Thermodynamics. H is positive or H > 0 Reaction endothermic, energy absorbed (added into the system), i.e.

solid to liquid, ice melts. H is negative or H < 0 Reaction exothermic, energy is released (has left the system). i.e. liquid to solid (freezes, heat is removed). G = H T S Gibbs free energy. The free energy in a system is the heat minus the temperature times the disorder. G > 0 non spontaneous reaction - Keq < 1 G < 0 spontaneous reaction - Keq > 1 For a spontaneous reaction, the change in free energy is negative because it has been used up in getting over the hill. 1st law thermodynamics: Euniverse = Esystem + 2nd law thermodynamics: Suniverse = Ssystem +

Esurroundings = 0

Ssurroundings = > 0

3rd law thermodynamics: Perfect crystal = zero entropy S > 0 Solid Liquid Gas = more disorder S < 0 Gas Liquid Solid = less disorder Ssurroundings = H/T An exothermic reaction makes S (the surroundings) positive as heat is released so the disorder increases in the surroundings because of it. Spontaneous change favours disorder i.e. Suniverse = Ssystem + Ssurroundings = > 0 S increases as temperature rises. Entropy of a dissolved solid, liquid, gas is greater than the entropy of a pure solute or gas.

T always positive as it is in Kelvins. Exothermic reactions are more likely to be spontaneous A positive change in S(tot) corresponds to a negative change in G (exothermic, energy released into universe) Q increases as products are generated and G changes with it. G = 0 at equilibrium between K and Q H S G - + - Spontaneous at all temperatures. + - + Non spontaneous at all temperatures. + + +/- Spontaneous above certain temperatures - - -/+ Non spontaneous at higher temperatures Equilibrium. Reaction quotient Q taken at a time before equilibrium reached (an instantaneous concentration). Determines direction of reaction time when compared with K. Q < K reaction will shift right Q > K reaction will shift left Q = K reaction at equilibrium Keq < 1 more reactants than products Keq > 1 more products than reactants Add reactants reaction will shift right Remove reactants reaction will shift left Add heat to exo reaction will shift left (heat added as product) Add heat to endo reaction will shift right (heat added as reactant. Rate Laws Rate of a reaction = X/ T

The larger the rate constant, the shorter the half life. Also, the faster the reaction, the shorter the half life.

Zero Order Reaction The reaction rate is constant, and the reaction stops when the reactants are completely consumed. R=K The rate constant, k, has units of mole L-1 sec-1. [A] vs T = straight First order Reactions The rate of reaction is directly proportional to the concentration of one of its reactants. r = k [A] The rate constant, k, has units of sec-1. Ln[A] vs T = straight Second order reactions Rate is directly proportional to the square of one of the reactants (a single second order reactant), or on two first order reactants. r = k [A]2 OR r = k [A] [B] 1/[A] vs time = straight Double or halve A+B and the reaction rate will quadruple or quarter Double A and triple B, reaction rate will be 2x3 Doubling or halving A alone will double or halve the rate. Oxidation and reduction. Oxidation side: [X] [X]2+ + 2e- (Reduced species -> oxidized species + ne-) Reduction on the reactant side, oxidation is at the products side Reduction side: [X]2+ + 2e- [X]- (Oxidized species + ne- ->

reduced species) Reduction is on the product side, oxidation is at the reactant side. An increase in charge # (ie + or on the ion) implies oxidation. A decrease in charge # implies reduction. Oxidation is the loss of electrons or hydrogen, and the gain of oxygen, nitrogen or a halide. Reduction is the gain of electrons or hydrogen and loss of oxygen, nitogren, or a halide. In o-chem, if both happens (i.e. oxygen is lost and gained, or oxygen is lost and nitrogen gained, then it is not a redox reaction. Species 1 Loses electrons It thus supplies electrons Undergoes oxidation Is the reducing agent Increases charge # Species 2 Gains electrons It removes electrons Undergoes reduction Is the oxidizing agent Decreases charge #

In some reactions an element is both oxidized and reduced do it in steps. The oxidant (oxidizing agent) removes electrons from the other substance is thus reduced itself. Reduction Potential (E) how likely something will undergo a reduction reaction. Large E more likely to undergo reduction than a smaller E Large NEGATIVE E more likely to undergo oxidation than a more positive E Ecell = oxidation potential + reduction potential Eocell = Eocathode (reduction) - Eoanode (oxidation) The stronger a reducing agent (the species that is oxidized), the more negative its E. The stronger an oxidizing agent (the species that is reduced), the more positive its E

Anode: Oxidation half, loses the electrons and is designated negative (it is the supplier). Negative in a voltaic cell, positive in an electrolytic (i.e. battery being recharged) cell. Cathode: Reduction half, gets the electrons (is positive because it is receiving). Positive in a voltaic cell, negative in an electrolytic cell. Standard Hydrogen Electrode (SHE): Reference half-cell by which reduction potentials E are calculated. The E reference is 0V and is calculated as 2H+ + 2eH2 E= 0 O = -2 except for peroxide which is -1. Halogens are -1. To combine two half reactions facing the same way, flip the one with the smaller E and reverse the sign. This will become the oxidized side if you have two reduction half reactions. E changes sign when a reaction is reverse. Multiples of half cell reactants/products do not alter E Voltaic: energy is released from a spontaneous redox reaction with an E cell overall being > 0 Electrolytic: energy is supplied to drive a non spontantaneous reaction with overall E cell being < 0 A strong oxidizing agent is more likely to undergo reduction it makes a good electron thief! Acids and Bases Acids < Ph 7 Protonated keeps the H Deprotonated has lost the H Releases H+ ions in water Proton donor Electron pair acceptor Becomes neutral or negative upon dissociation Bases > Ph 7

Produced OH- ions in water Proton acceptor Electron pair donor Becomes neutral or pos upon dissociation Strong acid = weak conjugate base Conjugate acid formed after base accepts H+ i.e. H2O = base H3O+ = conjugate acid Strong acid = fully dissociated = strong base Weak acid = mostly protonated (hasnt lost H+) Weak base = mostly deprotonated (yet to accept H+) pH = H+ ions -log[H+] =pH ---------- pKa below = dissociated ----------pH-----------pKa above = protonated not dissociated When pH = pKa , the ionizable compound in question (whether acid or base) will be half protonated and half deprotonated. COOH (strongest) --- Phenol (weaker) --- Alcohol (weakest) Buffers Resist pH changes and are generally a weak acid or base, they follow Le Chateliers principle (i.e. if an acid is added to an acid it will shift away from that). High Ka / Low pKa Strong acid Weak conjugate base More dissociated Low pH < 7 Low Ka / High pKa Weak acid Strong conjugate base Less dissociated High pH > 7

Buffer capacity: Amount in moles of H3O+ (H+) or OHneeded to change the PH by 1

Non metal hydride acidity (hydrogen no oxygen, i.e. HF) increases right, THEN increases down Oxoacids (acids containing oxygen i.e. HSO4) acidity increases with electronegativity and number of oxygen atoms. Alkyl groups are basic. Resonance enhances acidity (more acidic when electrons distributed over benzene ring, delocalization of charge) Alpha hydrogens are acidic in aldehydes and ketones A complete pH change happens over 2 units for indicators. At the equivalence point, moles of OH = moles of H this is at 7 for strong acids and bases, and >7 for weak acid, and < 7 for weak bases. Solubility Solubility product constant is Ksp Where AcBd + H2O cA+ + dBKsp = (A)c(B)d i.e. [Ca2+][PO43-]2 Small Ksp = Low solubility High Ksp = High solubility Bonding potential similar types of intermolecular forces in substances will dissolve in each, like dissolves like. NaCl more likely to dissolve in CH3)H than in a long chain hydrophobic molecule (not so soluble) Temperature solubility increases with temperature if solution process is endothermic. (reverse if exo) - solubility decreases with temp if solution process is exothermic (reverse if endo) Common ion decreases solubility by causing a shift away

from itself (a precipitate will form) pH a compound containing the anion of a weak acid with the addition of H+ ions (i.e. acid) will increase in solubility by removing an ion and pushing the compound to dissolve more ions. Pressure only affects gas. Henrys law solubility = Kh x partial pressure Increase the partial pressure and you increase the solubility. To work out the molar values for the reactant in solution, you write Ksp as c(A)cd(B)d The vapour pressure inside the solvent does not exist. Imagine a closed container. The container contains the pure solvent and some space above it. The space above it is not a vaccuum. There are molecules escaping from the solvent into this area. There are also gas molecules returning to the solvent. When the rates of evaporation and condensation are equal, the system is in equilibrium. The resulting pressure of the gas molecules in this closed container is called vapour pressure. A 'nonvolatile and unreactive' solute is now added to the pure solvent. The fact that it is nonvolatile is important. It means that it will occupy some of the surface area at the top of the liquid. This makes it harder for solvent molecules to escape into the space above the liquid. Fewer gas molecules means lower vapour pressure. Atmospheric pressure is outside the closed container, not in the solvent. The energy required to get each solution to boiling point varies according to their respective vapour pressures. Vapour Pressure

Energy needed to raise Vapour Pressure t Boiling Pt

Original solution Solution with solute

higher

lower

lower

higher

In both situations, atmospheric pressure is constant. Isomers Constitutional isomer same molecular formula, different links between atoms, i.e. OH might be at different spots. Keto enol tautomerism alpha H will migrate to the =O (keto) to form OH (enol) spontaneously. Keto form is more stable 99% of the time, except in vitamin C which is more stable in the enol form. Stereoisomers enantiomers or diastereomers, there are 2n diastereomers where n is the number of chiral centres. Dextro (+) goes right. Laevo (-) goes left chiral only. Meso (plane of symmetry) are not optically active. Anomers where two isomers mutate into another form. Alpha anomer has the same config at anomeric centre as the last similar asymmetric centre. Beta anomer has opposite config at anomeric centre to its last similar asymmetric centre. anti conformation: A type of staggered conformation in which the two big groups are opposite of each other in a Newman projection. gauche conformation: A type of staggered conformation in which two big groups are next to each other Resonance Resonance forms are theoretical and not real They differ only in the placement of electrons

The rules of valency apply Resonance hybrid is the most stable and resonance = stability Different resonance forms dont have to be equivalent. When not equivalent, actual resonance hybrid is closer to the more stable form. More nearly equivalent resonance forms = greater stability. These are more stable than equivalent non resonance hybrid. No unlike separation of charges contribute MORE than forms with separation of charges. Forms with negative charge on the more electronegative atom contribute more than forms with negative charge on any less electronegative atom. No separation contributes most Negative charge on more electronegative atom contributes next. Negative charge on less electronegative atom contributes least. Hydroxyl (OH), methoxyl (-OR), and amino (NR2) cause electron flow onto the ring and four resonance forms. Nitro (N+) and carbonyl (COOH, =O) cause electron flow OFF the ring onto the substituents and four resonance forms. When one subsituent is on an aromatic ring, this will dictate where the second substituent added to the ring will go. The first substituent is an ortho/para or a meta director. Ortho/para directors: 1) an alkyl group 2) if the atom directly attached to the ring has one or more electron pairs Meta directors: 1) if the atom directly attached to the ring has multiple bond 2) if the atom directly attached to the ring has a formal + charge Diels Alder Reactions

Two carbon carbon bonds are formed in a single step and there are no intermediate step and its not a polar or radical reaction. Reaction is endo only (i.e. heat must be applied) Diene Can be simple Electron rich Alkyl or Alkoxy Groups release electrons Can increase reactivity Poor dienophile Dienophile Alkene or alkyne Not simple Usually has C=O or C=N Electron poor, needs electron withdrawing group

Reaction always contains one more ring than the reactants. The dienophiles double or triple bond becomes single or double respectively. Diene must generally be in s-cis conformation to work, in trans the p-orbitals are too far apart. Dienes with functional groups that hinder the trans conformation (ie. Block it from switching to that) react faster than butadiene. Electron donating groups of diene and dienophile in the end reaction generally bear a 1,2 or 1,4 relationship, but not a 1,3. Addition and Substitution Reactions Hydrogenation: Addition of hydrogen across a double bond. Substitution reaction: When two reactants exchange parts of molecules to form a new product i.e. a nucleophilic substitution at saturated carbon. Addition reaction: Occurs when two molecules add to form a single molecule with no atoms left over. Electrophilic addition occurs when an electrophile attacks an unsaturated carbon carbon bond. Elimination Reaction: Occurs when a single reactant loses

two groups from adjacent carbons. The two groups that have left form a product, and the original product has a double bond (the major product) Nucleophiles Lone pair of electrons on N, O, S Double or triple carbon bonds Nucleophiles with a neg charge is a more powerful nucleophile than its conjugate acid. OH- stronger nucleophile than H2O Nucleophilicity runs opposite to electronegativity and increases going DOWN the table. SN2 reaction. (second order with respect to leaving group and base) Molecule attacked by nucleophile (generally a strong base) and another atom on the opposite side of the molecule displaced, usually a halogen. Reaction rate affected by strength of attacker, concentration of nucleophile and target molecule, and nature of target molecule. Methyl halides are best candidates for attack as there is no hindrance to the attacker (i.e simple strong base) does not occur in tertiary halides or vinylic halides and only in some secondaries (competes with E2 will win if a weak basic nucleophile is used). Chirality swaps SN1 (first order with respect to leaving group) Molecule contains a molecule that leaves on its own, and is THEN replaced by another atom. It breaks apart on its own. Usually occurs in the presence of a base. Reaction rate influenced by polar solvents (increase rate), weaker halide ions (i.e. big ones) dissociate more easily from the molecule. Best leaving group molecules for SN1 reactions leave behind

the most stable carbocations i.e. tertiary and secondary halides. The Br will fall off the already crowded molecule and something stronger will take its place. Primary and methyl halides are unsuitable theyd fall apart!! Will occur on the secondary with benzylic and allylic halides Chirality doesnt swap. E2 Reactions Strong base attacks molecule removing H+ and breaking C-X bond. X and H+ leave, leaving behind a molecule with a double bond. Happens across two carbons. Occurs where geometry is anti (opposie sides of the carbon bond). Carbons adopt a staggered relationship across the double bond. Favoured by tertiary carbocations for stability reasons, secondary where a strong base is present, and primary if a strong or sterically hindered base is used. E1 reactions. Halide eliminated in rate determining step. H+ quickly follows. Can occur on tertiary halides (rarely) in a hydroxylic solvent, secondary with benzylic and allylic halides. Not at all with methyl and primary alkyl halides. Strong bases are: OH-, OR- (e.g. CH3CH2O-), NH2Weak bases are: H2O, ROH Depends on stability of the carbocation intermediate: E1 vers us E2

Primary carbocations favour E2 because they cannot remain stable long Secondary/tertiary carbocations favour E2 when the nucleophile is a stro base ionises readily and removes a H from the organic compound. Secondary/tertiary carbocations favour E1 when the nucleophile is a wea does not ionise readily, thus promoting stability of the secondary/ter stable carbocation is a pre-requisite for E1.

Depends on steric hindrance, nucleophilic strength and base strength: SN2 vers us E2

Primary carbocation SN2. Primary carbocations have little steric hindran Secondary carbocation E2 with good nucleophile/strong base (OH-, CH3 Secondary carbocation SN2 with good nucleophile/weak base (I-, CH3C Tertiary carbocation E2 with strong base. E2 reactions are encouraged b secondary/tertiary carbocations.

Aldol condensation. Aldehyde or ketone will lose the hydrogen on its alpha carbon to react with itself. Number of alpha carbons contributes to number of products. When two different aldehydes or ketones react, and both can take the loss of H, four different products will result. 1. The self product of the aldehyde 2. The self product of the ketone 3. The product of the ketone and aldehyde occurring at the alpha carbon of the ketone. 4. The product of the ketone and aldehyde occurring at the alpha carbon of the aldehyde. Formaldehyde has no alpha carbon so cannot participate in the first reaction, however it can participate in the second step. Aldols easily dehydrated to form aldehydes or ketones, condensation followed by dehydration is a common way to prepare double bonded aldehydes and ketones. The product formed when an aldol is dehydrated, always contains a conjugated enone C=C-C=O.