Chemical quantities and formulae Definitions - Elements are substance which cannot be broken down by chemical means into

other substances - Atoms are the smallest part of any element that can take part in chemical reaction - Ions are formed when an atom gains or loses electrons charged particles - Compounds are formed when two or more elements are chemically attached - Molecule is the smallest part of a covalent compound or an element that can exist alone - Empirical formulae is the simplest atom ratio of the elements of a compound Step 1 2 3 Method P Divide by smallest value Input whole number ratio to formulae Example H

2 CH2O

Molecular formulae the exact number of atoms /ions that make up a compoundexact multiple of its empirical formula X Empirical formula
E

Balancing equations and ionic equations - Include ions in ionic equations which have changed state from one side of the equation to the other - The rest of the molecules are spectator ions which are not involved with the reaction 1. Put state symbols and show separate ions Fe(s) + Cu2+ (aq) + SO42-(aq) Cu(s) + Fe2+ (aq) + SO42-(aq) 2. Remove spectator ions Fe(s) + Cu2+ (aq) C (s) + Fe2+ (aq) 3. Balance out charges y h - Half equations would show the molecules/ions which change oxidation state and you balance charges with electrons E.g. Cu2+ (aq) + 2e- Cu(s) Fe(s) Fe2+ (aq) + 2eSolution calculations: n = c x v and amounts of substance with n = Concentrations can be expressed as Parts per million = (amount by volume or mass) Av d h b x y b -12 which equals 23 6.02 x 10 - can also show how many particles in a given number of moles of a solid or gas - moles x (6.02 x 1023) Chemical equations can be used to determine the masses of reactants and vice versa, the mass of reactants can confirm a balanced equation - however due to rounding to the nearest mole the balanced equations may not be entirely accurate - Practice the calculations

Reactions with gases - Molar volumes is the volume occupied by 1 mol of any gas= 24dm3 at standard pressure and temp - Ratio of gas volumes used to calculate reacting masses. E.g. 6dm3 of methane = = molar volume - Also able to find chemical equations from experimental data as volumes of gases as s.t.p are proportional to their amount E.g. 4.5 dm3 oxygen dm3 nitrogen xy Percentage yields - Must work out theoretical yield first: Step Method 1 Balance equation 2 Molar mass Divide by smallest Mr 3 Multiply by known or starting 4 mass Input end mass into percentage 5 yield equation Percentage yield = x100

Example 2Mg (s) + O2 (g) 2MgO (s)

1.00g x 2.00g 2.00g

1.66g x 2 3.32g

Atom economy- based on the assumption that the yield is 100% X 100% A reaction with a high atom economy has few waste products Reduces the cost of waste treatment and disposal which is good for industrial processes. Atom economy can be improved by finding used for by-products

Salt and double salts are ionic compounds which have a metal/ammonium cation and an acid anion; double salts have more than one cation or anion. They are produced by - Acid + Alkali/Carbonate/Metal oxide - Acid + Reactive metal - The salt must be crystallised from a saturated solution- concentrated by evaporating water and filtering - An insoluble salts forms a ppt which can be filtered, washed and dried.

Enthalpy changes and enthalpy level diagrams H h y v taken in during a reaction under standard conditions. - Between a systems and surroundings - H = HProducts - Hreactants Enthalpy level diagrams show relative energy levels of reactants and products - Exothermic reactions have a negative H d v y into surroundings - Endo h h v v H d k y d Reactants Products Reactants Products

Definitions - H wh d d = d - - H wh b yb xy = - d - H wh d d h - H wh w d by h d + alkali - ALL ENTHALPY CHANGES ARE UNDERSTANDARD CONDITIONS Enthalpy changes can be determines from calorimeter experiments by measuring the heat change of surroundings= mass x c (specific heat capacity) x T This value give the enthalpy change of surroundings produced by the combustion of a known volume of fuel- energy produced per mole = these reactions give out heat so are always exothermic so negative enthalpy sign must be in place Assumptions of the experiment are: - All energy from combustion is transferred into water - The calorimeter does not absorb any heat - There is no heat loss from the water - Fuel has undergone complete combustion Hesss Law states that the total enthalpy change of a reaction is independent of the route taken provided the initial and final conditions are the same - U H wy h H h H H = H - H - H w w y measure enthalpies of formation indirectly using experimental values for example: 1. Add HCl to CaO and CaCO3 in separate containers and H measures the temp changes CaO(s) + CO2 (g) CaCO3(s) 2. Input values into enthalpy equation E =mcT 3. E/n = kj produced per mol 4. Endothermic or exothermic C(s) + Ca(s) +1 O2 (g) depending on whether the temp change was positive or negative Bond enthalpy is the energy associated with 1 mole of I particular bond w y 5. a H - Energy required to break 1 mole of bonds - Energy required to make 1 mole of bonds Mean bond enthalpy is the bond enthalpy of a particular bond in a range of compounds which can be used to calculate the enthalpy change of a reaction however is limited by: - They are average values which may be different in certain environments - Values given are gaseous bond enthalpies o If a liquid is in the calculation the energy of vapourization must be included. - They are calculated under standard conditions H = b d b k ( ) B d d ( h) You can input the values into a H L w y - You need to make sure that the intermediate reaction products are all in the gaseous state so include the enthalpy of atomisation and vapourisation Bond enthalpy is also linked to stability and the larger the bond enthalpy the stronger the bond which gives indication to which bonds will break at a certain energy and what will break first. It can also determine how fast the reaction may take place.

Mass spectrometry - Relative atomic mass is the average weighted mass of an atom relative to 1/12th of C12 - Relative isotopic mass of an atoms isotope is the average weighted mass of an isotope relative to 1/12th of C12 - Deduce relative isotopic composition through relative abundance - Calculate the relative atomic mass of a compound ( ) ( ) Relative molecular mass can also be determined by a mass spec. Not only is the vapourised sample ionized but is also fragmented which gives corresponding m/z peaks. The molecular ion peak (M+) will give the RMM as the molecule has only been ionized and not fragmented Basic principles include: Vaporised Ionized bombardment of electrons creating positive ions Accelerated- an electric field Deflection- magnetic field Detection Uses of mass spec include; radioactive dating, space research, detection of illegal drugs, pharmaceutical industry research Ionization energy and electron shells - Energy required to remove 1 mole of electrons from 1 mole of atoms in the gaseous state which is an endothermic process - Ionization energy provides evidence for quantum shells and electron sub shells Evidence for electrons shells- successive ionization energy Ionisation energy - High energy to remove inner most electrons - Jump suggests new shell - Increasing IE is due to atomic radii and shielding Along with increasing Zeff - Lowest IE due to the outer most electrons Na [1s12s22p63s1] - 1st ionization energy trend increases across a period but decreases down a group.
1 2 3 4 5 6 7 8 9 10 11

Evidence for electron subshells

2500 2000 1500 1000 500 0 Li 3 Be 4 B 5 C 6 N 7 O 8 F 9 Ne 10

Drop between Be and B show that B has a new subshell which is less stable and therefore more easily ionized. N has relatively high ionization energy due to it having a half full subshell which is stable. Noble gases have the highest ionization energy as they have full subshells

Ionisation energy increases across a period as proton number will increase which increases the effect of the positive nucleus on the electrons also reducing the atomic radii. - Subshells orbitals are s, p, d and f. They can hold 2 electrons each of opposite spin - Subshells have varying different energy levels (4s has a lower energy than 3d) - Use subshells to write out electronic configurations (easy) PERIODIC PROPERTIES melting temp and ionization energy

Giant molecular structures are held together in a covalent lattice and are very strong - C and Si Metallic has the sea of delocalised electrons which strengthen the bond - Li, Mg, Al Simple non-metal molecules only have weak intermolecular forces so have low boiling points - N, O, C , P

Ionic Bonding- omnidirectional electrostatic force of attraction between oppositely charged ions Evidence that ions exist - Physicality such as high melting temp, soluble in polar solvents and conduct electricity when in solution - Electron density maps will show separate ions with zero density between - Electrolysis and separate attraction to anode and cathode Ions try and achieve noble gas configuration (octet rule or isoelectronic) either as an anion (+) by gaining electrons or a cation (+) by losing electrons - Dot and cross diagrams (easy) IONIC LATTICES are formed when each ion is surrounded by an oppositely charged ion can also produce a giant ionic structure Trends in ionic radii - Cations < Anions - Increases down a group due to the increase in shells - Isoelectronic ions radii are dependent on the number of electrons gained or lost. N3- > O2- > F- > Ne > Na+ > Mg2+ > Al3+ Ionic lattices formations 1. Atomization of the metal 2. Atomization of the non-metal Calculated using enthalpy level 3. Ionization of the gaseous metal diagrams application of 4. Electron affinity of the gaseous non-metal H w 5. Formation of the crystal from gaseous ions N.b when calculating the ionisation of the metal you must consider what group and there for whether it is 1st or 2nd I.E - Stability of an ionic compound is relative to the H v Th x h the most stable and endothermic compounds are not feasible unless under very harsh/cold conditions

Polarization of ions- distortion of the ionic cloud away from completely spherical, a cation will distort an anion. This may influence the Born-Haber values away from theoretical values which are based upon the assumption that ions are completely spherical and separate. - Polarizing power it proportional to the cationic charge density and the electron cloud of the anion - Testing the ionic model The values given with sodium halides are very Lattice energy/ kJ mol-1 close to the theoretical value which suggests that Compound BornTheoretical there is very little polarization. Haber NaF 918 912 Silver halides however show a great deal of bond NaCl 780 770 polarization possible due to Ag having a large NaBr 742 735 electron cloud which is distorted more easilyNaI 705 687 increase tendency for covalency in silver halides AgF 958 920 - This is supported by lower melting temps in AgCl 905 883 AgX compared to NaX AgBr 891 816 Covalent bond is the strong electrostatic AgI 889 778 b w h h w involved and the shared pair of electrons - Dative covalent bond are formed when both shared electrons are from one atom - Double/triple bonds - Lone pairs of electrons affect the shape of the molecule as they contribute to areas of electron density. They must also be shown on dot-cross diagrams and H bonds but be an electronegative atom with a lone pair of electrons Evidence for covalent bonds includes: - Electron density maps which show high density between 2 atoms - Giant molecular structures physical properties show that very strong bonds exist. Such as diamond which has very high melting temps. Dot and cross diagrams (easy) Metallic bonding - is the strong attraction between metal ions and a sea of delocalized electrons (vibrating), their properties include: - Electrical conductivity, movement of delocalized can move in direction of electric field - Thermal conductivity, the delocalized electrons transmit kinetic energy (heat) - High melting temp, strong attraction - Malleable and ductile due to layer of positive ions can slide and still remain surrounded by delocalized electrons Alkanes- saturated hydrocarbons which have the general formula CnH2n+2; alkanes can have the same molecular formula but produce different structural isomers through branching - Alkanes are used and fuels as they combust in excess oxygen such as methane CH4 + 2O2 CO2 + 2H2O - Fuels are produced via fractional distillation, cracking and reforming o Cracking produces smaller chain alkanes and alkenes o Reforming is also the breakdown of long chain HC but will increase the proportion of aromatic compounds o Fractional distillation is simply the separation of components of a mixture such as crude oil Alternative fuels to crude oil, which is non-sustainable, are being developed to reduce carbon emissions and global warming - Combustion of hydrogen only produces water which is considered cleaner; however water vapour is a greenhouse gas! - Hydrogen can combine with oxygen in fuel cells and again only produce water - Production of hydrogen from electrolysis is expensive and requires vast amounts of energy- producing greenhouse gases - Biofuels production absorbs CO2 from atmosphere and release when burnt as a fuel which makes them more carbon neutral

Reactions of Alkanes - Combustion produces carbon dioxide and water when fully combusted, if excess xy b xd d wh h h h y x E.g. car engines: C8H18 + 8 O2 8CO + 9H2O - Substitution, such as free radical substitution- curly arrows MECHANISM 1. Initiation : involves UV light to break down Cl2 (h y y) C 2. Propagation: maintains the concentration of free radicals. Reaction must have one free radical on either side of equation CH4 + C CH3 + HCl CH3 + Cl2 CH3Cl + Cl 3. Termination: combination of 2 free radicals Cl + Cl Cl2 C + CH3 CH3Cl CH3 + CH3 C2H6 Alkenes d HC wh h d b b d , CnH2n - Carbon-Carbon double bonds have a sigma and pi bond and are not rotational o p orbitals overlap to produce 2 areas of electron density, above and below the H H sigma bond C C - these bonds produce geometric isomers depending H on the functional groups and what side of the H double bond they exist on - Cis- Trans Isomerism. Cis = same side, Trans = different. This is not based apon molecular weight of groups and therefore is limited - E-Z Isomerism is based in molecular weight, Z = same, E = different - Geometric isomerism is used in the food industry Reactions of alkenes - Addition of hydrogen (Ni catalyst at 200C) k - Addition h d -substituted halogenoalkane - Add hyd h d -substituted halogenoalkane - Oxidation with acidified KMnO4 D - Polymerization involves the removal of the double bond Reaction mechanisms - Bromine + Alkene

Hydrogen Bromine + Alkene

Hydrogen Bromine + Propene

Evidence of reaction mechanisms Mixing Cl- ions with the Br2 solution and the alkenes will be substituted with Cl and Br producing 2 compounds - Di-bromoethane and 1-bromo, 2- chloroethane Bromine water as a test for C=C - Aqueous bromine produces two nucleophiles, Br- and OH- , which attack the carbocation - If the compound contains at least 1 double bond the bromine water will be decolorized because it is reduced - Potassium manganite (VII) reacts the same way, decolorized with the presence of double bonds