CHEM5 Chapter 12.1 Enthalpy change When we measure heat change at a constant pressure we call it enthalpy change.

Standard enthalpy of formation is the enthalpy change when one mole of a compound is formed from its constituent elements under standard conditions and all reactants and products in their standard states. H2(g) + O2(g) H2O(l)

Standard enthalpy of atomisation is the enthalpy change when one mole of gaseous atoms is formed from its element in its standard state under standard conditions. Mg(s) Mg(g)

First ionisation energy is the enthalpy change when one mole electrons is removed from one mole of gaseous atoms. Na(g) Na+(g) + e-

First electron affinity is the enthalpy change when one mole of electrons is added to one mole of gaseous atoms. O(g) + eO-(g)

Lattice formation enthalpy is the enthalpy change when one mole of solid ionic compound is formed from its gaseous ions. Na2+(g) + Cl2-(g) NaCl(s)

Enthalpy of lattice dissociation is the enthalpy change when one mole of solid ionic compound is broken into its constituent gaseous ions. Enthalpy of hydration is the enthalpy change when water molecules surround one mole of gaseous ions. Na(g) Na(aq)

Enthalpy of solution is the enthalpy change when one mole of solute dissolves completely in sufficient solvent to form a solution which the ions are far enough apart to not interact. NaCl(s) Na2+(aq) + Cl2-(aq)

Mean bond enthalpy is the enthalpy change when one mole of gaseous molecules each break one covalent bond to form two free radicals, averaged over a range of compounds. CH4(g) 12.2 Born-Haber cycles The Born-Haber cycle is a thermochemical cycle that includes all the enthalpy changes involved in the formation of an ionic compound. CH3(g) + H(g)

Trends in lattice enthalpies: With smaller radius positive ions and negative ions the lattice enthalpy of formation is more negative and therefore easier to form. 12.3 More enthalpy changes (Born-Haber cycle again) 12.4 Calculating enthalpy changes using mean bond enthalpies If you are not given enthalpy of combustion or formation but are given bond enthalpies of certain covalent bonds you can work out the enthalpy change of a reaction by doing a simple triangle.

Elements of the reaction

Reactants

Products

The arrows go the wrong way because you are given Bond enthalpy which is the change in breaking a bond and so in effect forming the elements. All you do is total up the sum of each arrow, swap one round and add them together. (when you swap the arrow make sure you swap if its negative number to a positive or visa versa) 12.5 Why do chemical reactions take place? Use feasible to describe if a reaction will occur on their own accord. Entropy is the measure of how disordered a reaction is. A gas is more disordered than a solid because of its randomness and so it has a higher entropy. A reaction producing more moles of a gas than its reactants is increasing the entropy. Gibbs free energy change is the measurement if a reaction is feasible at a certain temperature. G = H TS S = entropy change. For a reaction to happen G must be zero or below.

Be careful.. the units for S is JK-1mol-1 the units for H is KJmol-1 so you must divide S by 1000 to obtain the same KiloJoules
Kinetic factors: Neither enthalpy or entropy changes tell us anything about how quickly or slowly a reaction is likely to go. So if we predict a reaction is spontaneous it might go so slowly for practical purposes it might not happen at all. 13.1 Periodicity The elements: Na, Mg, Al are metallic Si is semi-metal P S Cl are non-metals Ar is a nobel gas

Reactions with water: Na, Mg and Cl are the only ones that react with cold water 13.2 the oxides of elements in Period 3 The metal oxides are giant ionic lattices. The bonding in aluminium oxide has some covalent character, this is because Al forms a very small ion that can get close to O and distort its electron cloud. Silicon oxide is macromolecular P and S oxides are simple covalent molecules. Reaction of oxides with water: Oxide Na2O MgO Al2O3 SiO2 P4O10 SO2 SO3 Equations: Na2O + H2O MgO + H2O P4O10 + 6H2O SO2 + H2O SO3 + H2O 2Na+ + 2OHMg(OH)2 4H3PO4 H2SO3 H2SO4 Mg2+ + 2OHH+ + H2PO4H+ + HSO3H+ + HSO4Bonding ionic ionic ionic/covalent covalent covalent covalent covalent Ions present after reaction Na+, OHMg2+, OHinsoluble no reaction insoluble no reaction H+, H2PO4H+, HSO3H+, HSO4Approx pH 13-14 10 7 7 0-1 2-3 0-1

13.3 Oxides of the elements of period 3 and their reaction with acids and bases
Oxide
Na2O MgO Al2O3 SiO2 P4O10 SO2 SO3

Reaction with H2SO4

Na2O + H2SO4 = Na2SO4 . + H2O

Reaction with HCl

MgO + 2HCl = MgCl2 + H2O Al2O3 + 6HCl = 2AlCl3 + 3H2O

Reaction with hot conc. NaOH

Al2O3 + 2NaOH + 3H2O = 2NaAl(OH)4 SiO2 + 2NaOH = Na2SiO3 + H2O H3PO4 + 3NaOH = Na3PO4 + 3H2O SO2 + 2NaOH = Na2SO3 + H2O SO3 + 2NaOH = Na2SO4 + H2O

14.1 Redox equations Balancing redox equations: 1. Write the half equations 2. Balance the electrons by multiplying 3. Combine the equations ( you may cancel out species that appear both side of the equation such as H+ or H2O 14.2 Electrode potentials and the electrochemical series To calculate the emf of a cell you take the electrode potential on the right of the cell representation takeaway left.

Oxidation left Reduction right (OR) 14.3 Predicting the direction of redox reactions When we have the voltage of two half cells you know that the electrons from the more negative voltage will go to the more positive voltage. This means the more negative one is going to be producing electrons and getting oxidised. If a cell ends up having a negative emf it is not feasibl.

14.4 Electrochemical cells Non-rechargable cells: Zinc/Carbon cell using carbon as the anode Zn2+ Zn 2NH4+ 2NH3, H2

As the cell discharges the zinc is used up and the walls of the zinc canister become thin and prone to leakage. The ammonium chloride used is acidic and can be corrosive. Rechargable batteries: Lead-acid batteries. reaction when cell discharges: PbO2 + 4H+ + 2SO42- + Pb Portable batteries: Nickel/Cadmium overall equation: 2NiO(OH) + Cd + 2H2O The fuel cell (hydrogen cell) Its only product is water and the overall equation is 2H2 + O2 2H2O However, this may not to be as green as it seems as the source of hydrogen at the moment is from crude oil but could be made from electrolysis.. which need electricity that is made by burning fossil fuels and releasing CO2. 15.1 The general properties of transition metals The definition of a transition metal is that it forms at least one stable ion with a partially filled d orbital. Sc forms only Sc3+ which is 3d0 Zn forms only Zn2+ which is 3d10 They are therefore not transition metals. Chemical properties: Variable oxidation states Catalysts Complex formation Coloured 2Ni(OH)2 + Cd(OH)2 2PbSO4 + 2H2O

15.2 Complex formation and the shape of complex ions

All transition metal ions can form co-ordinate bonds by accepting electron pairs from other ions or molecules. The number of dative/co-ordinate bonds a complex has is called the co-ordination number. The electron pair donor to a transition metal is called: (one electron pair)- ligand (two) - bidentate (three or more) - multidentate Co-ordination number of 6 is usually octahedral 4 is usually tetrahedral 2 is linear (such as [Ag(NH3)2] One square planar complexes is cisplatin as shown below

15.3 Coloured ions Why are transition metal ions coloured? Transition metal compounds have partly filled d-orbitals Therefore it is possible for electrons to move from one d-orbital to another In a compound the presence of other atoms nearby makes the d-orbitals have slightly different energies When electrons move from one d-orbital to another of higher energy they absorb energy in the visible region of the light spectrum equal to the difference in energies The colour is therefore missing from the spectrum and we see the colours that are not absorbed (E = hv) Therefore you can use a colorimeter to find out the concentration of metal ions in a solution by using known samples and comparing the colour.

15.4 Variable oxidation states of transition elements

Potassium manganate(VII) as an oxidising agent: MnO4- + 5e- + 8H+ Mn2+ + 4H2O

Potassium dichromate(VI) can be used in titration to find out the concentration of Fe2+ ions: 6Fe2+ + Cr2O72- + 14H+ 6Fe3+ + Cr3+ + 7H2O (the colour change cannot be seen though so an indicator of diphenylaminesulfonate is used which turns from colourless to purple) Typical transition metal species: [M(H2O)6]2+ [M(H2O)4(OH)2] [M(H2O)2(OH)4]22CrO4- is yellow Cr2O72- is orange acid solution neutral alkaline

15.5 Catalysis Heterogenous catalysts are in a different phase than the reactants Homogenous are in the same phase. Ways to improve catalysts: Surface area Spread catalyst on an inert support medium However catalysts do not last forever. Over time the surfaces may become covered with impurities this is called poisoning The finely divided catalyst may gradually be lost from the support medium. The haber process uses iron catalyst which is heterogeneous.. it lasts for about 5 years until gets poisoned by impurities in the gas stream such as sulphur. The contact process. (used in the process for producing H2SO4) SO2 + V2O5 2V2O4 + O2 SO3 + V2O4 2V2O5

This is an example of the use of variable oxidation states as a two step catalyst The overall equation is 2SO2 + O2 2SO3 Homogenous catalysts:

When the catalyst is in the same phase an intermediate species is formed (such as chlorine in the decomposition of ozone) In an energy profile diagram it would show as two lower bumps rather than one large one due to the 2 step process, the first step being making the reactive intermediate.

Autocatalysis occurs when one of the products of a reaction is the catalyst for the reaction. This means it starts slowly at the uncatalysed rate and then builds up as the product is formed but then slows back down as the reactants are used up.

16.1 Lewis acids and bases Lewis acids are electron pair acceptors Lewis bases are electron pair donors Amphoteric hydroxides: This means showing both acidic and basic properties. Anionic transition metal compounds: Transition metals are usually found as a positive ion in a complez but some have a negative charge such as MnO4- ions and CrO4- and Cr2O72-. 16.2 Ligand substitution reactions Water ligands can be replaced by neutral ligands, negatively charged ligands, bi or multidentate ligands (this is called chelation) and replacement can be complete or partial. Chelation is the formation of complexes with multidentate ligands. An EDTA molecule can displace all 6 H2O ligands from [M(H2O)6]2+.

16.3 A summary of acid-base and substitution reactions of some metal ions The orange highlighted compounds are ones that do not follow the pattern of either the M2+ or M3+ metal ions.