 1s 2s 2p 1s 2s 2p To ionize N you must break up a half-full sublevel, cost extra energy N 1s 2s 2p O+ 1s 2s 2p
When you ionize O you get a half-full sublevel, costs less energy
Trends in Successive Ionization Energies

removal of each successive
electron costs more energy
shrinkage in size due to having more protons than electrons outer electrons closer to the nucleus, therefore harder to remove
regular increase in energy for each
successive valence electron large increase in energy when start removing core electrons
64
energy released when an neutral atom gains an electron

gas state M(g) + 1e- M-1(g) + EA
Trends in Electron Affinity
defined as exothermic (-), but may actually be

endothermic (+)
alkali earth metals & noble gases endothermic, WHY?
more energy released (more -); the larger the EA generally increases across period
becomes more negative from left to right not absolute lowest EA in period = alkali earth metal or noble gas highest EA in period = halogen
66
Metals
Metallic Character
Nonmetals
malleable & ductile shiny, lusterous, reflect light conduct heat and electricity most oxides basic and ionic form cations in solution lose electrons in reactions - oxidized brittle in solid state dull electrical and thermal insulators most oxides are acidic and molecular form anions and polyatomic anions gain electrons in reactions - reduced
metallic character increases left metallic character increase down

67
68
69
Example 8.9 Choose the More Metallic Element in Each Pair

1) 2) 3) 4) Sn or Te Te, Sn is further left P or Sb, Sb Sb is further down Ge or In In, In is further down & left S or Br? opposing trends
70
atomic radius increases down the column ionization energy decreases down the column very low ionization energies
Trends in the Alkali Metals
electron affinity decreases down the column melting point decreases down the column density increases down the column
all very low MP for metals
good reducing agents, easy to oxidize very reactive, not found uncombined in nature react with nonmetals to form salts compounds generally soluble in water found in seawater
except K in general, the increase in mass is greater than the increase in volume
2 Na(s) + 2 H2O(l) 2 NaOH(aq) + H2(g)

atomic radius increases down the column ionization energy decreases down the column very high electron affinities
good oxidizing agents, easy to reduce very reactive, not found uncombined in nature react with metals to form salts compounds generally soluble in water found in seawater
Trends in the Halogens
reactivity increases down the column react with hydrogen to form HX, acids melting point and boiling point increases down the
column density increases down the column
in general, the increase in mass is greater than the increase in volume

74
Example 8.10 Write a balanced chemical reaction for the following.
reaction between potassium metal and bromine

gas
K(s) + Br2(g) K(s) + Br2(g) K+ Br 2 K(s) + Br2(g) 2 KBr(s)
(ionic compounds are all solids at room temperature)
75
reaction between rubidium metal and liquid

water
Rb(s) + H2O(l) Rb(s) + H2O(l) Rb+(aq) + OH(aq) + H2(g)
2 Rb(s) + 2 H2O(l) 2 Rb+(aq) + 2 OH(aq) + H2(g)
(alkali metal ionic compounds are soluble in water)
76
reaction between chlorine gas and solid iodine

Cl2(g) + I2(s) Cl2(g) + I2(s) ICl
write the halogen lower in the column first assume 1:1 ratio, though others also exist
2 Cl2(g) + I2(s) 2 ICl(g)

(molecular compounds found in all states at room temperature)
atomic radius increases down the column ionization energy decreases down the column
Trends in the Noble Gases
very unreactive melting point and boiling point increases down the
column
only found uncombined in nature used as inert atmosphere when reactions with other gases would be undersirable
very high IE
density increases down the column

in general, the increase in mass is greater than the increase in volume
all gases at room temperature very low boiling points
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Chem 101 Chapter 08 LEC

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Chemistry: A Molecular Approach, 1st Ed.

Chapter 8 Periodic Properties of the Elements

Tro, Chemistry: A Molecular Approach

What vs. Why

Tro, Chemistry: A Molecular Approach

if there is an even number of electrons, about half

Electron Spin Experiment

Tro, Chemistry: A Molecular Approach

Spin Quantum Number, ms

spins must cancel in an orbital

ms can have values of

no two electrons in an atom may have the same set of

Pauli Exclusion Principle

Tro, Chemistry: A Molecular Approach

Allowed Quantum Numbers

Quantum Number Principal, n

Quantum Numbers of Heliums Electrons

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

orbital with 1 electron

orbital with 2 electrons

Sublevel Splitting in Multielectron Atoms

for multielectron atoms, the energies of the sublevels

caused by electron-electron repulsion

Penetrating and Shielding

Penetration & Shielding

Tro, Chemistry: A Molecular Approach

3p Notice the following:

Order of Subshell Filling in Ground State Electron Configurations

Filling the Orbitals with Electrons

energy no more than 2 electrons per orbital

when filling orbitals that have the same energy, place

1. Determine the atomic number of the element

Tro, Chemistry: A Molecular Approach

2. Draw 9 boxes to represent the first 3 energy

Tro, Chemistry: A Molecular Approach

3. Add one electron to each box in a set, then

Tro, Chemistry: A Molecular Approach

4. Use the diagram to write the electron

Tro, Chemistry: A Molecular Approach

Electron Configuration of Atoms in their Ground State

there are 28 core electrons and 8 valence electrons

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

Electron Configuration & the Periodic Table

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

f2 f3 f4 f5 f6 f7 f8 f9 f10 f11 f12 f13 f14 f14d1

Tro, Chemistry: A Molecular Approach

Electron Configuration from the Periodic Table

P = [Ne]3s23p3 P has 5 valence electrons

Zn Z = 30, Period 4, Group 2B [Ar]4s23d10

for the f block metals, the principal energy level is two

Electron Configuration from the Periodic Table

As = [Ar]4s23d104p3 As has 5 valence electrons

Na (at. no. 11)

Na (at. no. 11) [Ne]3s1

Te (at. no. 52) [Kr]5s24d105p4

Tc (at. no. 43) [Kr]5s24d5

Properties & Electron Configuration

Electron Configuration & Element Properties

since the number of valence electrons follows a Periodic pattern,

Tro, Chemistry: A Molecular Approach