Section 7.1 ~ 7.

2 Periodic Properties of the Elements in the Periodic Table Periodicity refers to elements in same group have similar chemical properties and the properties recur after an interval.

Syllabus Periodic variation in physical properties of the elements H to Ar

Variations in first ionization enthalpies, atomic radii, electronegativities and melting points. Interpretation of these variations in terms of structure and bonding.

Periodic relationship among the oxides of the elements Li to Cl

Bonding and stoichiometric composition of the oxides of these elements, and their behaviour with water, dilute acids and alkalis.
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The Periodic Table

Do. Q. 1b

The elements are arranged in the order of atomic number

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Elements were first arranged in order of increasing atomic masses by Dimitri Mendeleev (1834 - 1907) The elements were observed to repeat their properties periodically
Periodic Table (early forms)

(a)

(b)

Modern periodic table: (p.1) Rows periods Columns groups Classified into 4 areas:

s-block

p-block d-block transition elements

f-block

inner transition elements

s-block elements (p.2): Group IA: alkali metals 1 e in outermost shell (ns1) (e.g. Li, Na, K) Group IIA: alkaline earth metals 2 e in the outermost shell (ns2) (e.g. Be, Mg, Ca) p-block elements: Groups IIIA, IVA, VA, VIA, VIIA, 0 Group VIIA : halogens (ns2 np5) Group 0 : noble gases (ns2 np6)

d-block elements: Electronic configuration : (n 1)d1ns2 to (n 1)d10ns2 (Group IIIB) (Group IIB) Transition elements

f-block elements: Lanthanide series and actinide series : 4f and 5f orbitals are filled up with 1 to 14 einner-transition elements
Aims of Periodic Table: (p. 4): 1. Similar elements to be grouped together as families; 2. Gradual changes in properties such as electronegativity, ionization enthalpies.

The following periodic variations of the elements will be discussed:

Atomic Radius
First Ionization Enthalpy Electronegativity Structure and Bonding

Melting Point

Atomic Radius (p.9) How can scientists measure the sizes of atoms? (1) For non-metals, atomic radius refers to the covalent radius: Covalent radius is defined as half the internuclear distance between two covalently bonded atoms in a molecule of the element. (2) For metals, atomic radius refers to the metallic radius: Metallic radius is defined as half the internuclear distance between atoms in a metallic crystal.

Variation in atomic radius of the first 20 elements

Across the period, the atomic radii decrease progressively Down the group, the atomic radii increase progressively
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The atomic radius is governed by two factors: (p.6, notes p.9)

(1) Screening/Shielding of electrons (repulsion between electrons)

(2) Attraction of the nucleus (protons) for the electrons

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Down a group:
Increase in number of electron shells. Increase shielding effect from inner shells electrons. Across a period: Electrons add to the same outermost shell not much increase in shielding effect More protons greater attraction to e outweighs increase in shielding effect smaller size Decrease along the period of transition series is small: Electrons are added to inner d-orbitals screen the outermost electron shell.
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Melting point (notes p.11)

Melting Temperature depends on the magnitude of forces between particles Metals: Metallic Bond Giant Covalent Crystals: Covalent Bond Molecular Crystals: Van der Waals forces permanent dipole permanent dipole

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Variation in melting point of the first 20 elements

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Structure and Bonding (p.4)

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Across a Period (p.11)

1. Steady increase in melting point from Li to Be and Na to Al no. of outermost/delocalised electrons increases

no. of protons increases

metallic bond strength increases similar forces exist in liquid melting point not very high.

2. Carbon and silicon correspond to the maxima in Periods 2 and 3 both have giant covalent structures. Atoms are held together by strong covalent bonds.

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Across the Period of transition elements (p.13)

1. Metallic structures Very strong metallic bond because of the availability of d electrons / orbitals for metallic bonding. Maximum reaches in the middle except manganese as it has stable half-filled structure. 2. Carbon and silicon correspond to the maxima in Periods 2 and 3 both have giant covalent structures. Atoms are held together by strong covalent bonds.

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More on carbon: (p.7, 11) Carbon has two allotropes: graphite and diamond. Which of them is more stable?

The (C-C) bond distance in graphite is 1.415 A while that in diamond is 1.54 A.
Diamond is hard while graphite can be used as lubricant? Why? 3. The melting points of elements from N to Ne and P to Ar are relatively low they exist as discrete molecules which held by weak van der Waals forces
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 S has a higher melting point than P although the atomic size of P is larger than S. (Why?) S exists as S8 molecules in its molecular crystal whereas

P exists as P4 molecules in its molecular crystal

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Down a group (p.13)

1. For Group I Metals, melting point decreases down the group. Size increases

Shielding effect of inner shell e- increases

Metallic bond strength decreases

2. For halogens and noble gases, melting point increases down the group. Do Q. 2, Q.6 on p. 32 Size increases

Van der Waals forces increases

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a.

Giant covalent structure Large amount of energy used to break the strong covalent bonds. Metallic bond. Valence electrons & Size Metallic bond Metals: metallic bonds persist in liquid. Non-metals: weak van der Waals forces. Van der Waals forces determine the m.p. in non-metals. S8 largest size strongest van der Waals forces.

b.

c.

d.

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First Ionization Enthalpy (p.7, notes p.16)

X(g) X+(g) + e

The first ionization enthalpies of the first 20 elements

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Four factors affecting the magnitude of ionization enthalpy:

Electronic configuration (s, p, half-filled?) Nuclear charge

Screening/Shielding effect
Atomic radius

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Variation in the first ionization enthalpy of the first 20 elements

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1. Noble Gases have the highest I.E. (p.17)

The electronic configuration of noble gases is very stable (completely filled octet) 2. Alkali Metals have the lowest I.E. in a period (p.18) It has the lowest effective nuclear charge in the period

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3. Across a Period: (notes p.18)

1. General increase across periods 2 and 3 increase in nuclear charge outweighs the increase in shielding effect of additional electron of the same shell. stronger attraction to outermost electrons 2. Irregularities with the general increase Peaks in the general increase due to the extra stability provided by full-filled s sub-shell (Be) and half-filled p sub-shell (N)

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Explain why Group III elements have a lower first I.E. than Group II elements? (p. 19) i. ii. Extra stability is gained for completely filled s orbital in Group II elements. For Group III elements, electron is removed from p-orbital which is further away (at higher energy level) from the nucleus and shielded by the s electrons.
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Explain why Group VI elements have a lower first I.E. than Group V elements? (p.20) i. ii. Extra stability is gained for half filled p orbital in Group V elements. For Group VI elements, repulsion exists between the first paired p-electrons

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4. Down a group: (notes p.18)

Decrease down a group i. outermost electrons are further away from the nucleus

ii. Shielding effect of inner shells electrons. weaken attraction to outermost electrons

Arrange the following in increasing first I.E.: i. N, C, B ii. B, Be, Li iii. S+, S, S29
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Electronegativity (notes p.22) Electronegativity is the measure of the relative tendency of an atom to attract bond pair(s) electrons towards itself in a covalent bond Electronegativity values on an arbitrary scale from 0 to 4

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Electronegativity values of the first 20 elements

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Across the period, electronegativity increases from left to right Down the group, electronegativity decreases
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Explanations:
1. General increase across periods 2 and 3 increase in nuclear charge outweighs the increase in shielding effect of additional electron of the same shell. stronger attraction to outermost electrons

2. Decrease down groups

i. increase in size

ii. the increasing number of electron shells creates a greater shielding effect. smaller attraction to bonding electrons
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Diagonal Relationship (notes p. 23)

Li and Mg; Be and Al; B and Si show similar properties: like 1st I.E. and electronegativity Why? Shielding effect increases down a group and nuclear charge increases across a period.
Ionization enthalpy/ electronegativity of elements diagonally below one another are similar They form bond with similar strength / show similar chemical properties (will be discussed later)

However, C and P, N and S show NO diagonal relationship. Why? C and N has no low lying empty d-orbital

The END

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