Everything to Remember for H2 Chem on One Sheet of Paper (no organic)

Jeremy Teoh (10) 12S03M RI(JC)

Atomic Structure
Aufbau: fill lowest energy orbitals first Hunds: If more orbitals of equal energy available, electron enters degenerate empty orbital to minimise IER PEP: Spin opposite, max 2e- per orbital Note that 4s is higher than 3d when both are filled Isotopes: Same p, different n, different mass Same e-, same electronic configuration, same #valence, same chemical properties s: non-directional, spherical p: directional, dumbbell shape, different orientations e- configuration: the way e- are distributed Orbital: region in space where P(find e-) > 0.95 Fully-filled 3d orbitals unusually stable, symmetrical e- distribution Angle of deflection PROP q/m Average mass of <whatever> relative to 1/12 mass of 1mol of C Formula unit: smallest collection of atoms from which formula of ionic compound can be established

Solubility Arguments Lute-Vent > Lute-Lute, Vent-Vent Strong enough to overcome latter then will be soluble What needs to be broken Interaction and molecule type Strength comparison / Extent Conclusion

Energetics
Hhyd (-) = Hlatt (+) + Hsoln (-) All dH @ Standard state 298K 1atm Hsoln: energy released when 1mol of substance dissolved in pure water to yield infinitely dilute solution of M+ ion Hc: energy released when 1mol of substance completely burned in excess O2 Bond energy: 1mol of X-Y bond broken in gaseous state to form gaseous atoms Bond dissociation energy: energy required to break 1mol of the particular X-Y bond in particular compound in gas phase Hf: energy released or absorbed when 1mol of substance formed from constituent elements (NAME) in standard state etc. Hneut: energy released when aqueous acid and base react to form 1mol of H2O upon neutralisation EA/IE applies to gaseous species Hess Law dH dependent on Hf Hi Independent of path taken Allow calculation of dH without performing the reaction BE and Variations BE is average energy absorbed when breaking the X-Y bond in gaseous state Inaccuracy since different from breaking in liquid / aq phase OR because exact X-Y BE varies across different molecules Strength of bond influenced by neighbouring atoms Deviation from Calculated LE Theoretical assumption that bonding is purely ionic, between point charges Neglects polarising power of M+ / polarisability of XHence deviation from calculated Hlatt due to partial covalent character in ionic bond Hhyd PROP charge density Entropy Higher T: More packets of E to distribute in system More E to move, more disorder Phase change: particles more randomly arranged, occupy more volume ngas increase: more ways to arrange particles in vessel, more collusions Mixing: increased disorder; mixing is complete and spontaneous dG Considerations dG < 0 implies reaction is spontaneous and thermodynamically feasible TERM outweighs TERM, so as T varies, dG varies For any process, qutoe dG = dH TdS Comment on fixed sign, then comment on variation and significance High charge density M+ can have negative dS of solution if they are able to form extensive hydration shells that order the H2O molecules about them and reduce disorder

Periodicity Trends
Big jumps in IE: removed from different orbital / inner PQ shell Large amount of energy required to remove nth electron Infer that nth electron resides in an inner PQ shell Hence n-1 electrons in valence shell, element is in group X Successive IE increases Removing e- from ion of increasingly ++ charge Requires more E to overcome stronger ESFOA Across period e- added to same outer PQ shell More p, Z increase S constant as same number of inner PQ shells Hence valence e- feel greater Zeff, ESFOA increases More E to remove, higher IE / drawn closer so radius decreases Down group More p, Z increases S increases due to greater number of inner PQ shells YET Valence e- reside in PQ shell of higher energy Further away from nucleus Experience less strong ESFOA S effects > Z effects, Zeff smaller down group Hence lower IE or larger atomic radius Ionic radius: Radius of ion in ionic compound vdW radius: Inter-nuclear distance between two adjacent atoms Covalent radius: IND in bonded molecule

Chemical Bonding
Covalent bond: ESFOA between nuclei and shared electrons localised between the nuclei Larger orbitals, more diffuse, overlap leads to less accumulation of electron density in inter-nuclei region Giant ionic crystal lattice / Giant metallic lattice / Giant covalent macromolecular structure / Simple covalent molecular structure Ionic/Covalent Arguments Polarising power of M+ PROP charge density PROP q+/r+ Polarisability of XLend covalent character to an ionic bond Difference in EN between X-Y Adds additional ESFOA between d+-, making the covalent bond polar Strengthens covalent bond IMFOA id-id: polarisability of e- cloud pd-pd: strength of overall DM HB: H covalently bonded to high EN atom More e-, larger e- cloud / greater SA More easily polarised Stronger id-id VSEPR Note seesaw (4/5), T-shaped (3/5), V-shaped (2/4) VSEPR: regions of electron density arrange themselves as far apart as possible to minimise repulsion, LPLP>LPBP>BPBP Miscnotes NOTE: BeF2 and BeCl2 are not ionic Electrical conductivity CORREL availability of mobile charge carriers free to move O2F electron deficient and hypervalent No low-lying vacant d orbitals to expand octet SIG: head-on PI: lateral, side-on C=C: greater electron-density between nuclei, greater ESFOA between nuclei and shared electrons Metallic bonding: Metal cations in a sea of delocalised electrons Strong ESFOA between the two Diamond has strong C-C, extensive covalent arranged tet, no sliding allowed without breaking covalent Layered, weak vdW

Kinetics
Ea = minimum amount of E that reactant particles need to possess before they can collide to react Rate of reaction: dc/dt If [H+] is a catalyst, then can approximate rate = k[H+][rct] to be pseudo-first order since [H+] remains constant throughout the reaction RDS: slowest step in a reaction mechanism Order = coefficient of rct in RDS and preceding steps leading to it Effect of T on Rate number of particles with given energy / KE T increases, average KE increases, more collisions / unit t (frequency) More particles have E > Ea, more effective collisions / unit t leading to reaction Autocatalytic reactions Generate cat as one of the products (justify) Beginning, as [cat] increase, rate increase End, as [rct] decrease, rate decrease Active-Site Saturation Saturation of AS for catalysed reactions At high [rct] concentration, AS saturated, 0-order kinetics At low [rct], AS not saturated, rate PROP [rct]

Equilibria
Reversible reaction in dynamic equilibrium Concentration of all species constant Forward and backward reactions continue to occur at the same rate K relates concentrations and allows quantification of position of equilibrium LCP: When a system at eqm is subject to change, system responds to counteract imposed change and reestablish eqm Acidic buffer pH in acidic range Solution of weak acid with Ka higher than weak conjugate base within 10:1 ratio LCP Model When change made, By LCP, Eqm shifts position to <direction> To counteract <change in parameter> Rate of <direction> reaction increases / favoured <direction> reaction Hence more rct/pdt formed at eqm pH = pKa + log10[A-]/[HA]

CIE: reduced solubility of a salt due to presence of a common ion Buffer region of a titration: region where minimal pH change occurs despite addition of H+/OHIndicator Suitability of indicator: Working range of In coincides with region of sharp pH change on titration curve When Qsp > Ksp, then precipitation will occur

Kinetic, stability, favourability, feasibility

Proteins
pI: pH at which the molecule is neutral Proline introduces kink in PP backbone, limited flexibility of the 2 o amine Definitions for Protein Structure 1o Specific sequence and composition of AA 2o Specific folding patterns stabilised by HB between parts of PP backbone a-Helix: HB // long axis of helix Right-handed, spring-like R groups point outwards b-pleated: // or anit/// 3o Specific complex 3D arrangement stabilised by Interactions between R groups of AA 4o Spatial arrangement and association of >1 PP Denaturation In the presence of salts, acids and enzymes Disrupted 2/3/4o of protein R-group interactions maintaining native conformation of protein Broken and disrupted if non-covalent Leading to unfolding and exposing of non-polar, hydrophobic groups Leaving a randomly coiled PP Aggregation due to id-id interaction can occur leading to an insoluble coagulated mass Heat kills: HB, ionic, vdW, SS pH kills: HB, ionic (but alkaline makes SS [o] facile) Hg2+ kills: ionic, SS [O/H] kills: SS

Electrochem
Higher Ecell = eqm lies right ANODE (reduction) || CATHODE (oxidation) Solid electrodes are always on extreme left/right Concentration effect Higher concentration species preferentially reacted, even if Ecell for process is slightly disfavoured Invoke especially if non-standard conditions used Partitioning Electrolysis of brine requires partitioning of the two half-cells only to 1. Prevent H2 and Cl2 from combining and reacting 2. Prevent Cl2 from being further oxidised to ClO-, ClO3Ehalf-cell: EMF produced when the half-cell is connected to a SHE Measurement done at 298K 1atm all concentrations of reacting species 1M Ecell: Maximum potential difference between 2 half-cells at SC Primary batteries: electrochemical cells where the redox reactions are not reversible Secondary cells: electrochemical reaction that generates electric current can be reversed by electrical rechanging Faradays 1st Law: m or V directly proportional to C Faradays 2nd Law: Amount of charge required to discharge 1mol of substance depends on z, charge on ion

Group VII
Br2: light brown (aq), reddish-brown (org) I2: light yellow (aq), violet (org) X- (HX) oxidation by c. H2SO4 NaCl + H2SO4 HCl + NaHSO4 NaBr + H2SO4 HBr + NaHSO4 / Br2 + SO2 + H2O NaI + H2SO4 I2 + NaHSO4 / SO2 / S / H2S + nH2O X2 disproportionation Cold: X2 +2OH- X- + XO- + H2O Hot: 3X2 + 6OH- 5X- + XO3- + 3H2O Noting that 3XO- 2X- + XO3X2 reduction with S2O324X2 + S2O32- + 5H2O 8X- + 2SO42- + 10H+ I2 + 2S2O32- 2I- + S4O62H2 with X2 F: explosive even in the dark Cl: explosive in hv, slow below 200oC in dark Br: slow at 300oC with catalyst I: slow, reversible at 300oC with catalyst

TM
Similar atomic radius Going from Cr to Cu, atomic radius similar More protons, Z increases Yet S increases as well since e- added to penultimate 3d subshell Zeff roughly constant, same shielding experienced by 4s valence eStarkly small atomic radius compared to s/p block Ca to V More protons, Z increases Electron added to penultimate 3d subshell Relatively poor shielding for 4s compared to shielding provided by s, p electrons since 3d electrons occupy diffuse orbitals Much greater Zeff than expected so atomic radius decreases High electrical conductivity, variable oxidation state 3d 4s orbitals have similar, close energies Hence small energy difference between 3d, 4s orbitals Both 3d and 4s electrons contribute to delocalised sea of eHence more delocalised eGreater ESFOA between e- and cations stronger bonding Can make use of different numbers of 3d/4s electrons in bond formation For GI/II elements, changing the usual number will create salts with less exothermic LE / call for unfavourable IE to remove e- from inner PQ shell Can exist in different oxidation states, change oxidation states easily High density Smaller atomic size, greater relative atomic mass More mass per unit volume, higher density Ligand At least one lone pair available for donation into Vacant low-lying orbital of central metal cation / atom To form a dative covalent bond and hence complex formation Acidity of some M+ (aq) Appreciable hydrolysis effected by M+ Small size, high charge, high charge density and polarising power (formula) Polarises and distorts electron cloud of H2O Can serve as proton donor Slight excess of H3O+ leads to acidic character of (aq) solution QUOTE the eqm Colour of M+ (aq) Ligands are bonded to central metal cation via dative covalent bonds Splitting of originally degenerate 5 3d orbitals into two sets of orbitals, SLIGHTLY different E levels Partially filled d-orbitals allow for d-d electronic transitions to occur Electrons can absorb energy in visible region, excited and promoted from lower set of d orbitals to higher set Colour observed is complementary to colour of photon absorbed For the rest, excitation and promotion does not involve ABS of EMR in UV region Catalysis by TM Homogeneous catalysts increase rate by lowering Ea / providing alternative reaction mechanism Ecell < 0, but non-standard conditions Reaction between oppositely charged ions favourable since ESFOA increases chance of collision Avoids repulsion between like charges The catalyst will react and be regenerated, not consumed Heterogeneous catalysis Partially-filled vacant low-lying 3d subshell provides sites for rct to ADSORB Accept lone pairs from rct, provide 3d electrons to form bonds with rct EFFECT: WEAKEN covalent bonds to be broken through the course of the reaction Increase local concentration of rct molecules (CLOSECONTACT) to increase chances of reaction occurring Orientate rcts correctly to encourage reaction Pdts easily DESORB, freeing up active sites to catalyse more reactions Stability of some TM complexes towards [O/H] CN- ligand stabilises +3 charge complex Easier for converse + charge aqua complex to accept oppositely charged electron Since repulsion due to like charges avoided

Group II
M+ high charge density Attracts electron density of polyatomic anion Sufficient polarising power to distort O-H bond Weaken X-Y bond, easier to break Hence thermally decompose at lower T

QA
BaCrO4 yellow solid PbCrO4 bright yellow solid AgCl white, AgBr cream, AgI yellow NO3- test using NaOH / Al: 3NO2- + 8Al + 5OH- + 18H2O 3NH3 + 8[Al(OH)4]3NO2- same as NO3NOTE: NO2- + 2H+ NO + H2O, NO oxidised easily in air to yield NO2 SO32- will precipitate out with Pb2+ and Ba2+ as per SO42NOTE: SO32- + 2H+ SO2 + H2O Cr(OH)3 grey-green solid [Cr(OH)6]3- dark green solution ZAP will all complex with OH- but only Zn will form [Zn(NH3)4]2+

Misc
SiO2 + 2OH- (heat, concentrated) SiO32- + H2O Fehlings: Cu2+, NaOH (aq), tartrate Tollens: [Ag(NH3)2]+ Nitroaryl: Yellow oil Tribromophenols: white ppt DLPP: Ptot = sum(Pgas) as if it occupied the container by itself CuCl2 (aq) will conproportionate with Cu and c. HCl to form [CuCl 2]- which is colourless V(n): 5 yellow, 4 blue, 3 green, 2 violet Cu2O red solid, CuO black solid CuI cream Mn(OH)2 off-white / buff solid MnO2 brown / black solid Mn2O3 brown solid MnCO3 white / buff solid [Ag(S2O32-)2]- and [Ag(CN)2]-: Colourless complexes Haber: Fe / 250atm, 450oC