Chapter 8: ATOMIC ELECTRON CONFIGURATIONS AND PERIODICITY

Arrangement of Electrons in Atoms

Electrons in atoms are arranged as

SHELLS (n) SUBSHELLS (l) ORBITALS (ml)

Arrangement of Electrons in Atoms

Each orbital can be assigned no more than 2 electrons! This is tied to the existence of a 4th quantum number, the electron

spin quantum number, ms.

Electron Spin Quantum Number, ms

Can be proved experimentally that electron has a spin. Two spin directions are given by ms where ms = +1/2 and -1/2.

Electron Spin Quantum Number

Diamagnetic: NOT attracted to a magnetic

field

Paramagnetic: substance is attracted to a

magnetic field. Substance has unpaired electrons. electrons.

QUANTUM NUMBERS
n ---> shell ---> l ---> subshell ---> ml ---> orbital ---> ms ---> electron spin ---> 1, 2, 3, 4, ... 0, 1, 2, ... n - 1 -l ... 0 ... +l +1/2 and -1/2

Pauli Exclusion Principle

No two electrons in the same atom can have the same set of 4 quantum numbers.
That is, each electron in an atom has a unique address of quantum numbers.

Electrons in Atoms
When n = 1, then l = 0 this shell has a single orbital (1s) to which 2e- can be assigned. 2eWhen n = 2, then l = 0, 1 2s orbital three 2p orbitals TOTAL = 2e2e6e6e8e8e-

Electrons in Atoms
When n = 3, then l = 0, 1, 2 3s orbital three 3p orbitals five 3d orbitals TOTAL = 2e2e6e6e10e10e18e18e-

Electrons in Atoms
When n = 4, then l = 0, 1, 2, 3 4s orbital 2e2ethree 4p orbitals 6e6efive 4d orbitals 10e10eseven 4f orbitals 14e14eTOTAL = 32e32eAnd many more!

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Assigning Electrons to Atoms

Electrons generally assigned to orbitals of successively higher energy. For H atoms, E = - C(1/n2). E depends only on n. For many-electron atoms, energy depends manyon both n and l.
See Figure 8.5, page 295 and Screen 8. 7.

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Assigning Electrons to Subshells

In H atom all subshells of same n have same energy. In many-electron atom: manya) subshells increase in energy as value of (n + l) increases. b) for subshells of same (n + l), the subshell with lower n is lower in energy.

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Electron Filling Order

Figure 8.5

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Effective Nuclear Charge, Z*

Z* is the nuclear charge experienced by the outermost electrons.
Explains why E(2s) < E(2p) Z* increases across a period owing to incomplete shielding by inner electrons. Estimate Z* by --> [ Z - (no. inner electrons) ] --> Charge felt by 2s e- in Li eZ* = 3 - 2 = 1 Be Z* = 4 - 2 = 2 B Z* = 5 - 2 = 3 and so on!

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Effective Nuclear Charge

Figure 8.6

Electron cloud for 1s electrons

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Writing Atomic Electron Configurations

Two ways of writing configs. One is called the spdf notation.

spdf notation for H, atomic number = 1

1s

no. of electrons value of l

value of n

Writing Atomic Electron Configurations

Two ways of writing configs. Other is called the orbital box notation.
ORBITAL BOX NOTATION for He, atomic number = 2

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1s

2
1s

Arrows depict electron spin

One electron has n = 1, l = 0, ml = 0, ms = + 1/2 Other electron has n = 1, l = 0, ml = 0, ms = - 1/2

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See Toolbox for Electron Configuration tool.

Effective Nuclear Charge, Z*

Atom Li Be B C N O F Z* Experienced by Electrons in Valence Orbitals +1.28 ------+2.58 Increase in +3.22 Z* across a +3.85 period +4.49 +5.13

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General Periodic Trends

Atomic and ionic size Ionization energy Electron affinity

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Higher effective nuclear charge. Electrons held more tightly Smaller orbitals. Electrons held more tightly.

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Atomic Size
Size goes UP on going down a group. Because electrons are added farther from the nucleus, there is less attraction. Size goes DOWN on going across a period.

Atomic Radii

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Figure 8.9

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Trends in Atomic Size

See Figures 8.9 & 8.10
Radius (pm)
250

K
200

3rd period 2nd period Li Na

1st transition series

150

Kr
100

Ar Ne
50

He
0 0 5 10 15 20 25 30 35 40

Atomic Number

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Ion Sizes
Li, 52

Do s th siz go + u + or ow Li , 60 wh losi g 2 l ctro to for c tio ?

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Ion Sizes
+
Li,152 pm 3e and 3p Li + , 78 pm 2e and 3 p

Forming a cation.

CATIONS are SMALLER than the atoms from which they come. The electron/proton attraction has gone UP and so size DECREASES. DECREASES.

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Ion Sizes
Do s th siz go u or - wh g i i g ow F- ,l ctro to for 36 io ? 9

F,6 9

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Ion Sizes
F, 71 pm 9e and 9p F- , 133 pm 10 e and 9 p

Forming an anion.

ANIONS are LARGER than the atoms from which they come. The electron/proton attraction has gone DOWN and so size INCREASES. INCREASES. Trends in ion sizes are the same as atom sizes.

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Trends in Ion Sizes

Figure 8.13

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Redox Reactions
Why do metals lose electrons in their reactions? Why does Mg form Mg2+ ions and not Mg3+? Why do nonmetals take on electrons?

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Ionization Energy
See Screen 8.12

IE = energy required to remove an electron from an atom in the gas phase.

Mg (g) + 738 kJ ---> Mg+ (g) + e---> e-

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Ionization Energy
See Screen 8.12

Mg (g) + 735 kJ ---> Mg+ (g) + e---> eMg+ (g) + 1451 kJ ---> Mg2+ (g) + e---> e-

Mg2+ (g) + 7733 kJ ---> Mg3+ (g) + e---> eEnergy cost is very high to dip into a shell of lower n. This is why ox. no. = Group no.

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Trends in Ionization Energy

1st Ionization energy (kJ/mol)
2500

He
2000

Ne

Ar
1500

Kr

1000

500

0 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35

Li

Na

Atomic Number

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Trends in Ionization Energy

IE increases across a period because Z* increases. Metals lose electrons more easily than nonmetals. Metals are good reducing agents. Nonmetals lose electrons with difficulty.

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Trends in Ionization Energy

IE decreases down a group Because size increases. Reducing ability generally increases down the periodic table. See reactions of Li, Na, K

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Electron Affinity
A few elements GAIN electrons to anions. form anions. Electron affinity is the energy change when an electron is added: A(g) + e- ---> A-(g) e- ---> E.A. = E

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Electron Affinity of Oxygen

O atom [He] oq

oq o

+ electron O- ion [He] oq

E is EXOthermic EXOthermic because O has an affinity for an e- .

oq o

EA = - 141 kJ

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Electron Affinity of Nitrogen

N atom [He] oq

o o

+ electron N- ion [He] oq

E is zero for Ndue to electronelectronelectron repulsions.

EA = 0 kJ

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Trends in Electron Affinity

Atom EA Affinity for electron F -328 kJ increases across a period (EA becomes Cl -349 kJ more negative). Br -325 kJ Affinity decreases down I -295 kJ a group (EA becomes
less negative).

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Trends in Electron Affinity