C11

Kw value in neutral water

1×10^-7

Kw =

[HO-][H+]

what does the rate equation include

the species involved up to and including the rate determining step

what is usually the y axis of a reaction profile

gibbs free energy

what does a multi-term rate equation mean

the reaction can take place via 2 different routes

what is the Yukawa-Tsuno correction

adjusting the sigma value when conjugation affects the varying constituent

what does a positive ro value indicate on a Hammett plot

EWG gives a faster rate

a negative ro on the Hammett plot suggests

EDG increases rate

what is a More-O’Ferrall-Jencks (MOJ) map

classic reaction pathway map that shows reactants, intermediates and products

what does a straight line between reactants and products mean on a MOJ map

Synchronous concerted line, when the lg leaves and nu joins in a concerted mechanism

what does a straight line between intermediates on a MOJ map mean

when lg=nu, the TS must lie on this line and its a plane of symmetry

what is a Bronstead plot?

plots log(kx) against pKa

what does a kink in a Bronstead plot mean

there is a change in the RDS, kink occurs at Pka(Nu) = pKa(Lg)

what does the slope mean in a Bronstead plot

β(nuc/lg depending on whats varied)

steep slope on a bronstead plot means… (+ve)

stronger dependence on the nucleophile

what does a kink in a bronstead plot signify

• there has been a change in the RDS

• kink occurs when pKa(Nuc) = pKa(Lg)

X axis of MOJ plot

C-Lg bond breaking

Y axis of MOJ plot

C-Nu bond forming

βeq = … (βlg, βnuc)

βnuc - βlg

how can βeq be determined experimentally

plot log(keq) vs pKa

what does a kink at pKa(nuc)=pKa(lg) mean

an intermediate is formed

what does it mean if there is no kink in a bronstead plot

no intermediate formed so concerted reaction

α nuc = (βnuc, βeq)

βnuc / βeq

meaning of α nuc

the degree that the nuclephile has formed its new bond, can be plotted on MOJ diagram

meaning of α lg

degree to which the lg bond has broken, can plot on MOJ diagram

β defined in terms of charge

the change in charge between nuc or lg from reactant to TS