Thermodynamics, Statistical Thermodynamics, & Kinetics

164 SOLVED PROBLEMS

Question: 6.11

Using the result of Example Problem 6.10 and the data tables, consider the dissociation equilibrium Cl2(g)→←2Cl(g).a. Calculate KP at 800. K, 1500. K, and 2000. K for P=0.010 bar. b. Calculate the degree of dissociation α at 300. K, 1500. K, and 2000. K. ...

a.   \Delta G°_{R}=2\Delta G°_{f}\left( Cl,...
Question: 6.10

In this example, n0 moles of chlorine gas are placed in a reaction vessel whose temperature can be varied over a wide range, so that molecular chlorine can partially dissociate to atomic chlorine. a. Define the degree of dissociation as α=δeq/n0 , where is 2δeq the number of moles of Cl(g) ...

a. We set up the following table: Cl_{2...
Question: 6.9

a. Using data from Table 4.1 (see Appendix A, Data Tables), calculate KP at 298.15 K for the reaction (CO(g)+H2O(l)→CO2(g)+H2(g). b. Based on the value that you obtained for part (a), do you expect the mixture to consist mainly of CO2(g) and H2(g) or mainly of CO(g) +H2O(l) at equilibrium? ...

a.  \ln K_{P}=-\frac{1}{RT}\Delta G°_{R}[/l...
Question: 4.4

The enthalpy of solution for the reaction Na2SO4(s)→2 Na^+(aq)+SO4^2-(aq)is determined in a constant pressure calorimeter. The calorimeter constant was determined to be 342.5 J K-¹.When 1.423 g of Na2So4 is dissolved in 100.34 g of H2O(l),ΔT=0.031 K. Calculate ΔH°solution for Na2SO4 from these ...

\Delta H°_{solution}=-\frac{M_{salt}}{m_{sa...
Question: 19.6

The reactant 1,3-cyclohexadiene can be photochemically converted to cis hexatriene. In an experiment, 2.5 mmol of cyclohexadiene are converted to cis-hexatriene when irradiated with 100. W of 280. nm light for 27.0 s. All of the light is absorbed by the sample. What is the overall quantum ...

First, the total photon energy absorbed by the sam...
Question: 19.7

The experimental results presented earlier demonstrate that a maximum in the rate constant for electron transfer (∼2.0×10^9 s-¹) occurs when -ΔG°=1.20 eV. Given this observation, estimate the rate constant for electron transfer when 2-naphthoquinoyl is employed as the acceptor for which -ΔG°=1.93 ...

The rate constant for electron transfer is predict...
Question: 18.10

The thermal decomposition reaction of nitrosyl halides is important in tropospheric chemistry. For example, consider the decomposition of NOCl:2 NOCl(g)→2 NO(g)+Cl2(g) The Arrhenius parameters for this reaction are A=1.00×10^13 M-¹ s-¹ and Ea=104.0 kJ mol-¹.Calculate ΔH and ΔS for this reaction ...

This is a bimolecular reaction such that \D...
Question: 19.3

Consider the following reaction of methane with molecular chlorine:CH4(g)+Cl2(g)→CH3CHcl(g)+HCl(g)Experimental studies have shown that the rate law for this reaction is one-half order with respect to Cl2. Is the following mechanism consistent with this behavior? Cl2→2Cl·Cl·+CH4→HCl+CH3·CH3·+Cl2→ ...

The rate of reaction in terms of product HC...
Question: 19.5

You are designing a FRET experiment to determine the magnitude of the structural change introduced by substrate binding to an enzyme. Using site specific mutagenesis, you have constructed a mutant form of the enzyme that possesses a single tyrosine residue and a single tryptophan residue, and ...

Using the initial separation distance and r...
Using Equation (19.171), a plot of \left(\t...