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Bonding and intermolecular Forces: Electron Pair repulsion theory can help you predict shapes of molecules and

ions - Linear 180 - Triganol Planar 120 - Tetrahedral 109.5 - Triganol Bipyramidal 90 and 120 - Octahedral 90 - Lone pairs of electrons count toward an area of electron density but as they repel to a much greater extent they reduce the bond angle by 2.5 Bond lengths are subject to bond strength- the stronger the bond the smaller the bond length such as dipoles and double/triple bonds Electronegativity is the ability of an atom to attract the shared pair of electrons in a covalent bond giving the bond ionic properties. - Differences in electronegativity will cause permanent Diapole interactions - Polar bonds are subject to difference in electronegativity - Polar molecules are non-symmetrical and have polar bonds Significance of polar bonds: - In organic chemistry they usually break first and always break heterolytically giving nucleophiles - Determines reaction mechanism Using bond character data you can determine whether a bond it likely to be ionic or covalent - Ionic bonds can be distorted by electronegativity giving covalent characteristics Experiments to determine whether molecules in liquids are polar or non-polar - Stream of polar liquid will be deflected away from a charged rod - Mixing Solutions in known polar solvents. Non-polar and polar liquids are immiscible London (van der Waals) forces - Exist between all atoms - Size of force is relative to size of electron cloud - Susceptible to distortion and electron density shifts (induced instantaneous dipoles) Permanent Dipole - Differences in electronegativity (polar molecules) - Aldehydes, Keytones, Carboxylic acids, Esters and Amides Hydrogen Bonding - H must be bonded to one highly electronegative atom(nitrogen , fluorine or oxygen) with an unpaired electron - 180 - H bonds are the strongest intermolecular forces and give molecules unusually high melting and boiling points because H is electron deficient and so it will be strongly attracted to the lone pair of electrons Carbon Allotropes - Diamond- 4 sigma bonds in a tetrahedral arrangement gives very strong properties (giant covalent structure) - Graphite- 3 sigma bonds with the 4th electron delocalized which allows for electrical conductivity and weak bonds between graphite layers

Fullerenes- C32 or more very strong ball shape such as the Bucky ball with a delocalized electron Nanotubes- tube versions of fullerenes however if embedded in polymers will conduct electricity

Physical Properties in relation to intermolecular forces - Carbon chain length increases = boiling temp increases as there are more London forces which requires more energy to break - Branching increases = boiling temp decreases as less overlap between chains so less London forces - Hydrogen bonds reduce volatility of molecules such as alcohols compared to alkanes, they are much stronger than London dispersion forces Hydrogen halides boiling temps increase down the group due to increase in electron cloud (London) with the exception of HF which can form hydrogen bonds which are very strong Experiments into solubility by mixing various solvents together Ionic compounds are soluble in water as dipoles on H20 bond with the oppositely charged ions - Hydration (where ions are surrounded by water molecules) enthalpy ionic lattice enthalpy - Alcohols are also soluble in water due to the ability to H bond although increase in C chain length = decrease in solubility Polar and non-polar solvents are immiscible as forces present before mixing do not equal the potential for new forces (separating funnel) Compounds are soluble in solvents which have similar intermolecular forces

Inorganic Chemistry- Group 2 and Titrations Oxidation number rules Group1 Group 2 Al H O F Cl Br I +1 +2 +3 +1 -2 -1 -1 -1 -1

In a metal hydride -1 Combined with F +2 and in a peroxide -1 Combined with F or O +1 Combined with F, O or Cl +1 Combined with F, O, Cl or Br +1

Oxidation is the loss of electrons and Reduction is the gain of electrons Mg + 2HCl MgCl2 + H2 0 +1-1 +2 -1 0 - Mg is oxidised - H is reduced Disproportionation reactions are when a substance is both oxidised and reduced Cl2 + 2NaOH NaCl + NaClO + H20 0 -1 +1

PRACTICE WRITING IONIC AND HALF EQUATIONS, PRACTICE BALANCING REDOX EQUATIONS Ionization energies decrease down group 2 because - Atomic radii increase so less influence from positive nucleus - Electron shielding increases Reactions of group 2 elements with: - Oxygen solid metal oxides - Water hydroxides and H2 (only elements below Ca) - Chlorine solid metal chlorides Reactions of group 2 oxides with: - Water hydroxides - Dilute acid corresponding chlorides and nitrates with H20 Group 2 hydroxides will also neutralize dilute acids production chlorides or nitrates with 2H20 Group 2 sulfates solubility decreases down the group - BaS04 is highly insoluble and is used in x-ray meals - Addition of sulfates to BaCl2 gives a white ppt of BaS04 Group 2 hydroxides solubility increases down the group - Ca is slightly soluble in water limewater Thermal Stability Group 1 carbonates dont decompose whereas group 2 carbonates decompose forming corresponding oxides and carbon dioxide - Stability of nitrates and carbonates increase down the group as cation and anionic radius increases so they are less likely to be broken down into more stable oxides - Polarization of the ionic bond is less feasible Li Be Na Mg Nitrates decompose forming K Ca oxygen, nitrogen and oxides Rb Sr Cs Ba Thermal decomposition of group 1 and 2 nitrates can be determined by experiments such as 1. Solid is dissolves and solution is heated in test tube 2. Solution boils and waste vapor is lost 3. Solid is left 4. Solid melts on heating releasing a brown gas which relights splints (NO2) Nitrates decompose forming nitrite and oxygen Flame colours: - Na - K and Cs - Li, Ca and Sr - Ba - Mg Flame colours arise when energy from the flame allows the outer electron to jump to a higher energy level shell and when the electron returns it emits a wave length which is seen as visible light 1. Mix ground salt with HCl (conc HCl as chlorides are chlorides are soluble and volatile) 2. Dip nichrome wire (inert metal) 3. Put wire in flame and observe colour Indicators for acid base titrations

Methyl orange is used for strong acids Red in acid, yellow in alkali and orange end point - Phenolphthalein is used for weaker acids Pink in acid, colorless in alkali and pale pink end point To minimize uncertainties in results you use more accurate apparatus such as a pipette and to calculate percentage uncertainties= (() uncertainty in value value ) x 100 Inorganic chemistry: Group 7, Equilibria and Reaction Rates Physicality of halogens - F is the most electronegative element so has a very stable hydrogen halide formation and a high carbon halogen enthalpy. Due to its small electron cloud is a gas - Cl is a green/yellow gas and this colour continues in hydrocarbon solvents and water - Br is a volatile red/black liquid which easily turns to a red/black gas. It is partially soluble is water and highly soluble is hydrocarbon solvents giving the same colours - I is a black solid and when heated becomes a purple gas, it is slightly soluble in water giving a yellow solution and in HC solvents the colour varies from pink/red to yellow for KI - At has the lowest electronegativity and there for have a low C-X enthalpy but the hydrogen halide is still soluble. It is commonly a solid due to the greater number of electrons Halogens are oxidising agents and their strength decreases down the group. - Halogens oxidise other halogens as long as they are below them in the group (Cl I) - Halogens oxidise metals and non-metals o Cl can act as a reducing agent by oxidising Fe Disproportionation depends on whether the alkali solution is hot or cold - Cold produces halides and halates - Hot will further decompose halogen so oxidation number change is much greater Iodine thiosulfate titrations - Known volume of an oxidising agent such as potassium iodate (V) reacts with excess iodide ions (usually KI) IO3- + 5I- 3I2 + H2O This liberates iodine I2 this can then be titrated with thiosulfate: I2 + 2e- 2I2S2O3 2- S4O62- + 2eWhen titrated with sodium thiosulfate the colour change is from yellow to colourless and to provide a more accurate end point you add starch which is blue/black to colourless

Trends in reducing agent strength is shown by the reaction of potassium halides with conc sulphuric acid Reaction H2SO4 + KCl H2SO4 + KBr Observation KHSO4 + HCl Initially same as Cl so HBr is produced, But HBr is oxidised by acid into Br and H2SO4 is reduced Test HCl gas is seen as white fumes SO2 turns acidified potassium dichromate(VI) paper yellow to green

to SO2

H2SO4 + KI

HI is immediately oxidised to I2 consequently H2SO4 is reduced to hydrogen sulfide

Hydrogen sulfide turns lead ethanoate paper white to black

Halides in AgNO3 and solubility of precipitates in ammonia Cl white ppt (darkens in sunlight) + dilute NH3 dissolves Br cream ppt (darkens in sunlight) + conc NH3 dissolves I yellow ppt (will not darken) + conc NH3 insoluble Hydrogen halides with water and ammonia

The strongest reducing agent has a less stable H-X and it is immediately oxidised I- > Br- > Cl-

Pure samples of HBr and HI are produced from their potassium salts using phosphoric (V) acid (which is a weaker oxidizing agent than sulfuric acid) - see above - All fume is moist air - All are extremely soluble in water producing acids - All react with NH3 predicting an ammonium halide seen as white smoke Reaction Rates are influenced by - Concentration - Pressure - Temperature - Surface Area - Catalyst They all relate to the collision theory which states that particles, in order to successfully react must collide with sufficient energy to break existing bonds and with the correct orientation. Maxwell-Boltzmann Molecular energy distribution curve can show and explain the influence of increasing conc/pressure, temp and the addition of a catalyst - Temp 1 < Temp 2 - Conc 1< Conc 2 No. mol ecu les wit ha giv en en erg y Kinetic energy

Conc 2 Temp 2 Temp 1 Conc 1

Catalysts reduce activation energy by providing a lower energy alternative reacting pathway which can be shown with a reaction profile Factors influencing reaction rates can be demonstrated practically: - Evolution of gas - Colour change - Change in mass - Titrimetric analysis - Conductimetric analysis (ions present) Equilibrium - Dynamic state which can only be established in closed systems - Reversible reactions also never go to completion Equilibrium is subject to: - Changes in temperature, endothermic reactions favour hotter temps and exothermic favour cold temps - Changes in pressure/concentration- from high to low gradient

- Equilibrium will shift in favour of products or reactants depending on conditions Experimental evidence shows the changing conditions on the reaction below: o Heating the solution will shift equilibrium right in favour N2O4 (g) 2NO2 (g) of the reactants as the enthalpy is positive. Increase in nitrogen dioxide will darken the colour of the gas o Cooling the solution will shift equilibrium left in favour of products. Increase in nitrogen tetroxide will turn the solution more pale. Alcohols and Spectroscopy Name and draw alcohols (easy) relate to stability- the number of methyl groups the C-OH is bonded too the more stable the molecule Reactions of alcohols: - Combustion releases energy using O2 in the form of CO2 and H2O only. o Bioethanol is produced by the fermentation of plants and can be used as a combustion fuel, raises debates into carbon neutrality and food vs. fuel - Alcohol and Sodium produce hydrogen gas and a white precipitate with is an ionic salt such as sodium propanoxide o Alcohol also acts as a weak acid by donating a H+ - Substitution with a halogen produces halogenoalkanes - Oxidation of primary alcohols requires an oxidising agent such as K2Cr2O7 in H2SO4. If you distil the product you produce an aldehyde and if you complete oxidation via reflux then you produce a carboxylic acid - Oxidation of secondary alcohols undergo in the same conditions as above however only Keytones will be produced. Test for organic products: - Alcohols + potassium dichromate (IV) orange to dark green - Aldehyde + benedicts reagent red ppt - Carboxylic acids + NaCO3 is neutralized - Keytones + Bradys reagent yellow/orange ppt

Interpret ion peaks in mass spectra - Furthest right peak it the molecular ion peak which is the species with has not undergone any fragmentation only 1e- is lost - M+1 peak is due to uncommon isotopes such as C13 - m/z values can be used to determine functional groups and isotopes due to how molecule is split E.g. the difference between propanal and propanone IR spectroscopy monitors the vibrations of chemical bonds each bond has a specific wave length which is dependent on bond strength (double/triple and bond enthalpy) - only molecules which can change polarity when they vibrate absorb IR this will also help work out what molecules are greenhouse gases such as water, carbon dioxide and methane all are able to shift diapoles whereas oxygen and nitrogen cannot Halogenoalkanes and Green Chemistry Name, classify and draw halogenoalkanes (easy) Structures affect reactivity through: - Halogen present Bond C-F C-Cl C-Br C-I H (kjmol-1) 467 346 290 228 Strength of bond decreases which is independent of polarity

Number of methyl groups attached to C-X o More methyl groups = increase in reactivity as is draw electron density away from C-X bond thus weakening it - Hot aqueous silver nitrate solution can determine the rate of reaction by how quickly the ppt is formed Prepare halogenoalkanes from alcohols via indirect of direct substitution: Chloro-alkane can prepared with HCl and shaking with alcohol, as Cl is highly reactive no catalyst is required

Iodo/Bromo-alkanes require an acid catalyst however has sulfuric acid is a very strong oxidising agent some of the KBr used in the substitution reaction make be oxidised which reduced the yield. As for KI the reaction will not complete so a weaker acid is required o K-X acts as a halide carrier which is reacted with the sulfuric acid in to the HX Purifying organic liquids 1. 2. 3. 4. Add anhydrous CaCl2 (only required when preparing cholroalkanes) Shake in a separating funnel Discard the aqueous layer Remove the residue by washing with sodium hydorgencarbonate until no more CO2 is given off 5. Repeat 6. Dry with anhydrous Sodium sulfate 7. Filter through glass wool

8. Redistill Halogenoalkanes are generally uncreative so are used as refrigerants and will not combust easily so are used as fire retardants Cholroalkanes can contribute to global warming via the depletion of the ozone layer Free radical substitution when under UV light in the stratosphere.

Reactions of halogenoalkanes: Alkene Reflux and heat Hot aqueous alkali Conc. alcoholic alkali Alcoholic ammonia Heat under pressure Amine



Classification of reactions - Addition - Elimination (see above alkene) - Substitution (see above alcohol and amine) - Reduction, show [H] in equation - Oxidation, show [O] in equation - Hydrolysis, OH- group may come from water, alcohol or inorganic compound - Polymerization, removal of double bond Bond breaking can occur differently and is usually subject to the polarity of the bond - Homolytic bond fission : electrons are shared between the 2 species in the bond producing free radicals Cl2 2Cl - Heterolytic bond fission: electrons are kept by one atom producing electrophiles and nucleophiles HCl H+ + :ClIt is useful to classify reagents as you can predict what time of reaction mechanism will occur - Polar bonds always break heterolytically - Non-polar bonds usually break homolyticaly - Nucleophiles attack + - Electrophiles attack electron rich areas such as double bonds () Application of free radical substitution to the ozone and greenhouse gases 1. Oxygen undergoes homolytic bond breaking forming 2O 2. O combines with O2 and forms ozone which prevents harmful UV reaching earth surface However ozone is broken down by free radical substitution involving CFCs and Nitrogen oxides. - CCl2F2 CClF2 + Cl - Cl + O3 ClO + O2

The cycle is continued as Cl free radicals are regenerated: ClO + O3 2O2 + Cl The same process occurs with NO2 and NO Green chemistry see other notes