Inorganic Chemistry, tips and summary Section A. Constructing equations.

Please realize that concepts learnt in other topics are still useful. The most important thing is to figure out the type of reaction. There are a few usual types of reactions, namely 1. Acid-base 2. Redox 3. Precipitation 4. Decomposition 5. Hydrolysis 6. Displacement 1. Acid-base reactions. Look for H+ donors or H+ acceptors. Look for OH- donors or OH- acceptors. Eg. Metal oxides are basic: MO + 2HCl > MCl2 + H2O The O2- ion is actually a H+ acceptor : O2- + H2O > 2OHAluminium oxide and hydroxide are amphoteric and can act as acid. Al2O3 + 2NaOH + 3H2O > 2Na[Al(OH)4] Al(OH)3 + :OH- > [Al(OH)4] Lewis acid (accepts lone-pair from OH) Notice how the two salts are the same If you are constructing equation, focus on the ions that transfer H+ or OH first. Balance charge with OH or H+ or use counter-ions (such as Na) Always balance H or O with H2O LAST.

2. redox reactions: Watch out for i) common oxidizing agents (with particles in high oxidation state) eg MnO4 (Mn is +7) ii) common reducing agents ( metals, and particles at low oxidation state) eg Na, I iii) period trends - oxidizing power increase across period (electronegativity increases) -reducing power decreases across period Group trends - Reducing power increase down a group (I is best reducing agt among halides, K is more reducing than Na in Gp I) - Oxidizing power increase up a group (F is best oxidizing agt among halogens) To construct equations: you can use the half equation mtd from notes (which is slow) or use this: i) Identify the starting material and product in the redox reaction. ii) Determine the in oxidation states, from there, determine the no. of e transferred. iii) Determine the stoichiometric ratio of the reagents by using the LCM of no of e transferred. iv) make sure the non H and O atoms are balanced first. v) balance charge with H+ or OH

vi) balance H or O atoms with H2O last. This is extremely useful for GpVII and transition elts. Example 2.1 Disproportionation of Cl2 in hot NaOH. (must remember oxidation state 0> -1, 0 > +5) i) Cl2 > Cl + ClO3 ii) Cl takes in 1 e to give Cl, Cl gives out 5 e to become ClO3 (V) The mol ratio is 5:1 (LCM is 5) iii) Cl2 > 5Cl + ClO3 iv) Balance non O, H atom first 3Cl2 > 5Cl + ClO3 v) 6 ve charge on RHS, so, 3Cl2 + 6OH > 5Cl + ClO3 vi) balance H and O with H2O: 3Cl2 + 6OH > 5Cl + ClO3 + 3H2O Example 2.2 Reaction of NaBr and NaI with conc. H2SO4 Recognize that a) H2SO4 has acidic H+, 1st proton is very acidic, so acid base rxn takes place first. b) the sulphur in H2SO4 is +6, so it has some oxidizing ability. c) I is a good reducing agent. Acid-base: Redox : NaBr + H2SO4 > NaHSO4 + HBr HBr (-1) can reduce S from +6 to +4 (in SO2) HBr + H2SO4 > Br2 + SO2 (-1) (+6) (0) (+4) 2HBr + H2SO4 > Br2 + SO2 balance H or O with H2O Acid-base: Redox : 2HBr + H2SO4 > Br2 + SO2 + 2H2O (1 e for I, 2 e for S, ratio should be 2:1)

NaI + H2SO4 > NaHSO4 + HI HI(-1) is a good reducing agent and can even oxidize S from +6 to -2 (in H2S) HI + H2SO4 > I2 +H2S (-1) (+6) (0) (-2) 8HI + H2SO4 > 4I2 + H2S (1 e for I, 8 e for S, ratio is 8:1)

Balance H or O with H2O

8HI + H2SO4 > 4I2 + H2S + 4H2O

You can see right now if you have a good ability to construct equations, memory work is reduced/made easier when studying inorganic chem. You should not simply memorize equations without understanding what sort of reactions are taking place, and how the starting materials become the products. Predicting if a redox reaction takes place: Use Eo value. For spontaneous reaction Eo >0, or G<0 Note: G = -nFE

3. Precipitation You have to be familiar with the solubilities of ionic cpds. Soluble All nitrates (NO3) Most halides (Cl, Br, I) Most sulphates (SO42) Exceptions: Oxides of Na+, K+, NH4+ and larger group II cations, eg. Ca2+, Sr2+, Ba2+. Exceptions: Hydroxides of Na+, K+ and larger group II cations, eg. Ca2+, Sr2+, Ba2+. Exceptions: Sulphides of Na+, K+, NH4+ and group II cations, eg. Mg2+, Ca2+, Sr2+, Ba2+. Exceptions: Carbonates/ phosphates of Na+, K+ and NH4+. Exceptions: Chromates of Na+, K+, NH4+ and Mg2+ (Small group II cations) Sparingly soluble (Often known as insoluble) Nil. Exceptions: Halides of Ag+, Pb2+, Cu2+ Exceptions: Sulphates of Pb2+, Ca2+, Ba2+ Most oxides (O2) Most hydroxides (OH) Most sulphides (S2) Most carbonates (CO32) & phosphates (PO43) Most chromates (CrO42)

Spot some trends above. For example, all Gp I metal salts are soluble. Be aware especially of hydroxides, since an acid-base problem can incorporate solubility. For example, if a reaction produced hydroxide, and metal ions are present, there is a high chance of metal precipitate forming. For a good summary and examples: Refer to pg 11-12 of your Solubility Equilibria notes, and the QA summary of your Transition element chemistry notes. 4. Decomposition Watch out for 1 compound reacting by itself, to break down to give more compounds/elements. Usually stable small molecules of gases are released. Stable solids with high LE such as oxides are usually residue. You are expected to be familiar with the decomposition of Gp II nitrates, carbonates, hydroxides. For unfamiliar decomposition reactions, clues are usually provided by the question. Read carefully and use the context. Many decomposition reactions are also redox reactions. Example 4.1 Heating of ammonium dichromate causes decomposition to the oxide Cr2O3 and other gases. Construct the equation for the reaction. Solution Cr2O72- (Cr +6) Cr2O3 (Cr+3); Cr is reduced. In decomposition reaction, if one species is reduced, another species from the same cpd is oxidized. Each Cr gains 3 electrons. The only other species left behind is the ammonium ion. Note also that since the mol ratio of NH4+ to Cr2O72- is 2:1 [MF: (NH4)2Cr2O7] , each ammonium ion needs to lose 3 electrons. Probable oxidation of NH4+ (N: -3) to N2 (N: 0) (NH4)2Cr2O7 (-3) (+6) Cr2O3 + N2 + 4H2O (+3) (0)

5. Hydrolysis Involves splitting water. 2 major types for inorganic chem.. 1) For ionic cpds. Cation hydrolysis. Cation with high charge density M3+, have high polarizing power. Polarization of water molecules take place and the O-H bond will break more easily, releasing H+. 2) For covalent cpds. Eg Covalent chlorides. Similar to nucleophilic substitution (please do not use this term!, simply name the reaction as hydrolysis). Water donates lone pair (as a nucleophile) to central atom eg, P in PCl3, and HCl is released. For period 3 *low lying vacant d orbitals easily accept lone pair electrons from water, and hydrolysis takes place readily Section B Learning inorganic chem. 1. Dont go straight into memorizing equations! Key approaches: -Big picture view first! Use general trends, relate structure + bonding to property, and familiarize with general character of the compound/element. -Relate specific reactions/equations to these big picture properties - It is more important to remember the identity of the starting material and product and type of reaction; the equation can be constructed on the spot. a. Structure (ionic vs covalent, oxidation state, Zeff) influences property (acidity, basicity, reducing power, oxidizing power) 2. trends. Eg. Oxides and chlorides across period, increasing covalency, increasing acidity. -Ionic oxide, O2, basic. Covalent oxide, adds water to give XOOH, acidic -Ionic chlorides, Cl doesnt do much, Mx+ has increasing polarizing power, cation hydrolysis. - Covalent chlorides, hydrolysis with water (like nucleophilic sub.) acidic solution Eg. Gp II, polarizing power of M2+ decreases going down the group Eg. Gp VII, oxidizing power of X2 is greatest at top of group, reducing power of X is greatest at bottom of group 3. When solving questions, make use of characteristic chemistry, as well as context and clues from the question. Eg. 1)Metal ions, lookout for : cation hydrolysis, precipitation, complex formation, redox 2) OH, lookout for: neutralization, precipitation with metal ions, hydrolysis of organic/covalent cpds, redox reactions (sets alkaline conditions, affects equilibrium, especially for gp VII) 3) Gp VII, redox reactions.eg X2 is oxidizing X2 can disproportionate in OH X is reducing.(reactions with H2SO4) Precipitation. X with Ag+, Pb2+