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CH2416Interpreting Data

Transition state theory G is defined as the change in the Gibbs energy of a system in which 1 mole of activated complex is hypothetically formed from reactants at a constant temperature, with all species in a standard state, usually defined as 1 mol dm-3. Thermodynamic Parameters G describes the difference in Gibbs activation energies at different pressures. V is positive for dissociate reactions, and negative for associative reactions. Charge formation leads to electrostriction of solvent molecules and a negative volume of activation.

Mechanistic feature Bond breaking/ forming

Contribution to V (cm3 mol-1) +/-10

Synchronous displace- -5 ment Bond deformation and cyclisation ~0

A change in the standard state will effect the energy profile, as will a change in entropy. These effects depend on the form of the reaction being studied - i.e. at a lower concentration standard state the recombination of two species will be more difficult and so requires more energy. Michaelis-Menten kinetics originate from this, a reaction showing firstorder dependence on a species, [A], at low concentrations and zero-order dependence at higher concentrations suggests a change in identity of the rate determining stepG increases for the step involving [A] as the statistical likelihood of it combining with reactant, [B], decreases.

Charge neutralisation/ +/-20 ionisation Charge dispersal/ concentration +/-5

H is positive and large for bond formation, negative and large for bond breaking and small when bonds are both formed and broken. Values can be predicted by Benson group additivity, molecular mech. and quantum calculations. S is positive when breaking bonds and negative when forming bonds although solvent action must be accounted for.

CH2416Interpreting Data
Determining a pH-rate Profile pH-rate profiles provide evidence of base or acid catalysis, an important aspect of many mechanisms. Using buffer solutions it is possible to perform a reaction across a range of pH values. The innocence of the buffer is assessed by plotting kobs against [buffer]tot - a flat line shows no interference by the buffer. A plot of pH against log k can then give information on how a reaction is catalysed and if the mechanism changes under different pH values. The gradient of the slope is Specific Acid Catalysis Specific Base Catalysis

Mechanisms giving rise to specific base catalysis include; Mechanisms giving rise to specific acid catalysis include; Rapid protonation forming a pre-equilibrium followed by a rate determining step that does not involve proton transfer Rapid deprotonation forming a pre-equilibrium followed by a rate determining step that does not involve proton transfer
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OH behaving as a nucleophile generates the same rate law

General Acid Catalysis Solvent Kinetic Isotope Effects In general acid/base catalysis, in which there is a ratedetermining proton transfer, a normal isotope effect will be seen, i.e. kH2O>kD2O. In specific acid/base catalysis there is an inverse isotope effect, i.e. kD2O>kH2O. The O-H bond in H3O+ has a very broad potential energy well and so even an increase in potential energy leads to a narrower potential energy well by comparison. D3O+ has a lower zero point energy and is therefore subject to either a lower energetic barrier, or achieves greater energetic gain and so kD20 is increased. Diagram showing the zeropoint energy benefit in moving from (H/D)3O+ on the left to X-H/D on the right. hydrogen deuteron

General Base Catalysis

Mechanisms giving rise to general acid catalysis include; Rate-determining proton transfer Rapid protonation of substrate in preequilibrium followed by a rate-determining deprotonation at another site by any base Rate determining acid-assisted nucleophillic attack

Mechanisms giving rise to general base catalysis include; Rate-determining proton transfer Rapid deprotonation of substrate in pre-equilibrium followed by a rate-determining protonation at another site by any acid Rate determining base-assisted nucleophillic attack

Grunwald-Winstein Equation Using the hydrolysis of tbutylchloride as a reference, the Grunwald-Winstein equation is used to define the ability of a solvent to stabilise a charge, this ability is denoted as Y.

m is specific for a reaction under defined reaction conditions.

CH2416Interpreting Data
Linear Free Energy Relationships (LFERs) Related processes have energetics that share common features, it is possible to related trends in reactivity between compounds and extract information. It is also possible to relate trends in reactivity with trends in equilibrium constants. Brnsted values; /=0 ; reaction is insensitive to difference in acid/base strength, the proton transfer is minimal in the activated complex /=0.5 ; the proton is symmetrically shared by the substrate and the acid/base, i.e. A/B--H-In general acid catalysis a stronger acid will act as Substrate. a better catalyst; /=1 ; high sensitivity to the difference in acid/ base strength, proton transfer is complete in activated comlex Non-linear Brnsted plots; Similarly in general base catalysis a stronger base These arise when; will act as a better catalyst; The reaction becomes diffusion controlled The reaction becomes specific acid catalysed The mechanism changes

ET(30) Solvochromatic Probe ET(30) is a charge-separated species stabilised by polar solvents and H-bond donors. Increased stability=increased energy photons required to form the biradical species.

The Hammett Equation Used to relate the activation Gibbs energy for reactions to the (de)protonation equilibria of substituted benzoic acids. It is assumed that the reaction under study has commonality with the equilibrium, particularly the formation of charge. For benzoic acid;

with X and is defined for a given substituent, is defined for specific reaction conditions. only accounts for inductive effects, where resonance is possible there are alternate standards, and +. + uses the solvolysis of substituted cumyl chlorides as a reference reaction, uses the dissociation constant of substituted phenols as reference. Typically all 3 graphs are plotted, the one with the least scatter is considered the best model. >0 ; negative charge formed or positive charge dissociated on reaction centre of interest in the activated complex <0 ; positive charge formed or negative charge dissociated on reaction centre of interest in the activated complex Non-linear Hammett plots describe a change in mechanism.

Generally;

provides a value, in kJ mol-1, of the charge stabilisation energy achieved by substitution