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Chemistry Unit 5 Notes

Thermodynamics
1) Be able to Define: a. Enthalpy of formation the enthalpy change when one mole of compound is formed from its elements in their std states under std conditions. Eg: b. Ionisation enthalpy - the enthalpy change when one mole of electrons is removed from one mole of gaseous atoms to form one mole of gaseous ions with a single positive charge. Eg: c. Enthalpy of atomisation of an element and of a compound the enthalpy change when one mole of gaseous atoms if formed from an element or compound Eg: d. Bond dissociation enthalpy the enthalpy change when one mole of bonds of the same type are broken. Eg: e. Electron affinity the enthalpy change when one mole of electrons is gained by one mole of gaseous atoms to form one mole of ions with a single negative charge. Eg: f. Lattice enthalpy (defined as either lattice dissociation or lattice formation) the enthalpy change when one mole of ionic solid is separated into its gaseous ions. Eg: g. Enthalpy of hydration the enthalpy change when one mole of separated gaseous ions is dissolved completely in water to form one mole of aqueous ions. Eg: h. Enthalpy of solution the enthalpy change when one mole of an ionic substance is dissolved completely in a volume of water large enough to ensure that the ions are separated and do not interact with each other. Eg: 2) Be able to construct Born-Haber cycles to calculate lattice enthalpies from experimental data : a. Start with DHF arrow points down b. Above that write DHat for both elements and DHie for the one the becomes positive arrows pointing up c. Parallel to the DHie, write DHea for the one that becomes negative arrow pointing down d. Underneath write the DHlatt (pointing down for formation, up for dissociation). This should end up at the same enegy level at the orginal DHf. e. DHlatt = Dhea Dhie Dhat Dhat + DHf Note that when you follow the cycle and are going against the direction of an arrow, the value becomes negative. Watch out for tricks: elements that have minus or plus 2 charge have a 1st and 2nd IE or EA If the compound has 2 of one element (eg: MgCl2) then you need to double the value for that element (eg: 2 atomisation enthalpy and electron affinity of chlorine)

Jessica Horsburgh

3) Be able to compare lattice enthalpies with those from calculations based on a perfect ionic model to provide evidence for covalent character in ionic compounds a. Some ionic compounds have more covalent character than others. Covalent character increases when the positive ion has high polarizing power it is small and has a high charge and therefore has high charge density and the negative ion is most easily polarised it is large and has a high charge. These are Fajans rules b. % difference = 4) Be able to calculate enthalpies of solution for ionic compounds from lattice enthalpies and enthalpies of hydration this involves Hess Law: the enthalpy change of a reaction is the same regardless of the rout taken (otherwise known as the triangle method ) DHsoln = DHlatt + DHhyd of both elements - both are following the direction of the arrows (unlike bond enthalpy calculations) so the original values can be used without worrying about changing the sign. 5) Be able to use mean bond enthalpies to calculate an approximate value of DH for other reactions the triangle method can be used for this where the products and the reactants can both be made into a common product which is the bottom point of the triangle both arrows point down towards this. If DHa is the arrow from the reactants to the common product and DHb is the arrow from the products to the common product: DHf = DHa DHb because you are going against the direction of DHb. Free-energy change (DG) and entropy change (DS) 1) Understand that DH, whilst important, is not sufficient to explain spontaneous change (e.g. spontaneous endothermic reactions) whether a reaction is feasible depends also on entropy (DS) and temperature (T) 2) Understand that the concept of increasing disorder (entropy change DS) accounts for the above deficiency, illustrated by physical change (e.g. melting, evaporation) and chemical change (e.g. dissolution, evolution of CO2 from hydrogencarbonates with acid) 3) Be able to calculate entropy changes from absolute entropy values: Entropy change = Entropy of RHS- Entropy of LHS 4) Understand that: a. the balance between entropy and enthalpy determines the feasibility of a reaction b. this is given by the relationship DG = DH TDS (derivation not required) 5) Be able to use this equation to determine how DG varies with temperature plot a graph where y = mx + c is equivalent to DG = -DST + DH. When the value is below 0 (DG is negative), the reaction is feasible.

6) Be able to use this relationship to determine the temperature at which a reaction is feasible rearrange the equation to DG = 0 So: DH = T DS and T =

Jessica Horsburgh

Periodicity 1) Be able to describe trends in the reactions of the elements with water, limited to Na and Mg . a. Na reacts vigorously with water: 2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) b. Mg reacts slowly with water: Mg + 2H2O Mg(OH)2 (aq) + H2 (g) Mg reacts vigorously with steam: Mg (s) + H2O (g) MgO (s) + H2 (g)
2)

Be able to describe the trends in the elements Na, Mg, Al, Si, P and S with oxygen, limited to the formation of Na2O, MgO, Al2O3, SiO2, P4O10 and SO2. a. 4Na (s) + O2 (g) 2Na2O (s) Burns vigorously in air with a yellow flame. b. 2Mg (s) +O2 (g) 2MgO (s) Burns vigorously in air with a brilliant white flame. c. 4Al (s) + 3O2 (g) 2Al2O3 (s) - Protected by the oxide layer on the surface, but powered Al burns vigorously in air. d. Si (s) + O2 (g) SiO2 (s) Also protected by an oxide layer up to 900C when it reacts to produce SiO2. e. P4 (s) + 5O2 (g) P4O10 (s) ignites spontaneously in air. f. S (s) + O2 (g) SO2 (g) melts easily when heated and burns readily in air.

3) Be able to explain the link between the physical properties of the highest oxides of the elements Na S in terms of their structure and bonding. a. Na2O giant ionic lattice, high melting point due to strong attraction between ions b. MgO giant ionic, higher MP than Na2O because it forms Mg2+ ions so stronger attraction between ions. c. Al2O3 lower MP than MgO because the Al3+ ions attract electron density from the O2- ions creating partially covalent bonds. d. SiO2 giant molecular structure, in order to separate the atoms covalent bonds would have to be broken so it has a very high MP. e. P4O10 - low MP, simple molecular structure only has weak dipole-dipole and Van der Waals forces holding molecules together. f. SO2 also simple molecular, low MP. 4) Be able to describe the reactions of the oxides of the elements Na S with water, limited to Na2O, MgO, Al2O3, SiO2, P4O10, SO2 and SO3, know the pH of the resulting solutions and explain the trends in terms of the type of bonding present. a. Na2O ionic substances dissolve in water to form hydroxides. Sodium is more soluble than magnesium. Results in pH 12-14. Na2O (s) + H2O (l) 2NaOH (aq) b. MgO - substances dissolve in water to form hydroxides. Magnesium is less soluble so results in a lower pH of 9-10. MgO (s) + H2O (l) Mg(OH)2 (aq) c. Al2O Insoluble in water. d. SiO2 - Insoluble in water. e. P4O10 Simple covalent structures form strongly acidic solutions of pH 0-2. P4O10 (s) + 6H2O (l) 4H3PO4 (Phosphoric (V) acid). f. SO2 Simple covalent structures form strongly acidic solutions of pH 0-2. SO2 (g) + H2O (l) H2SO3 (aq) (sulphurous acid or sulphuric (IV) acid) g. SO3 Simple covalent structures form strongly acidic solutions of pH 0-2. SO3 (g) + H2O (l) H2SO4 (aq) (sulphuric (VI) acid)

Jessica Horsburgh

5) Be able to write equations for the reactions which occur between these oxides and given
simple acids and bases

a. Na2O and MgO are bases and react with acids to form salts and water. b. Al2O3 is amphoteric it acts as both an acid and a base. c. SiO2 acts as an acid and reacts with bases for example it can cause glass stoppers to get stuck inside bottles of NaOH. P4O10 and SO2 are also acidic and react with bases to form salts and water Equilibria 1) Be able to apply the electron transfer model of redox, including oxidation states and half equations to d block elements d block elements can form at least one stable ion with a partially filled d sub-shell. They have several characteristics including variable oxidation states which makes it possible for them to undergo redox reactions. For a redox reaction: i. Write out the two elements: MnO4- Mn2+ ii. Add water on the RHS to balance out the oxygen on the LHS: MnO4- Mn2+ + 4H2O iii. Add H+ on the LHS to balance the hydrogen from the water on the RHS: 8H+ + MnO4- Mn2+ + 4H2O iv. Add electrons to make the total charges on each side the same: 5e- + 8H+ + MnO4- Mn2+ + 4H2O

2) Know the IUPAC convention for writing half-equations for electrode reactions half cell reactions are conventionally written as reduction reactions, showing electrons gained by the species. 3) Know and be able to use the conventional representation of cells an electrochemical cell is made up of 2 half cells where 2 half-reactions are taking place: one oxidation and one reduction. A cell diagram is used to represent them: Zn (s) | Zn 2+ (aq) || Cu2+ (aq) | Cu (s) The single line separates two phases (eg: solids and solutions) and the double line represents the salt bridge. The most positive substances is always nearest to the salt bridge and the least positive is always on the outside. If a half cell has a solid and a mixture of 2 aqueous ions a comma is used to separate them: Fe (s) | Fe2+, Fe3+ ||... 4) Understand how cells are used to measure electrode potentials by reference to the standard hydrogen electrode use a platinum electrode dipped in acid where the concentration of H+ is 1 mol dm-3. H2 (g) is bubbled through at 298K and 100kPa. This has a value of 0V. The electrode is connected by a high resistance voltmeter and a salt bridge (usually paper soaked in KNO3) to the electrode that you want to measure. A voltage reading is taken and the Ecell is worked out using the equation: Ecell = ERHS - ELHS where the 0v of the std hydrogen electrode is on the LHS, therefore Ecell = ERHS. 5) Know the importance of the conditions when measuring the electrode potential, E (Nernst equation not required) a change in conditions could change the equilibrium (according to Le Chateliers principal) and therefore the e.m.f. created in the reaction. 6) Know that standard electrode potential, E , refers to conditions of 298 K, 100 kPa and 1.00 mol dm-3 solution of ions

Jessica Horsburgh

7) Know that standard electrode potentials can be listed as an electrochemical series 8) Be able to use E values to predict the direction of simple redox reactions and to calculate the e.m.f. of a cell The electrochemical series gives the order of reducing or oxidising power. The more positive the electrode, the greater the tendency to undergo reduction, and the more negative the electrode, the greater the tendency to undergo oxidation Because you are given reduction values for both, just reverse the Ecell given for the right hand cell. When drawing a cell diagram, the more negative potential goes on the left and the reaction travels from left to right: Zn (s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s) ------------------------------------------> 9) Appreciate that electrochemical cells can be used as a commercial source of electrical energy half cell reduction reactions are given in the order of increasing oxidising power (becoming more +ve) or increasing reducing power (becoming more ve). 10) Be able to use given electrode data to deduce the reactions occurring in non-rechargeable and rechargeable cells and to deduce the e.m.f. of a cell - the Ecell must be positive for it to work, therefore using Ecell = ERHS - ELHS, the ERHS has to be a larger, positive value and the ELHS must either be small and positive or large and negative (because taking away a negative is the same as addition). In a Zinc Carbon battery the half equations are: Zn (s) Zn 2+ + 2eE= -0.76V 2MnO2 (s) + 2NH4+ (aq) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l) E= +0.75V The Zn reaction is more negative so goes on the left: Zn (s) | Zn2+ || MnO2 (s) | Mn2O3 (s) --------------------------------------------> So Ecell = +0.75 (-0.76) = +1.51V Rechargeable batteries have reversible reactions: Pb (s) + SO4-2 (aq) PbSO4 (s) + 2eE = -0.36V PbO2 (s) + SO42- (aq) + 4H+ + 2e- PbSO4 (s) + 2H2O (l) E = +1.69V Pb (s) | PbSO4 (s) || PbSO4 (s) | PbO2 (s) ------------------------------------------------->

11) Understand the electrode reactions of a hydrogen-oxygen fuel cell and appreciate that a fuel cell does not need to be electrically recharged. Hydrogen and oxygen are fed into two separate platinum-containing electrodes separated by an ion exchange membrane which allows H+ to pass through it. Hydrogen flows through the negative electrode: 2H2 4H+ + 4eThe electrons produced flow through an external circuit to the positive electrode and the H+ ions through the proton exchange membrane. Oxygen is fed through the positive electrode: O2 + 4e- + 4H+ 2H2O

Jessica Horsburgh