5022 (a) Write the chemical equation and algebraic expressions which define pK a in terms of molar concentrations present when an acid, HA, dissociates in water. (b) Methanol has acid-base properties that are similar to those of water. Write chemical equations which illustrate methanol functioning as an acid and as a base. 5027 Equal volumes of 1.0 molar solutions of malononitrile [(NC)2CH2, pKa 11.2] and the sodium salt of phenol [C6H5O–Na+] in water are mixed. [Phenol, C6H5OH, has a pKa 10.0]. What is the equation for the reaction which occurs and what is the equilibrium constant at room temperature for that reaction? Qualitatively, which species will be present in higher concentrations at equilibrium, and which will be present in lower concentrations? 5142 Most carboxylic acids dissolve in 0.1 M sodium bicarbonate solution, but most phenols do not. This difference forms the basis for an important separation procedure. Given that Reaction RCO2H + ArCO2H H2CO3 + + H2O H2O H2O ~Ka RCO2 + H3O+ 10–5 ArCO2 + H3O+ 10–10 HCO3 + H3O+ 10–7 show, by calculation, why the solubilities are as stated above. 5174 Using the pKa values given, decide whether the equilibrium will lie toward the right or the left. Give a justification for your choice. (a) – N+H + HCO3 + H2CO3 N pKa 6.5 5.2 (b) O O H3C pKa C 4.3 OH + –CH2NO2 H3C C O– + CH3NO2 10.2 5217 Given the pKa of ammonium ion (9.2) and of hydrogen cyanide (9.1) shown below, calculate the free energy in kilocalories or kilojoules for the reaction. NH4+ + CN– NH3 + HCN Which species will predominate at equilibrium in a 0.1 M solution of ammonium cyanide? 5242 Using the data below, account for the fact that p-aminobenzoic acid does not exist appreciably as the dipolar ion, but p-aminobenzenesulfonic acid does. Acid + C2H5NH3 C6H5CO2H C6H5NH3+ C6H5SO3H pKa 9.5 4.2 4.6 0.7