YEAR TWELVE CHEMISTRY CALCULATOR NOTES CHAPTER 14 Characteristics of equilibrium CHEMICAL EQUILIBRIUM In a closed system at constant temperature: 1.

Constant macroscopic properties: Inc. concentrations of reactants and products, colour, density, pressure 2. equal rates of forward and reverse reactions - A chemical equilibrium is a dynamic process forward and reverse reactions occur simultaneously PHYSICAL EQUILIBRIUM - Equilibrium exists in physical systems also: 1. equilibrium between liquid and vapour in a closed system 2. equilibrium between undissolved solid and dissolved solute in a saturated solution Equilibrium constant - Equilibrium constant (K) is a number which indicates the relationship between reactant and product concentrations at equilibrium - If pP + qQ <=> rR + sS K = [R]^r[S]^s / [P]^p[Q]^q K = products to the power of coefficient / reactants to the power of coefficient -K has the following characteristics: 1. It is a constant for a reaction at a given temperature 2. doesnt include solids or liquids in equation as their concentrations dont vary -value of K indicates relative proportions of reactants and products at equilibrium 1. K>>1 reaction strongly favours products - virtually goes to completion, 2. K<<1 reaction strongly favours reactants occurs to such a small extent it can be considered not to have taken place REACTING QUOTIENT - Reaction quotient (Q) includes the same concentration terms as K but can be used for concentrations other than equilibrium concentrations -value of Q indicates the direction which a reactant system will move to establish equilibrium 1. Q<K forward reaction favoured 2. Q>K reverse reaction favoured 3. Q=K system is at equilibrium Changes to equilibrium system LE CHATELIERS PRINCIPLE - states that if a chemical system at equilibrium is subjected to a change in conditions the system will adjust to re-establish equilibrium in such a way as to partially counteract the imposed change Ways of changing equilibrium pressure or volume of a gaseous system -If volume decreases (pressure increases) then the concentration of all particles increases. According to Le Chateliers principle the system adjust to alleviate the change by forming fewer particles

YEAR TWELVE CHEMISTRY CALCULATOR NOTES Ways of changing equilibrium - temperature -Only change that causes a change in the value of K -if temperature is increased then according to Le Chateliers principle the system tries to counteract the change by removing the heat. The endothermic reaction is favoured (when reactant combines with heat) -if temperature is increased then according to Le Chateliers principle the system tries to counteract the change by gaining/adding heat. The exothermic reaction is favoured (when reactants combine to produce heat) Ways of changing equilibrium - concentration - [] favours direction of reaction which consumes it - [] favours direction of reaction which produces it (a) By adding more solid to an aqueous solution at equilibrium Doesnt change the concentration of reactants or products -Solid will join the rest of the excess solute (b) Adding more ions of one of the species at equilibrium common ion effect E.g. NaCl(aq) added AgCl(s) <=> Ag+(aq) + Cl-(aq) - [Cl-] increases immediately, thus favouring the revers reaction (more particles means more collisions). As more AgCl(s) is produced the rate of the forward reaction increases, until a new equilibrium with equal but faster reaction rates is established (c) Adding more gas -Adding an inert gas or one that isnt part of the reaction wont affect the equilibrium N2O4 <=> 2NO2 E.g. NO2 is added -If NO2 is added the rate of the reverse reaction will increase (more particles means more collisions). Then more reactant forms so that the rate of the forward reaction starts to increase until a new equilibrium with equal but faster reaction rates is established -Originally the reaction was at equilibrium. When NO2 was added Q became greater than K. the reverse reaction was favoured to decrease the amount of product and increase the amount of the reactant. K was then re-established (d) Adding more water to an aqueous solution E.g CuSO4(s) <=> Cu2+(aq) + SO2-(aq) -Immediately [Cu2+] and [SO2-] ions decrease. Then according to Le Chateliers principal, the system adjusts to produce more [Cu2+] and [SO2-] ions. The forward reaction is favoured. The amount of CuSO4 will decrease because more dissolves so the solution once again become saturated Ways of changing equilibrium - catalyst -Adding a catalyst doesnt affect the yield of the product, has no effect of the concentration of reactants or products -Changes the rates of forward and reverse reactions equally -Equilibrium is reached faster and at a lower Ea

YEAR TWELVE CHEMISTRY CALCULATOR NOTES Applications of chemical equilibria -industrial chemical processes seek to achieve the maximum yield of product for the minimum cost -Factors affecting reaction rates, equilibrium and economics have to be considered in planning chemical plants -Sometimes factors affecting reaction rates and equilibrium are in conflict, a compromise set of conditions may be needed in which a reasonable yield is obtained at a satisfactory rate ECONOMIC FACTOR -Want to minimise cost -Achieved by cheap catalyst -Conditions such as high temperature and pressure are expensive REACTION RATE -Needs to be high -Achieved by high temperature and concentration and a catalyst EQUILIBRIUM -Want high yields -Achieved by adjusting factors to favour products Case study: N2(g) + 3H2(g) <=> 2NH3(g) + 92kJ TEMPERATURE -Reaction is exothermic; reactants are favoured -Le Chat principle says high yields favoured by low temperature -Low temperature gives slow reaction rate -Compromise at temperature of 500C PRESSURE -High pressure will increase NH3 yield and reaction rate -Because less molecules on products side -Compromise between ideal conditions and equilibrium constant at 400atm CATALYST -Only increases rate of production not change equilibrium position -Enable reaction to produce reasonable yields at lower temperature -Such as Fe/FeO (cheap but efficient) SPECIAL -If pressure is high enough NH3 is liquefied as formed and removed, meaning concentration of products is low -Liquid is drained off preventing system from reaching equilibrium -Therefore forward reaction is always favoured

YEAR TWELVE CHEMISTRY CALCULATOR NOTES CHAPTER 15 Acid & Base aqueous solutions ACIDS PROPERTIES/USES 1. turn blue litmus paper red 2. conduct an electric current - batteries 3. taste sour 4. react with metal oxide cleaning iron before galvanising 5. HCL reacts with carbonate cleaning cement & mortar from bricks 6. HCL adjusting pH of pool BASES PROPERTIES/USES 1. turn red litmus paper blue 2. conduct an electric current alkaline batteries 3. taste bitter 4. ammonia ability to form complex ion [Cu(NH3)4]2+ & [Ni(NH3)6]2+ - used in industrial processes e.g. extraction of nickel 5. dissolve amphoteric metal hydroxides extraction of Al 6. neutralise acids anti-acid tablets 7. dissolves grease & tat (as in the manufacture of soap) cleaning agent Arrhenius theory Theory is limited to aqueous solutions H+ ions are produced by the ionisation of acids in water. OH- ions produced by the dissociation(for ionic compounds) of bases in water. Neutralisation: H+ + OH- -> H2O More commonly, H+ ions exist as H3O+ (hydronium ions) Protons are very small so charge is concentrated and H+ and H20 are attracted to form coordinate covalent bond with one of the oxygens lone pair of electrons. H+ is the same as H30+ Eg. Strong acid ionising: HCL(g) -> H30+ (aq) + Cl-(aq) Eg weak acid ionising: CH3COOH (aq) <-> CH3COO- + H30 (aq) Eg strong base dissociating: NaOH(s) -> Na+ + OH- (aq) Eg weak base ionising: NH3(aq) + H2O <-> N4h4+ (AQ) + OH-(aq) Bronsted-Lowry theory ACID = PROTON DONATOR BASE = PROTON ACCEPTER CONJUGATE ACID/BASE PAIRS A conjugate acid is the base species with one extra hydrogen ion A conjugate base is simply the acid species with an extra hydrogen ion Some substances can react as acids OR bases in different reactions. The stronger an acid, the weaker its conjugate base IONISATION OF WATER Water is a weak electrolyte and therefore undergoes auto-ionisation BRONSTE LOWRY: 2H20(l) <-> H3O+(aq) + OH-(aq) ARRHENIUS: H20 (l) <-> H+(aq) + OH- (aq)

YEAR TWELVE CHEMISTRY CALCULATOR NOTES The equilibrium constant for the ionisation of water is: Kw = 1.0 X 10 ^(-14) at 298 K -Polyprotic acids (e.g. H2SO4, H3PO4) are those which contain more than one acidic or ionisable hydrogen per formula unit of the acid -For polyprotic acids successive ionisations occur to successively smaller extents pH scale -Acidic conditions when [H+] > [OH-] basic when [OH-] > [H+]. Neutral when equal -When non electrolytes or weak or strong electrolytes that DO NOT create H+ or OHare dissolved into solution, the solution remains neutral. ACIDS Strong: (completely ionise in water) HCl, HNO3, H2SO4 eg HCL(g) -> H30+ (aq) + Cl-(aq) Weak: (only partial ionise in water) all others eg HF, HBr, HI eg CH3COOH (aq) <-> CH3COO- + H30 (aq) BASES Strong bases: (completely dissociate in water) group I and II metal hydroxides and group I metal oxides that are soluble eg Na2O + H2O -> Na+ + 20HWeak bases: (only partially dissociate in water) NH3(g) + H2O <-> NH4+ (aq) + 6H- and CO3^(2-) (aq) + H2O <-> HCO3- (aq) + OHpH of salt solutions -Salts ionic compounds containing a cation other than H+ & an anion other than O2- or OH-salts are formed by the replacement of hydrogen in an acid by a metal ion or an ammonium ion -salt solutions can be acidic, basic, or neutral depending on the tendencies of the ions in the salt to undergo hydrolysis (how they react with water CATIONS -All cations are neutral e.g. Ba2+, Li+, Na+, Zn2+ -because they dont react with water :. Dont undergo hydrolysis Except: 1. (NH4)+, Al3+ & Fe3+ (acidic) [Al(H2O)6]3+ + H2O <-> [Al(H2O)5OH]2+ + H3O+ (NH4)+ + H2O <-> NH3 + (H3O)+ -if an ion is acidic in water it donates a proton to water to form hydronium ion ANIONS -All anions are basic (come from weak acids) e.g. CHCOO-, (CO3)2-, CN- ClO-, HSS2- & (HPO4)2-because in water they accept a proton from water to form hydroxide ions CH3COO- + H2O <-> CH3COOH + OH(CO3)2- + H2O <-> (HCO3)- + OH-Except: 1. Anions from strong acids are neutral e.g. Cl-, (NO3)-, I- & Br2. Acids derived from polyprotic acids are acidic e.g. (HSO4)- & (H2PO4)-

YEAR TWELVE CHEMISTRY CALCULATOR NOTES -some anions (those derived from polyprotic acids) can act as a acid or base, both reaction occur to a sml extent, but the one that occurs to the greater extent determines whether the sln will be acidic or basic (HSO4)- + H2O <-> H2SO4 + OH(HSO4)- + H2O <-> (SO4)2- + H3O+ (occurs to greater extent) Amphoteric equations Amphoteric metals: Al, Zn and Cr Amphoteric metal hydroxides: - Al(OH)3 - Zn(OH)2 - Cr(OH)3 Amphoteric complex ions: - Aluminate: [Al(OH)4)]- Zincate: [Zn(OH)4)]2- Chromite: [Cr(OH)4)]ACID + AMPHOTERIC METAL Same as any other acid and reactive metal reaction (salt and gas) ZINC: Zn(s) + HCl(aq) -> ZnCl2(aq) + H2(g) IONIC: Zn(s) + H+ (aq) -> Zn2+(aq) + H2(g) CHROMIUM: 2Cr(s) + 6HCl(aq) -> 2CrCl3(aq) + 3H2(g) IONIC: 2Cr(s) + 6H+ (aq) -> 2Cr3+(aq) + 3H2(g) ALUMINUM: 2Al(s) + 6HCl(aq) -> 2 AlCl3(aq) + 3H2(g) IONIC: 2 Al(s) + 6H+ (aq) -> 2Al3+(aq) + 3H2(g) BASE + AMPHOTERIC METAL Dissolve to give complex ion and hydrogen gas ZINC: 2OH(aq)

+ Zn(s) + 2H20(l) -> [Zn(OH)4)]2- (aq) +H2(g)

CHROMIUM: 2OH-(aq) + 2Cr(s) + 6H2O -> [Cr(OH)4)]-(aq) + 3H2(g) ALUMINIUM: 2OH-(aq) + 2 Al(s) + 6H2O -> [Al(OH)4)]-(aq) + 3H2(g) BASE + AMPHOTERIC HYDROXIDES Dissolve in base to form complex ion ZINC: Zn(OH)2(s) + 2OH-(aq) -> [Zn(OH)4]2-(aq) CHROMIUM: Cr(OH)3(s) + OH-(aq) -> [Cr(OH)4]-(aq) ALUMINIUM: Al(OH)3(s) + OH-(aq) -> [Al(OH)4]-(aq) BASE + AMPHOTERIC OXIDES Dissolve in base to give complex ion ZINC: ZnO(s) + 2OH(aq)

+ H20

(l)

-> [Zn(OH)4]2-

(aq)

YEAR TWELVE CHEMISTRY CALCULATOR NOTES CHROMIUM: Cr2O3 ALUMINIUM :Al2O3

(s)

+ 2OH+ 2OH-

(aq)

+ 3H20 + 3H20

(l)

-> 2[Cr(OH)4]-> 2[Al(OH)4]-

(aq)

(s)

(aq)

(l)

(aq)

General equations 1. acid + reactive metal -> salt + hydrogen gas 2. acid + metal oxide -> salt + water 3. acid + sulfide -> salt + hydrogen sulfide (H2S) 4. acid + carbonate -> carbon dioxide + water + salt 5. acid + sulfite -> sulfur dioxide(SO2) + water + salt 6. acid + hydrogencarbonate -> water + carbon dioxide + salt 7. acid + ethanoate -> ethanoic acid + salt 8. acid + strong base -> salt + water 9. base + amphoteric metal -> hydrogen gas + complex salt 10. base + ammonium salt -> water + ammonia gas + salt Observations Ionic compounds are always solids unless mentioned as solutions GASES: colourless except CL2 pale green and NO2 brown H2S hydrogen sulfide rotten egg S02 sulfur dioxide pungent NH3 ammonia gas sharp or pungent METALS: silvery except for CU salmon pink and AU gold