CHAPTER 7

Periodic Properties of the Elements

CONTENT
7.1 Development of the Periodic Table 7.2 Effective nuclear charge and the Sizes of Atoms 7.3 Ionization Energy 7.4 Electron Affinities 7.5 Metals, Nonmetals, and Metalloids 7.6 Group Trends for the Active Metals 7.7 Group Trends for Selected Nonmetals
2

Learning outcomes
Able to relate effective nuclear charge to size, ionization energy and electron affinity of elements in periodic table
To differentiate metal, non-metal and metalloid

7.1 Development of The Periodic Table

The periodic table was first developed by Mendeleev and Meyer on the basis of the similarity in properties and reactivities exhibited by certain elements.
Elements in the same column of the periodic table have the same number of electrons in their valence orbitals.
4

Valence es for main group elements

Effective Nuclear Charge (Zeff or Z*)

Zeff is as an approximation of the net positive charge experienced by an electron in a multi-electron The term "effective" is used because the shielding effect of negatively charged electrons prevents higher orbital electrons from experiencing the full nuclear charge. We can estimate the effective nuclear charge on each electron present in a multi electron element by the equation below.

Approximation of (Zeff or Z*)

What is the effective nuclear charge for each? Therefore, Zeff(Na+) = 11 - 2 = 9+ Each has 10 electrons but the effective nuclear charge varies because each has a different atomic number: The sodium cation has the largest effective nuclear charge, meaning it has the smallest atomic radius. The shielding effect, approximated by the effective nuclear charge, is due to inner electrons shielding valence electrons from the nucleus

Effective Nuclear Charge

What keeps electrons from simply flying off into space? Effective nuclear charge is the pull that an electron feels from the nucleus. The closer an electron is to the nucleus, the more pull it feels. As effective nuclear charge increases, the electron cloud is pulled in tighter. The shielding effect is called the screening effect. The nuclear charge experienced by an electron depends on its distance from the nucleus and also the screening effect. Zeff = Z S

Question
Why is the 1s shell in Argon so much closer to the nucleus than the 1s shell in Helium? Nuclear charge of He is 2+ and Ar 18+. 1s electrons (innermost electrons of the atom), are not shielded from the nucleus.

Thus, as the nuclear charge increases (2+ 18+), the 1s electrons are pulled closer and closer to the nucleus.

10

Atomic Radius
Since a clouds edge is difficult to define, scientists use define covalent radius, or half the distance between the nuclei of 2 bonded atoms. Atomic radii are usually measured in picometers (pm) or angstroms (). An angstrom is 1 x 10-10 m. Two Br atoms bonded together are 2.86 angstroms apart. So, the radius of each atom is 1.43 .
2.86 1.43 1.43

Slater effective nuclear charge

Z* increases rapidly in periods (but there are gaps immediately after inert gases and the last of the delements). Z* increases also in groups but more slowly.
16 14

12

10

H He Li Be Be C

N O

F Ne Na Mg Al Si P

Cl Ar

K Ca Sc Ti

V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Atomic radii and Z*s form a base for understanding of a number of important atomic properties

(a) n , orbital size (b) n , Zeff remains relatively constant (c) Zeff , Atomic radius

Ionization Energy- Intro

This is the second important periodic trend. Ionization energy (measured in kilojoules, kJ) is the minimum energy required to remove an electron from an ground state atom. Removal of this electron results in the atom being ionized or charged. The number of protons and electrons in this atom is no longer equal. The larger the atom is, the easier its electrons are to remove. Ionization energy and atomic radius are inversely proportional. Ionization energy is always endothermic, that is energy is added to the atom to remove the electron.

Ionization Energy
First ionization energy, I1 (or IE1) - energy needed to remove the first electron from a neutral gaseous atom. Na (g) Na+ (g) + eSecond ionization energy, I2 (or IE2) - energy required to remove the second electron from a gaseous ion. Na+ (g) Na2+(g) + e Ionization energies I1, I2 are always positive (endothermic) where energy is absorbed from the surrounding. The greater the ionization energy, the more difficult to remove an electron. Magnitude I1 < I2 < I3 Reason: The positive nuclear charge remains the same, the number of electrons (produce repulsive interactions) decreases.
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Ionization Energy versus Atomic Number.

Within each row, the alkali metals show the lowest ionization energy and the noble gases the highest. 2. Each column (group), the ionization energy decreases with increasing atomic number. Ionization Energy He > Ne > Ar > Kr > Xe

Cont:

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Cont: 7.3 Ionization Energy

The outermost electrons take part in: a) chemical bonding b) reaction
The core (noble-gas core) tightly bound to the nucleus.

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Ionization Energy (Potential)

How does ionization energy change across a period and down a column?
The first ionization energy increases as you move from left to right across a period. Why? Nuclear charge increases while shielding is constant. Attraction of the electron to the nucleus increases. Move down a column it decreases, WHY: The atomic radius increases, while Zeff remains constant

Attraction , Ionization energy

Cont: 7.3.1 Periodic Trends in Ionization Energies

Irregularities:
a)

Decrease in ionization energy from: Beryllium [He] 2s 2 Boron [He] 2s 2 2p1

o The electrons in the filled 2s orbital shielding the electrons in 2p. o Zeff decreases from 2+ 1+. b) Decrease in ionization energy from: Nitrogen [He] 2s 2 2p 3 Oxygen [He] 2s 2 2p 4
o Due to repulsion of paired electron in the p4 configuration.

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Cont: 7.3.1 Periodic Trends in Ionization Energies

b) Decrease in ionization energy from: Nitrogen [He] 2s 2 2p 3 Oxygen [He] 2s 2 2p 4
o Due to repulsion of paired electron in the p4 configuration.

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Example 1
Arrange the following atoms in order of increasing first ionization energy: Ne, Na, P, Ar, K Use trends to predict. 1. Na, P and Ar are in the same row. exhibit the order of Na<P<Ar(I1 increases from left to right) 2. Ne is a noble gas and above Ar. Ne exhibits the greater ionization energy. (I1 decreases from top to bottom) 3. K below Na. I1 K is less than Na. K < Na < P < Ar < Ne

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Electron Affinity- Intro

Electron affinity is defined as the energy process in which an electron is acquired by the atom in the gas phase OR is the energy change that occurs when an atom gains an electron (also measured in kJ/mol). The larger the affinity of an atom for an electron, the more negative the value Electron affinity results in the gain of electron Ionization energy results in the loss of an electron by an atom. Where ionization energy is always endothermic, BUT electron affinity is usually exothermic, but not always.

Electron Affinity
Electron affinity is exothermic if there is an empty or partially empty orbital for an electron to occupy. If there are no empty spaces, a new orbital or PEL must be created, making the process endothermic. This is true for the alkaline earth metals and the noble gases. the greater the affinity the more negative the value easier to gain electron

EA - trend down the column

Electron affinity decreases (less negative) as it goes down a column because: Increase in atomic radii results in decrease attractive forces between the nucleus and electrons. less effective nuclear charge
Electron affinity increases (more negative) as it goes left to right across a period because The octet rule states that atoms with close to full valence shells will tend to gain electrons. When they gain the electrons, they use energy, which allows the ion to become more stable 25 The outer electrons experience less effective nuclear charge

EA- Exceptions...
Nitrogen 2s2 2p3 atoms have no affinity - in N- ions, electron-electron repulsion makes these ions unstable Beryllium [He] 2s2 and Magnesium [Ne] 3s2 anion has no affinity - both ions are not stable, because the added electron is assigned to a higher energy subshell (2p and 3p respectively) than the valence electrons (2s and 3s respectively) (Hunds first rule). Noble gases have no affinity - they have full valence shells and by adding or taking away electrons, they become unstable

Cont: 7.4 Electron Affinities

N: [He] 2s22p3
strong electronelectron repulsion will not accept electron EA1 > 0 EA1 = -103 kJ/mol

Sb : [Kr] 5s

4d

10

5p

lower electronelectron repulsion

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Cont: 7.4 Electron Affinities

Positive Value of the Electron Affinity
The noble gases posses positive values of electron affinity. The anion is higher in energy than the atom.
Ar(g) + [Ne] 3s 2 3p e6

Ar-(g) EA1 > 0 [Ne] 3s 2 3p 6 4s 1

As EA1 > 0, the Ar- is not stable and will not form.
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Cont: 7.4 Electron Affinities

Group 5A
N, P, As, Sb N P As Sb [He] 2s 2 2p 3 [Ne] 3s 2 3p 3 [Ar] 4s 2 3d 10 4p 3 [Kr] 5s 2 4d 10 5p 3 0 -72 kJ/mol -78 kJ/mol -103 kJ/mol
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Cont:
g

30

Cont: 7.4 Electron Affinities

You can explain: F [He] 2s 22p 5
Br [Ar] 4s 2 3d1 0 4p I
5

- 328 kJ/mol - 325 kJ/mol - 295 kJ/mol

[Kr] 5s 2 4d 10 5p 5

5p 5 - away from nucleus, therefore less nucleus attraction.

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7.5 Metals, Nonmetals and Metalloids

Properties of individual atoms:
Metals Electronegavity Ionization energies Electron affinities Low Low Low Non Metals High High High Metalloids Medium Medium Medium

Ionization energy energy absorbed when electrons are lost from a neutral atom in the gaseous phase Electronegativity tendency for an atom to attract electrons to itself when it chemically combines with other elements Electron Affinity energy gained when electrons are gained by a neutral atom in the gaseous phase

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cont

34

Metals, Nonmetals and Metalloids

Metals
Fraction of element represented in Periodic Table Properties 2/3

Non-metals
1/3

Metalloids
7 elements (B, Si, Ge, As, Sb, Te, and At) Have some properties of metals and others of nonmetals. Generally intermediate in luster and conductivity

Luster, Malleability, Ductility, High thermal and electrical conductivity. High melting point (except Cs, Ga)

Dull, brittle, not ductile, not malleable, poor thermal and electrical conductors Melting points generally lower than those of metals (except diamond : 3570 C). Gases (oxygen, nitrogen), molecular solids or network solids at room temperature (carbon ) or a liquid (only bromine)

Physical State

Solids except mercury (liquid) at room temperature.

most are solids (B, Sb,Te etc.) Several metalloids are semiconductors ( most notably silicon).

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Metals
Metals, reacting with nonmetals, loses electrons and become cations. Most metal oxides are basic oxides. They dissolve in water, react to form metal hydroxides. Metal Oxide + Water Metal Hydroxide Na2O(s) + H2O(l) 2NaOH(aq) CaO(s) + H2O(l) Ca(OH)2(aq) React with acids to form salts and water: Metal Oxide + Acid Salt + Water MgO(s) + 2HCl(aq) MgCl2(aq) + H2O(l) NiO(s) + H2SO4(aq) NiSO4(aq) + H2O(l) Na2O(s) + H2SO4(aq) Na2SO4(aq) + H2O(l)

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Example 2
a) Write the chemical formula of aluminium oxide. b) Write the balanced chemical equation for the reaction of aluminium oxide with nitric acid. a) Aluminium has a 3+ charge, Al3+.The oxide ion is O2 Al2O3 b) Metal oxides react with acids to form salts and water. Al2O3(s) + 6HNO3(aq) 2Al(NO3)3(aq) + 3H2O(l)
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Nonmetals
o Nonmetals, reacting with metals, gain electrons and become anions. Metal + Nonmetal Salt 2Al(s) + 3Br2(l) 2AlBr3(s) Nonmetals gain electrons to fill their outer p subshell giving a noble-gas electron configuration. Most nonmetal oxides are acidic oxides (molecular substance).Those dissolve in water react to form acids. Example:
Selenium dioxide - SeO2 Tetraphosphorus hexoxide - P4O6(s) Tetraphosphorus decoxide - P4O10(s)

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Nonmetals
Reaction with water: SeO2(s) + H2O(l) H2SeO3 (aq) P4O6(s) + 6H2O(l) 4H3PO3(aq) P4O10(s) + 6H2O(l) 4H3PO4(aq)
Nonmetal oxide + base salt + water CO2(g) + 2NaOH(aq) Na2CO3(aq) + H2O(l) SO3(g) + 2KOH(aq) K2SO4(aq) + H2O(l)
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Effective nuclear charge (Z*)

Z* = nuclear charge experienced by the outermost electrons.

Estimate Z* by [ Z - (# of shielding electrons) ]

(Z = total number of electrons)

2nd Period atomic number

# of core electrons Z*

Li 3
2 1

B 5
2 3

N 7
2 5

F 9
2 7

Z* increases across a period

Write down the electronic configuration of the element as shown below. (1s) (2s, 2p) (3s, 3p) (3d) (4s, 4p) (4d) (4f) (5s, 5p) (5d) Fill the electrons according to Aufbau principle. Any electrons to the right of the electron of interest do not contribute to shielding constant. The shielding constant for each group is formed as the sum of the following contributions: All other electrons in the same group as the electron of interest shield to an extent of 0.35 nuclear charge units except 1s group, where the other electron contributes only 0.30. If the group is of the [s, p] type, an amount of 0.85 from each electron (n-1) shell and an amount of 1.00 for each electron from (n-2) and lower shell. If the group is of the [d] or [f] type then an amount of 1.00 for each electron from all lying left to that orbital.

41

(a) Calculate effective nuclear charge in Nitrogen for 2p electron. Electronic configuration- (1s2) (2s2, 2p3). Screening constant, = (0.35 4) + (0.85 2) = 3.10 Effective nuclear charge, Z* = Z = 7 3.10 = 3.90

b) Calculate effective nuclear charge and screening constant seen in 3p electron in

Silicon. Electronic configuration- (1s2) (2s2, 2p6)(3s2, 3p2). = (0.35 3) + (0.85 8) + (1 2) = 9.85 Z* = Z = 14 9.85 = 4.15

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c) Calculate effective nuclear charge in Zinc for 4s electron & for 3d electron.
Electronic configuration- (1s2) (2s2, 2p6)(3s2, 3p6)(3d10)(4s2). For 4s electron, = (0.35 1) + (0.85 18) + (1 10) = 25.65 Z* = Z = 30 25.65 = 4.35 For 3d electron, = (0.35 9) + (1 18) = 21.15 Z* = Z = 30 21.15 = 8.85

d) Calculate effective nuclear charge on one of 6s electron in tungsten.

(At. No. =74)Electronic configuration- (1s2) (2s2, 2p6)(3s2, 3p6)(4s2, 4p6) (3d10) (4f14) (5s2, 5p6)(5d4), (6s2) = (0.35 1) + (0.85 12) + (1 60) = 70.55 Z* = Z = 74 70.55 =3.45

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(a) Calculate approx effective nuclear charge in Nitrogen for 2p electron.

Electronic configuration- (1s2) (2s2, 2p3). Atomic weight = 7 Inner electron = 4 Electron electron repulsion (2P) = 3*0.5 = 1.5 Effective nuclear charge, b) Calculate effective nuclear charge and screening constant seen in 3p electron in Silicon. Electronic configuration- (1s2) (2s2, 2p6)(3s2, 3p2). = 7 - 4 -1.5 = 1.5

b) Calculate effective nuclear charge and screening constant seen in 3p electron

in Silicon. Electronic configuration- (1s2) (2s2, 2p6)(3s2, 3p2). Atomic Number = 14 Inner electron = 12 Side repulsion = 2*0.5 = 1 Z8* = 14-12-0.5 = 1.5

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Example 1: For a 2s electron in a Be atom (1s22s2, Z = 4) = 1(0.35) + 2(0.85) + = 2.05 Zeff = 4 2.05 = 1.95

Example 2: For a 3p electron in a phosphorus atom (1s22s22p63s23p3, Z = 15) = 4(0.35) + 8(0.85) + 2(1.00) = 10.20 Zeff = 15 - 10.20 = 4.80

Group 2A: The Alkaline Earth Metals

The elements are all solids with typical metallic properties. Compare to elements in Group 1A (alkaline metals), alkaline earth metals are harder, more dense and melt at higher temperatures. Their I1 are low, but not as low as those of alkali metals. Less reactive than alkali metals.
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Group 7A: The Halogens

As we move from group 6A to 7A, the nonmetallic behaviour of the elements increases. All the halogens are typical nonmetals (except At- metalloid). Melting points and boiling points increase with increasing atomic number. Each element consists of diatomic molecules: F2, Cl2, Br2, and I2. Br Fluorine (pale yellow) and chlorine (yellow-green) gas at room temperature. Bromine - reddish brown liquid Iodine greyish black solid (sublime easily)
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END OF CHAPTER 7

64

THE ELEMENTS VALENCE SHELL

1) Electron Shielding. Slaters rules If inner-sphere electrons in atoms were concentrated in thin inner layers near nucleus (onion -like structure), an outersphere electron would interact with nucleus, as it would in the hydrogen atom ( Z = 1), according to laws of electrostatics. In fact, the interaction is stronger and can be described by an effective nuclear charge Z*>1. Z* = Z S, here S is a shielding constant specific for each element subshell In the series of orbitals s, p, d, f the ability of electrons occupying them to shield outer sphere electrons decreases, while vulnerability to the shielding effect of inner sphere electrons increases. This trends result from the decreasing number of radial nodes for ns > np > nd > nf orbitals which is equal to n-l-1 and their decreasing penetration through inner sphere electron shield. The approximate value of the shielding constant S(ns, np) for electrons occupying ns or np orbitals can be estimated by applying Slater rules. Electrons occupying orbitals to the right of a subshell in the row below are considered to contribute nothing to the shielding of the electrons on that subshell: (1s) (2s, 2p) (3s, 3p) (3d) (4s, 4p) (4d) (4f) (5s, 5p) etc. S(ns, np) = 0.35[N(ns, np) 1] + 0.85N(n-1) + 1N(all other inner shells) here N(x) is the number of electrons occupying the shell (x) Example of the oxygen atom: the electronic configuration is 1s22s22p4; for oxygen 2p electrons S(2p) = 0.355+0.852 = 3.45 so that Z* = 8 - 3.45 = 4.55
Effective nuclear charges of elements by Clementi and Raimondi (more precise calculation of Z *): http://www.webelements.com/webelements/properties/text/image-flash/eff-nucl-charge-clem-1s.html

14.00 12.00 10.00 8.00 6.00 4.00 2.00 0.00

1s

1000*[r*R(r)]2

2p

2s
r
4 6 8

According to Clementi, for O S(2p)= 3.58 and Z*=4.42

2) Slater effective nuclear charge

Z* increases rapidly in periods (but there are gaps immediately after inert gases and the last of the delements). Z* increases also in groups but more slowly.
16

14

12

10

H He Li Be Be C

F Ne Na Mg Al Si P

Cl Ar

K Ca Sc Ti

V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Atomic radii and Z*s form a base for understanding of a number of important atomic properties

3) Some important properties of atoms. Ionization energy (IE)

The IE is the energy necessary to remove an electron from an isolated atom in the gas phase: A A+ + eThe first IE characterizes the energy of the highest occupied atomic orbital. Its value is affected by both the effective atomic nuclear charge Z* and atomic radius R (http://www.webelements.com/webelements/properties/text/image-flash/atomic-radiusemp.html ). Within a given family of non-transition elements heavier analogues have lower IE (Z* changes slightly while atomic radius R increases significantly). Within a given series of non-transition elements IE increases (Z* increases while atomic radius R decreases). Some local maxima are observed for the elements with half- or completely filled subshells. These maxima reflect the enhanced stability of such subshells.

4) Electron affinity (EA)

This is the energy released when an electron is added to an isolated atom in the gas phase, taken with the opposite sign: A + e- A The EA characterizes the energy of the lowest unoccupied atomic orbital. Within a given family heavier elements have lower EA mainly because of the increasing atomic radius (exception: elements of the 2nd row). Within a given series of non-transition elements EA tends to increase because of the increasing Z* and decreasing R. The effects of (half)filled subshell are responsible for the non-continuous character of this trend.
4.00

EA, eV

3.50 3.00 2.50

Cl Br I Au S Se Ag Nb Tc 40 60 Te Pt Ir Os W Pb Rn Po At

2.00 1.50 1.00 0.50 0.00 0 20 H C O Si P Al K Ga Cu Ge Ni Cr As

Li B

Na

Z
100

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5) Electronegativity
According to Pauling, electronegativity is the power of an atom in a molecule to attract electrons to itself. There are several scales of electronegativity, they correlate one with another: c(A)-c(B) = [(E(A-B) 0.5{E(A-A)+E(B-B)})1/2, eV],
Here E(A-B), E(A-A) and E(B-B) are energies of A-B, A-A and B-B bonds respectively

Paulings thermochemical Mulliken-Jaffe Allens spectroscopical

c = [0.118(IE+EA)-0.207, eV],
Here IE is ionization energy and EA is electron affinity of an atom

c = [(mep+nes)/(m+n)],

Allred-Rochows semi-empirical c = [0.744+3590Z*/r2] etc.

Here ep is the energy of p-electrons and es is the energy of s-electrons; m and n are populations of p- and s-orbitals respectively.

Here Z* is effective nuclear charge and r is atomic radius.

Electronegativity increases in series of non-transition elements and decreases in a given family as atomic number increases (see a fragment of the Pauling scale below): 0.98 0.93

Li Na

Be Mg

1.57 1.31

B Al

2.04 1.61

C Si

2.55 1.90

N P

3.04 2.19

O S

3.44 2.58

F Cl

3.98 3.16

Electronegativity, various scales: http://www.chm.davidson.edu/ronutt/che115/electroneg.htm http://www.webelements.com/webelements/properties/text/image-flash/electroneg-mulliken.html