Tutorial-6

1) The gas-phase decomposition of acetic acid at 1189 K proceeds by way of two parallel reactions
(a) CH3COOH → CH4 + CO2 ; k1 = 3.74 s−1 (2) CH3COOH → H2C=C=O + H2O ; k2 = 4.65 s−1 . What is
the maximum percentage yield of ketene CH2CO obtainable at this temperature?

2) From the biological standard half-cell potentials E⊕(O2,H+,H2O) = +0.82 V and E⊕(NADH+,H+,NADH) =
−0.32 V, calculate the standard potential arising from the reaction in which NADH is oxidized to NAD+
and the corresponding biological standard reaction Gibbs energy
3) The potential of the cell Pt(s)|H2(g)|HCl(aq)|AgCl(s)|Ag(s) is 0.312 V at 25°C. What is the pH of the
electrolyte solution? (Standard cell potential is +0.22 V)

4) The rate constant for the first-order decomposition of N2O5 in the reaction 2 N2O5(g) → 4 NO2(g) +
O2(g) with rate = kr [N2O5] is kr = 3.38 × 10−5 s−1 at 25°C. What is the half-life of N2O5? What will be the
total pressure, initially 78.4 kPa for the pure N2O5 vapour, (a) 5.0 s, (b) 5.0 min after initiation of the
reaction?
5) The elimination of carbon dioxide from pyruvate ions by a decarboxylase enzyme (CH3COCOO- (aq)
+ H+(aq) → CH3CHO (aq) + CO2 (g) ) was monitored by measuring the partial pressure of the gas as it
was formed. In one experiment, the partial pressure increased from zero to 100 Pa in 422 s in a
first-order reaction. What is the rate constant of the reaction?
6)The following mechanism has been proposed for the decomposition of ozone in the atmosphere: (1)
O3 → O2 + O and its reverse (k1, k1 ′) (2) O + O3 → O2 + O2 (k2). Use the steady-state
approximation, with O treated as the intermediate, to find an expression for the rate of decomposition of
O3. Show that if step 2 is slow, then the rate is second order in O3 and −1 order in O2.