KINETICS - Biochemistry 1.

Describe, with the aid of a sketch, how the rate of an enzyme catalysed reaction varies with substrate concentration.
N98 / IV / 2

2. Proteases, such as pepsin, are enzymes which hydrolyse protein into smaller units. (i) Write an equation for the hydrolysis of the peptide linkage in protein. (ii) Describe how the enzyme is able to make this hydrolysis possible.
N99 / IV / 2

3. Draw a large, labelled sketch to show how the rate of an enzyme-catalysed reaction varies as the substrate concentration increases with a fixed amount of enzyme.
N2002 / III / 10

4. Explain briefly how enzymes work.

J2003 / VI / 1

ENERGETICS - Thermodynamics 1. The standard enthalpy change of formation, Hf, and the standard free energy of formation, Gf, of CO(g) and CO2(g) are as follows. Hf / kJ mol-1 Gf / kJ mol-1 CO(g) -110.5 -137.2 CO2(g) -393.5 -394.4

Show that the reaction C(s) + CO2(g) 2CO(g) is not feasible at 298 K but is feasible at 1000 K.
N2002 / III / 15

2. Comment on the following in terms of free energy and/or entropy changes. (a) The enthalpy change of fusion of ice is +6.0 kJ mol -1. At 173 K, ice and water are in equilibrium but at 298 K, ice spontaneously changes into water. Ethanol and water mix in all proportions, but butan-1-ol and water have only a limited solubility. In biological systems, small glucose molecules are converted into large polysaccharides such as starch and cellulose. This polymerisation is accompanied by only a small enthalpy change but by a large decrease in entropy. This appears to contradict the Second Law of Thermodynamics.
N2002 / III / 16

(b) (c)

3. Reaction 1: C(s) + O2(g) CO2(g) Reaction 2: 2C(s) + O2(g) 2CO(g) Explain qualitatively the following, Why does G for reaction 2 become more negative with increasing temperature? Why is G for reaction 1 almost independent of temperature?
N2003 / III / 15

4. The standard enthalpy change of combustion of propane, C3H8, is -2220 kJ mol-1 (i) Write a balanced equation for the complete combustion of propane. Include state symbols that refer to standard conditions. (ii) Calculate the standard enthalpy change of formation of propane. [Hf H2O(l) = -285.9 kJ mol-1; Hf CO2(g) = -393.5 kJ mol-1; R = 8.310 J K-1 mol-1]
N2004 / III / 15

5. An extremely efficient rechargeable cell is based on the following reaction. Ag2O(s) + Zn(s) 2Ag(s) + ZnO(s) Unfortunately, the high cost of silver means that such cells are only used for military or space applications. They are used in rockets, and are activated during the launch by releasing an electrolyte of KOH(aq) into the empty cells. (a)
1

(i) Given the following values (all in kJ mol-1), calculate H and G for the forward reaction. [ans: H = -317.4 kJ mol-1, G = -307.4 kJ mol-

] [Hf (Ag2O) = -30.6, Hf (ZnO) = -348.0, Gf (Ag2O) = -10.8, Gf (ZnO) = -318.2] (ii) In use, the cell produces 1.50 V. Calculate the heat produced by the cell under these conditions. [ans: 27 kJ mol-1] (b) It is possible to design a cell based on the following reaction. Zn(s) + Fe2O3(s) ZnO(s) + 2FeO(s) For this reaction, H = -58.8 kJ mol-1 and G = -65.8 kJ mol-1. Suggest in terms of the entropy changes accompanying the reaction why G is more negative than H.
N2005 / III / 16

6. Chloroethene, CH2=CHCl, is a starting material for the manufacture of PVC. It is made by the addition of chlorine to ethene to give 1,2-dichloroethane, followed by elimination of hydrogen chloride to give chloroethene. (a) For the addition of chlorine to ethene at 360 K Cl2(g) + C2H4(g) C2H4Cl2(g) H = -190.0 kJ mol-1 and G = -146.2 kJ mol-1 Calculate S at 360 K. For the elimination of HCl from C2H4Cl2 C2H4Cl2(g) C2H3Cl(g) + HCl(g) H = +83.5 kJ mol-1 and S = +83 J mol-1 K-1 Assuming that H and S do not change with temperature, calculate the temperature at which this elimination reaction becomes feasible. Why is the sign of S for the elimination reaction different from that calculated in (a)?
N2006 / III / 15

(b)

(c)