F325 EQUILIBRIA, ENERGETICS AND ELEMENTS

RATE OF REACTION
RATE is the change in concentration of reactants over time measured in mol dm-3 s-1 Can be worked out from concentration-time graph, rate at point = gradient of tangent INITIAL rate = rate at t=0, worked out from gradient of tangent at t=0 Increasing concentration/pressure (more collisions), temperature (more energy) and catalysts (lowers Ea) INCREASE rate of reaction ORDER of reactants is how its concentration affects the rate, found by EXPERIMENT o ZERO order = rate unaffected by changing concentration o FIRST order = rate increases by same amount as change in concentration o SECOND order = rate increases by square of amount of change of concentration o Work out from a rate-concentration graph: 0= -, 1= /, 2= upwards curve o Work out from conc.-time graph: 0= \, 1= constant life, 2= steep down curve HALF-LIFE is the time taken for reactant concentration to reduce by half For A + B C + D: rate = k [A]m [B]n where m and n are orders of A and B o Any reactant with 0 order excluded o Must calculate units of k: rate units = mol dm-3 s-1, conc. units = (mol dm-3)order o k is RATE CONSTANT, affected by temp: large k fast rate, small k slow rate RATE-DETERMINING STEP is the slowest step in the reaction, which limits the rate. The orders in the rate equation are how many of that molecule in the rate-determining step o 2H2 + 2NO > 2H20 + N2, rate = [H2][NO]2 so H2 + 2NO H20 + N20 + 0 is slowest step

EQUILIBRIUM
DYNAMIC EQUILIBRIUM exists in a closed system where rate of forward reaction is equal to rate of reverse reaction. LE CHATELIERS PRINCIPLE states that the position of equilibrium will change to minimise any changes o Increasing concentration will shift away from excess o Increasing pressure will shift to side with fewer gas molecules o Adding a catalyst does not alter o Increasing temp shifts in ENDOthermic, Decreasing temp shifts in EXOthermic Equilibrium position calculated using Kc: EQUILIBRIUM CONSTANT o For aA + bB cC + dD: Kc = [C]c [D]d where a, b etc are balancing numbers [A]a [B]b o If equilibrium concentrations and balanced equation given, sub in o If amounts given, must divide by volume (if same moles on each side, vol cancels) o If initial amounts given, difference between that and equilibrium same for all o Units must be calculated each time: conc. units = mol dm-3 Kc indicates equilibrium position: Kc > 1 = right, Kc = 1 = equal, Kc < 1 = left Increased temp: If fwd ENDOthermic, Kc increases, if fwd EXOthermic, Kc decreases Kc constant if conc/pressure changes, equilibrium shifts to restore original Kc value

ACIDS AND BASES

HA + H2O H3O+ + AAcids donate protons, bases accept protons. A Acid 1 Base 2 Acid 2 Base 1 CONJUGATE PAIR is such that the acid donates a proton and the base accepts it. An equilibrium is established pH is defined as = -log10[H+]. To convert back, [H+] = 10-pH. A STRONG ACID dissociates completely in water, a WEAK ACID partially dissociates The extent of dissociation is calculated as Ka the ACID DISSOCIATION CONSTANT Ka Kc so = [H+][A-] / [HA] for HA H+ + A-. Large Ka = strong, Small Ka = weak Ka can, as pH, be expressed as pKa To calculate pH for a strong acid, we assume complete dissociation so [HA] = [H+] To calculate pH for weak acid, need Ka. As H+ and A- concs equal, top of Ka calc can be [H+]2. As only a negligible amount of dissociation occurs, bottom can simply be [HA]. Therefore [H+] = Ka x [HA]

Water ionises slightly to H+ and OH-. Therefore H20 conc. can be considered constant. Ka for ionisation of H20 (weak acid) with [H20] gives Kw IONIC PRODUCT OF WATER Kw is temp. dependent, at 25OC = 1.00 x 10-14 mol2 dm-6 As [H+][OH-] = Kw = 1.00 x 10-14 mol2 dm-6, either H+ or OH- can be found if other known STRONG BASE dissociates completely. WEAK BASE dissociates partially To calculate pH for a strong base, we assume complete dissociation so [OH-] = original base conc. [H+] = Kw / [OH-]

BUFFERS
A BUFFER solution minimises pH change on addition of small amounts of acid or base It is a mixture of a weak acid (HA) and its conjugate base (A-) o HA dissociates partially to H+ and Ao Either: [A-] added or HA partially neutralised by alkali, forming salt which completely dissociates to [A-] o Equilibrium pushed to left by high [A-], reducing [H+] o Buffer contains: high [HA], high [A-] and low [H+] Add ACID: [A-] removes, forming [HA] therefore more H+. Eqm shifts left restoring [H+] Add ALKALI: H+ removes, forming water. Eqm shifts right to restore [H+] Ka = [H+][A-] / [HA], therefore [H+] = Ka x [HA] x [A-] to calculate pH Assuming [HA] at eqm same as original acid, and [A-] at eqm same as original salt/base Curve from an acid-base titration can be plotted: o (1) when acid/base first added pH increases slowly as other in excess o (2) within 1cm3 of neutralisation, pH increases rapidly to EQUIVALENCE POINT, a vertical section o (3) as acid/base continues, pH increases slowly as that is now in excess Curve starts/ends higher/lower on pH axis if strong/weak base/acid INDICATORS have an acid colour and a base colour, when equal amounts at END POINT, aim is to have end point within equivalence point. As no vertical equivalence point, no indicator for weak acid-weak base titration STANDARD ENTHALPY OF NEUTRALISATION (Hneut) is enthalpy change when acid neutralised with base to form 1mol of water, under standard conditions

LATTICE ENTHALPY
LATTICE ENTHALPY is the enthalpy change accompanying the formation of 1mol of an ionic compound from its gaseous ions. It is difficult to measure directly. Using HESS LAW, Hlat can be calculated using other, known enthalpy changes. GREEN = BLUE. Hf = FORMATION = 1mol of (ionic) compound from elements in std states Hat = ATOMISATION = 1mol gaseous atoms from elements in std states (always O2) Hie = IONISATION ENERGY = 1mol gaseous atoms having 1 electron removed forming 1mol of gaseous 1+ ions DOWN = exothermic, UP = endothermic Hea = ELECTRON AFFINITY = 1mol of gaseous atoms having 1 electron added forming 1mol of gaseous 1- ions. Sometimes multiple Hie / Hea will be required As Hlat is unknown = Hf (rest of BLUE route) in diagram above Strength of ionic lattice: o IONIC RADIUS: smaller an ion is, closer ions can pack together and more they attract. As ionic radius decreases, Hlat gets more negative o IONIC CHARGE: as charge increases, attraction is stronger, reducing ionic radius and increasing attraction. As charge increases Hlat gets more negative o Across a period, Hlat becomes more negative as charge increases and radius decreases

HYDRATION
When an ionic solid dissolves, it breaks down into gaseous ions which are subsequently hydrated The enthalpy change breaking down the solid is hlat Hhyd = HYDRATION = 1mol of gaseous ions, dissolved in water, forming 1mol aqueous ions Hs = SOLUTION = 1mol of (ionic) compound being dissolved in water to form 1mol aqueous ions. Hs can be endo or exothermic To calculate Hlat = Hhyd Hs. A Hess Law diagram can also be drawn

ENTROPY
ENTROPY S is the measure of the disorder of a system. Entropy increases whenever a system becomes more disordered and the tendency is for systems to increase entropy ENTROPY CHANGE S is the entropy change accompanying a reaction in molar quantities of an equation, under std conditions: S = Sproducts Sreactants SPONTANEOUS processes occur on their own to lower energy and increase stability. Whether a process is spontaneous depends on S, H and temperature in KELVIN The relationship between them is FREE ENERGY CHANGE = G = H TS. Units of H and S must be the same, usually kJ K-1 mol-1. To change J to kJ /1000. K = OC + 273. A process can occur spontaneously when G <0

CELL POTENTIALS
Oxidation is loss of electrons / increase in oxidation number Reduction is gain of electrons / decrease in oxidation number Oxidation numbers: element 0, oxygen -2, hydrogen +1, ion its charge, fluorine -1 H+, OH- and H20 can be added to Redox equations in acidic, alkaline or aqueous cdns ELECTROCHEMICAL CELLS use electron transfer of redox reactions to produce electricity HALF-CELL: element in two oxidation states, e.g. Cu2+ ions in solution and Cu metal an equilibrium exists Cu2+ + 2e- Cu ELECTRODE POTENTIAL is half-cells tendency to lose/gain electrons. Measured in V CELL is two half-cells with different electrode potentials o Two half cells joined by a wire (electrons) and a salt bridge (ions) o A hydrogen half-cell has 1M HCl with H2 gas pumped in at 298K/1atm. A platinum electrode is used as it is inert. 2H+ + 2e- H2 o Half-cells can also comprise two solutions of the same element in different oxidation states in equimolar concentrations. An inert platinum electrode is used STANDARD ELECTRODE POTENTIAL, E, is the e.m.f. of a half-cell compared to a standard hydrogen half-cell under standard conditions STANDARD CELL POTENTIAL, Ecell, is the difference between the E of two half-cells o The half-cell with most negative E supplies the electrons and is negative terminal o Ecell = Epositive Enegative. Most negative has reverse reaction, i.e. Cu > Cu2+ + 2eThe larger the difference between E values, the more likely a reaction will take place, and E can be used to predict feasibility of redox reactions by treating them like two half-cells FUEL CELLS combine H2 and O2 to produce H20 and energy and can be used in vehicles o advantages: zero pollution, more efficient o limitations: infrastructure, storage, lifespan, producing H2 uses energy o hydrogen can be stored as (a) a liquid under pressure dangerous, (b) adsorbed onto a solid or (c) absorbed into a solid

TRANSITION ELEMENTS
... are d-block elements that form stable ions with an incomplete d sub-shell Scandium only forms Sc3+, which has no d-block elements and Zinc only forms Zn2+, which has a complete d-block so they are NOT transition elements 4s sub-shell fills before 3d sub-shell as 4s has a lower energy until filled 4s electrons are lost in reactions first, however, as when filled it has higher energy All [Ar] 4s2 3dx except Chromium and Copper which are 4s1 to or fully fill d-block All have VARIABLE OXIDATION STATES and form coloured compounds Are effective catalyst e.g. Iron in Haber process, Nickel for hydrogenation of alkenes PRECIPITATION REACTIONS combine soluble ions to form an insoluble precipitate o Cu2+ + 2OH- > Cu(OH)2 o Fe2+ + 2OH- > Fe(OH)2 o Co2+ + 2OH- > Co(OH)2 o Fe3+ + 3OH- > Fe(OH)3

COMPLEX IONS
... transition metal ions bonded to one or more ligands by co-ordinate (dative) bonds LIGAND = molecule which donates lone pair to form co-ordinate bond with transition elt Common ligands include :OH2 (water) and :NH3 (ammonia) Formulae show square brackets encompassing element and all ligands together Common shapes are TETRAHEDRAL (four bonds) and OCTAHEDRAL (six bonds) BIDENTATE ligands can donate two lone pairs, HEXADENTATE ligands can donate six (EDTA) STEREOISOMERISM is possible in complex ions o Cis-trans: in tetrahedral two types of ligand, cis has matching top/bottom, trans has opposite, in octahedral there can be four of one and two of the other and two swap 90O, when all four centre ligands are equal it is cis o Optical: only with polydentage ligands non-superimposable mirror-images LIGAND SUBSTITUTION is where a ligand is replaced by another o [Cu(H20)6]2+ + 4HN3 [Cu(NH3)4(H20)2]2+ + 4H20 o [Cu(H20)6]2+ + 4Cl- [CuCl4]2+ + 6H20 Cl from HCl, Cl bigger than H20 hence o [Co(H20)6]2+ + 4Cl- [CoCl4]2+ + 6H20 4 Cl ligands replacing 6 H20 ones Kstab = STABILITY CONSTANT is a special form of Kc for ligand substitution. As H20 is in excess throughout, it is not included. Kstab = [products]balancing no / [reactants]balancing no Large Kstab indicates equilibrium to the right

REDOX TITRATIONS
Similar to acid-base on electron transferred not protons Indicators usually unnecessary as natural colour change is present MnO4- and Fe2+ o Iron(II) readily oxidised by Manganese(VII) in Mno4o Results can be used to estimate the concentration of iron in an unknown solution, or the percentage composition of metal in a sample o MnO4- self indicating purple to colourless o (1) work out #moles MnO4-, (2) using equation, work out #moles Fe2+, i.e. 5:1 relationship, (3) therefore concentration of Fe2+ in solution etc I2 and S2O32o I2 reduced to I- ions by S2O32-, which is reduced o I2 can be formed from adding I- ions to an oxidising agent under investigation o Colour change uses starch o (1) work out no moles S2O32-, (2) work out #moles I2 used, (3) work out no moles of oxidising agent required to produce calculated #moles of I2, (4) therefore concentration of oxidising agent in solution etc

MMXI Philip Wright