Periodicity Periodicity: Trends, Patters, and variations within the periodic table.

Periodic table: elements in order of atomic (proton) number. Periods: rows = no. Of shells (energy levels/ 1st quantum number) Groups: Columns = No. Of valence electrons (electrons in the highest filled energy level outer shell) Groups 1-2: S-block (most energetic electrons are in the s orbital) Transition elements: D-block Group 3-8: P block Lanthanides and actinides: F block

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Trends in physical properties: 1- Ionization energy: 1st IE: The first ionization energy is the energy required to remove one mole of electrons from one mole of atoms in a gaseous state.

Because the e- is being taken from a higher energy level, the attraction between the valence e- and the nucleus is less due to: A. Increased distance. B. Increased shielding of the nuclear charge by inner shell electrons. Shielding is the decrease in attraction between the nucleus and electrons in any atom with more than one electron shell. There is a gradual general increase in 1st ionization energy within a period due to an increasing +charge in the nucleus with no extra shielding or distance to the valence electrons. There is a small decrease in the first ionization energy with a period between group 2 and 3 due to p orbital being at a higher energy than s and p electrons being slightly easier to take and between groups 5 and 6, due to group 6 having a p orbital with two opposite spinning e-s which repel each other making the 2nd e- easier to be removed. Electronegativity Trends Electronegativity: the ability of an atom to attract a bonding pair of e- (ie- a covalent bond) to itself. A small difference in electronegativity between 2 atoms gives covalent bonds. A big difference in electronegativity between 2 atoms gives ionic bonds. Electronegativity increases across a period, and decreases down a group.

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2 factors affect electronegativity: 1. Effective core/ nuclear charge: i.e., how many protons are attracting the outer shell e-? It is the net positive charge experienced by an electron in a multi-electron atom.

Nucleus: Proton No. No. Of inner e-s:

Li 3p+ 2e-

C 6p+ 2e-

F 9p+ 2e-

We can say that their inner electrons cancel out some of the nucleus charge. (shielding effect) Effective core charge: Li 3+2= 1+ C 6-2=4+ F 9-2=7+

A larger effective core charge can attract e- to the valence shell better. 2. Atoms lower down a group have valence shells further from the nucleus. The nucleus is therefore has less attractive power.

Atomic and ionic radius Atomic radius: distance from nucleus to outer shell. This cannot be measured directly (we dont know exactly where the valence electron will be) Atomic radius can be measured using x-ray diffraction.

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The noble gases do not form molecules so we cant find their atomic radii. We can mea.sure atomic radius in molecules since the atoms are held tightly together Atomic radii increases down a group more shells bigger atom. Atomic radii decreases across a period- effective core charge increases, which means valence electrons are held tighter.

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Ionic radius: Cation: +ion Down a group: increases (more shells) Across a period: only compare isoelectronic ions (i.e.- same electronic arrangement) Eg- Na+, Mg2+, Al3+, (All 1s2,2s2,2p6)
Ionic radius decreases

Anions (-ions): Down a group: increases (more shells) Across a period: only isoelectronic ions Eg- P3-,S2-,Cl- (All 1s1,2s2,3p3)
Ionic radius increases

Na+

Mg2+

Na3+

P3-

S2-

Cl-

2 Shells

3 Shells

Melting point Metals: decreases down group as attractive forces between nucleus and delocalized electrons decreases. Non-metals: increase down group as attractive forces between molecules (van der waals) increases. Across a period, the pattern is not so good due to metals bonding differently to non-metals.

Chemical properties of group 1 Alkali metals: react with water to form alkali. Form 1+ ions (unipositive ions) Soft, low melting points, stored in oil to prevent tarnish (oxidize in air) quickly. Reactivity increases down the group as the valence e- is easier to remove (1+ ions) 1- Reaction with H2O(l):

2- Reaction with halogens

Metal Halide

Group 7- Halogens Fluorine (F), Chlorine (Cl), Bromine (Br), Astatine (At) All diatomic molecules. Trends down the group: 1. 2. 3. 4. 5. Melting point/ Boiling point increases. Colour gets darker. Reactivity decreases. Toxicity decreases. Oxidizing ability decreases.

When halogens react, the form anions (halides, eg- Cl-) by gaining an electron and so being reduced. If they are reduced, the must be oxidizing another species.

The attractive power between the nucleus and the valence shell decreases as the number of shells increases (more distance, more shielding) Displacement reactions of halogens/ halides

The reaction only works if X is more oxidizing (higher up the group) than Y. We use colour changes as evidence for the reaction. If bromine is formed: orange/yellow in organic solvents. If Iodine is formed: Yellow/orange in water but purple in organic solvents.

Redox reactions:

Pale green colourless

Orange

Colourless

Reduction Oxidation Period 3

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Sodium, magnesium and aluminum are metals. They are shiny , and conduct heat and electricity. Silicon is a metalloid as it had some of the properties of a metal and a non-metal. Phosphorus, sulfur, chlorine and argon are non-metals. They do not conduct electricity.

Period 3- Oxides

The oxides of metals consist of the metal ions and oxide ion. Therefore they are ionic. They are white solids at room temperature. They have high melting and boiling points. The oxides of metals conduct electricity as a liquid, as they are decomposed to their elements, and the ions are free to move. As a solid, they are fixed in place as a lattice. Silicon dioxide has a giant covalent structure, so it has a high melting and boiling point and does not conduct electricity when molten. It is a bad conductor. It is insoluble in water, so it does not react to form an acid. It is still classified as an acidic oxide because it reacts with sodium hydroxide (base) at high tempretures.

Metal oxides are basic Non-metal oxides are acidic. Non-metal oxides are covalent since there is a small difference in electronegativity between the elements and oxygen.

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The oxides of sulfur, phosphorus, and chlorine have simple covalent molecular structures with low melting and boiling points. They do not conduct electricity in the liquid state.

Metal oxides react with water to form aqueous solutions of metal hydroxides, which are alkali. Sodium hydroxide is very soluble, while magnesium hydroxide is only sparingly so.

Na2O + H2O

2NaOH

Aluminum oxide is amphoteric. It can either be acidic or basic depending on weather it is reacting with an acid or a base.

The non-metals react with water to form acids.

All three non-metals form more than one oxide with oxygen. As per the syllabus, you need to know the following reactions too:

Period 3- Chlorides The physical properties of the chlorides are related to the structure. Sodium chloride and magnesium chloride are ionic. They conduct electricity when molten and have high melting points. Sodium chloride is neutral (pH 7 when dissolved in distilled water) Magnesium chloride is slightly acidic when dissolved in water. The density of the charge (measure of electric charge per unit volume of space) of magnesium is larger than that of sodium. Magnesium ions react with water molecules to form hydrogen ions. Aluminum chloride is covalent. When solid, it exists as aluminum and chloride ions. When it melts, Al2Cl6 is formed. This chloride is a poor conductor of electricity. In the gas state, there is equilibrium between Al2Cl6 (dimer) and 2AlCl3 (monomer). When anhydrous aluminum oxide is added to water, an exothermic reaction takes place, and hydrochloric acid is formed.

This does not directly happen. When the aluminum ions are in water, they become hexahydrated to form the ion [Al(H2O)6]3+ . The water molecules are attracted to the aluminum ion (high charge density), so three water molecules dissociate to give hydrated aluminum hydroxide and hydrochloric acid. The remaining elements in period 3 have simple molecular structures held by weak van der Waals forces. They have low melting and boiling points and form acidic solutions when dissolved in water. Both silicon and phosphorus react with water to produce aqueous hydrochloric acid (and fumes of it) and another acid depending on the element. Chlorine also reacts with water to form HCL and HCLO. The reaction of the chlorides of carbon and silicon with water
Monomer: A molecule that may bond chemically to other molecules to form a polymer. Dimer: A chemical entity consisting of two structurally similar monomers joined by bonds. Polymer: is a chemical compound or mixture of compounds consisting of repeating structural units

Both tetrachloromethane (CCl4) and silicon tetrachloride (SiCl4) are colourless liquids at room temperature and have a low boiling points. The two compounds share many similarities, yet carbon tetrachloride is immiscible (will form a layer over it) in water, while silicon tetrachloride reacts very exothermically with it. Both electron configurations end with the general formula [ns np]. (Carbon= 1s2 2s2 2p2) (Silicon= 1s2 2s2 2p6 3s2 3p2) Both atoms have empty 3d orbitals. Carbon cannot utilize them since theyre at a much higher energy level than the outer electrons. For silicon, the 3d orbitals are only slightly higher than the 3p orbitals, so they can be easily utilized. When water molecules collide with silicon tetrachloride, two non-bonding pairs of oxygen electrons utilize the empty 3d orbitals in the silicon atom to form a coordinate bond. Then a silicon-t-chlorine bond breaks, and is substituted by a water molecule, which gives out hydrogen in the process.

First row d-block Sc to Zn Transition elements (Metal): An element whose atoms or ions has an incomplete set of d-orbitals with one or more oxidation state. Oxidation state is the number of electrons to be added (or subtracted) from an atom in a combined state to convert it to elemental form. It is also known as oxidation number. Not all d-block metals are transition metals. Zinc: [Ar] 4s2 3d10 Zn2+ (only ion) [Ar] 3d10 Scandium: [Ar] 3s2 3d1 (incomplete, could be considered transition) Sc3+ (only ion) [Ar] (empty 3d orbital, so not transition metal) Properties: 1- Variable oxidation state- 4s and 3d orbitals are very close in energy. Aufbam: 4s filled before 3d but taken before 3d too. Different number of electrons can be taken to produce ions of different charge. 2+ is common as most transition metals can lose just their 2 4s electrons. Cu only has 4s1 but still forms 2+ 3+ ions exist (Fe3+) 4+ ions exist (Mn4+) but are rare due to the small ions having a high charge density, which polarizes surrounding ions/molecules leading to covalent bonding. 5+, 6+, 7+ are not ionic charges but oxidation states in covalently bonded ions. Eg- MnO4(Purple) Cr2O72(Orange) Cr has an oxidation number of +6 Mn has an oxidation number of +7

2- Complex ion formation-

Complex ion: A metal surrounded by ligands. Ligand: A species (ion or molecule) which bonds datively to the metal ion because they have a non-bonding pair of electrons to form coordinate covalent bonds. Dative (coordinate) bond: covalent bond where one species donates both electrons to the bond and the other species. This happens because transition metals are small and highly charged (high charge density) and are polarizing (attract electrons) Therefore, the ions are lewis acids because they are electron accepters. Coloured transition metal complexes A coloured compound absorbs certain wavelengths of light and the colour we observe is due to the combination of colours not observed. When ligands bond to the central metal ion, its d orbitals no longer have equivalent energy 2 orbitals have higher than 3. Electrons can be excited from the lower to higher set by absorbing wavelengths of visible light. The colour we observe depends on the wavelength absorbed which depends on the size of the split.

Both gaps are the same size

Co2+ (no ligands attached)

Co2+ (ligands attached)

Co2+ (having an excited e-)

The size of E and therefore the complexs colour depends on: The transition element The oxidation state/charge of the transition element The type of ligand. The shape of the complex.

Ligands can be replaced

hexa aqua copper (II) ion, complex ion in CuSO4(aq) When OH-(aq) or NH3(aq) is added a blue precipitate is formed contains When excess ammonia is added, the water ligands get replaced. which

tetra ammine copper (II) ion (deep blue) if concentrate HCL is added to the tetra aqua copper (II) ion, then yellow tetra chloro copper (II) complex ion is produced.

Catalytic properties Catalyst- Increase the rate of reaction by producing an alternative route with a lower activation energy. The catalyst is unchanged at the end of the reaction. Transition metals and their compounds are often catalysts for specific reactions. Elements provide a surface, which a reactant molecule can adsorb (stick) to. This makes it more likely that a different reactant will collide successfully with it. Different transition elements have different surfaces which allow different molecules to be adsorbed.

Transition metals can catalyse by providing an alternative way to transfer electrons between reactants (acting almost as an intermediary) Homogeneous catalysts Are in the same phase as the reactants.

Catalyst: MnO2(s)

Catalyst: Fe(s)

Heterogeneous catalysts- Are in a different phase to the reactants.

Alchohol(aq) + catalystic acid(aq)

ester

Haber process- Catalyst is Fe Contact process- Catalyst is V2O5 The position of equilibrium is not changed so the yield does not change. But rate increases so the equilibrium is reached quicker so more product/ unit time= more profit.