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chemistry
physical chemistry

General Chemistry 9th edition Darrell Ebbing, Steven D. Gammon - Solutions

List the four variables or factors that can affect the rate of reaction.
Compare the half-life equations for a first-order and a second-order reaction. For which reaction order is the value of the half-life independent of the reactant concentration?
Benzene diazonium chloride, C6H5NNCl, decomposes by a first-order rate law. C6H5NNCl ±£ C6H5Cl+ N2(g) If the rate constant at 20oC is 4.3 × 105/s, how long will it take for 75% of the compound to decompose?
What is the half-life of methyl acetate at 25oC in the acidic solution described in Problem 13.99?
What is the half-life of benzene diazonium chloride at 20oC? See Problem 13.98 for data.
A compound decomposes by a first-order reaction. If the concentration of the compound is 0.0250 M after 65 s when the initial concentration was 0.0350 M, what is the concentration of the compound after 88 s?
A compound decomposes by a first-order reaction. The concentration of compound decreases from 0.1180 M to 0.0950 M in 5.2 min. What fraction of the compound remains after 7.1 min?
Butadiene can undergo the following reaction to form a dimer (two butadiene molecules hooked together). 2C4H8(g) → C8H12(g) The half-life for the reaction at a given temperature is 5.92 × 102 s. The reaction is second order. a. If the initial concentration of C4H8 is 0.50 M, what is the rate
A plot of 1/[A] versus time for the hypothetical reaction A→ B+ C yields a straight line. a. What is the order of the reaction? b. If it took 57 s for the concentration to drop 40 percent from its initial value of 0.50 M, what is the rate constant for the reaction?
At 330oC, the rate constant for the decomposition of NO2 is 0.775 L/(mol∙s). If the reaction is second order, what is the concentration of NO2 after 2.5 × 102 seconds if the starting concentration was 0.050 M? What is the half-life of this reaction under these conditions?
A second-order decomposition reaction run at 550oC has a rate constant of 3.1 × 102 L/(mol∙s). If the initial concentration of the reactant is 0.10 M, what is the concentration of this reactant after 1.0 × 102 s? What is the half-life of this reaction under these conditions?
Plot the data given in Problem 13.95 to verify that the decomposition of azomethane is first order. Determine the rate constant from the slope of the straight-line plot of log [CH3NNCH3] versus time.
What two factors determine whether a collision between two reactant molecules will result in reaction?
The decomposition of aqueous hydrogen peroxide in a given concentration of catalyst yielded the following data:Verify that the reaction is first order. Determine the rate constant for the decomposition of H2O2 (in units of /s) from the slope of the straight-line plot of ln [H2O2] versus time.
In the presence of a tungsten catalyst at high temperatures, the decomposition of ammonia to nitrogen and hydrogen is a zero-order process. If the rate constant at a particular temperature is 3.7 × 106 mol/(L∙s), how long will it take for the ammonia concentration to drop from an initial
The reaction 2B → C + 2D is found to be zero-order when run at 990oC. If it takes 3.3 × 102 s for an initial concentration of B to go from 0.50 M to 0.20 M, what is the rate constant for the reaction? What is the half-life of the reaction under these conditions?
The decomposition of nitrogen dioxide, 2NO2(g) → 2NO(g)+ O2(g) has a rate constant of 0.498 M/s at 319oC and a rate constant of 1.81 M/s at 354oC. What are the values of the activation energy and the frequency factor for this reaction? What is the rate constant at 420oC?
A second-order reaction has a rate constant of 8.7 × 104/(M∙s) at 30oC. At 40oC, the rate constant is 1.8 × 103/(Ms). What are the activation energy and frequency factor for this reaction? Predict the value of the rate constant at 45oC.
Urea, (NH2)2CO, can be prepared by heating ammonium cyanate, NH4OCN.NH4OCN †’ (NH2)2COThis reaction may occur by the following mechanism:What is the rate law predicted by this mechanism?
Sketch a potential-energy diagram for the exothermic, elementary reaction A+ B→ C + D and on it denote the activation energies for the forward and reverse reactions. Also indicate the reactants, products, and activated complex.
Acetone reacts with iodine in acidic aqueous solution to give monoiodoacetone. A possible mechanism for this reaction is Write the rate law that you derive from this mechanism.
A study of the gas-phase oxidation of nitrogen monoxide at 25oC and 1.00 atm pressure gave the following results:2NO(g)+ O2(g) †’ NO2(g)a. What is the experimental rate law for the reaction above? b. What is the initial rate of the reaction in Experiment 4?
The reaction of water with CH3Cl in acetone as a solvent is represented by the equation CH3Cl H2O → CH3OH + HCl The rate of the reaction doubles when the concentration of CH3Cl is doubled and it quadruples when the concentration of H2O is doubled. a. What is the unit for k? b. Calculate k if
The reaction of thioacetamide with water is shown by the equation below: CH3C(S)NH2(aq)+ H2O → H2S(aq) + CH3C(O)NH2(aq) The rate of reaction is given by the rate law: Rate = k[H3O+][CH3C(S)NH2]
The reaction of methylacetate with water is shown by the equation below:CH3COOCH3(aq) + H2O → CH3COOH(aq) + CH3OH(aq)The rate of the reaction is given by the rate law:Rate = k[H3O+][CH3COOCH3]
Draw a potential-energy diagram for an uncatalyzed exothermic reaction. On the same diagram, indicate the change that results on the addition of a catalyst. Discuss the role of a catalyst in changing the rate of reaction.
Draw and label the potential-energy curve for the reactionThe activation energy for the reverse reaction is 23 kJ. Î”H and Ea on the diagram. What is the activation energy for the forward reaction? For which reaction (forward or reverse) will the reaction rate be most sensitive to a
What is meant by the term rate of a chemical reaction? Why does the rate of a reaction normally change with time? When does the rate of a chemical reaction equal the rate constant?
Briefly discuss the factors that affect the rates of chemical reactions. Which of the factors affect the magnitude of the rate constant? Which factor(s) do not affect the magnitude of the rate constant? Why?
Describe in general terms how chemists can follow the character of a reacting molecule using lasers.
Draw a structural formula for the activated complex in the following reaction:NO2+ NO3 → NO + NO2+ O2Refer to Figure 13.16, Step 2, for details of this reaction. Use dashed lines for bonds about to form or break. Use a single line for all other bonds.
Describe the potential-energy curve for the decomposition of cyclobutane to ethylene.
The rate constant for a certain reaction is 1.4 × 1005 M1 min1 at 483 K. The activation energy for the reaction is 2.11 × 1003 J/mol. What is the rate constant for the reaction at 611 K?
The decomposition of hydrogen peroxide is a first-order reaction:H2O2(aq) → H2O(l) + 1 / 2 O2(g)The half-life of the reaction is 17.0 minutes.a. What is the rate constant of the reaction?b. If you had a bottle of H2O2, how long would it take for 86.0% to decompose?c. If you started the reaction
A reaction of the form aA → Products is second order with a half-life of 307 s. What is the rate constant of the reaction if the initial concentration of A is 1.87 × 1002 mol/L?
A possible mechanism for a gas-phase reaction is given below. What is the rate law predicted by this mechanism?
Say you run the following elementary, termolecular reaction:2A+ B → DUsing the starting concentrations [A] = 2.0 M and [B] = 1.0 M, you measure the rate to be 16 M2∙s1. What is the value of the rate constant?
The hypothetical reaction A + 2B → Products has the rate law Rate = k[A]2[B]3. If the reaction is run two separate times, holding the concentration of A constant while doubling the concentration of B from one run to the next, how would the rate of the second run compare to the rate of the first
For the decomposition of one mole of nitrosyl chloride, ΔH = 38 kJ. NOCl(g) → NO(g) + 1 / 2 Cl2(g) The activation energy for this reaction is 100 kJ. a. Is this reaction exothermic or endothermic? b. What is the activation energy for the reverse reaction? c. If a catalyst were added to the
Given the following mechanism for a chemical reaction: H2O2+ I → H2O + IO H2O2+ IO → H2O + O2 + I a. Write the overall reaction. b. Identify the catalyst and the reaction intermediate. c. With the information given in this problem, can you write the rate law? Explain.
Rate constants for reactions often follow the Arrhenius equation. Write this equation and then identify each term in it with the corresponding factor or factors from collision theory. Give a physical interpretation of each of those factors.
The following data were collected for the reaction A(g) + B(g) †’ Products.a. Determine the rate law for this reaction. b. Calculate the rate constant. c. Calculate the rate when [A] = 0.200 M and [B] = 0.200 M. from the decomposition reaction of 1.00 mol H2O2 at 25oC and 740 mmHg after
Dinitrogen pentoxide, N2O5, undergoes first-order decomposition in chloroform solvent to yield NO2 and O2. The rate constant at 45oC is 6.2 × 104/min. Calculate the volume of O2 obtained from the reaction of 1.00 mol N2O5 at 45oC and 770 mmHg after 20.0 hr.
Hydrogen peroxide undergoes a first-order decomposition to water and O2 in aqueous solution. The rate constant at 25oC is 7.40× 104/s. Calculate the volume of O2 obtained from the decomposition reaction of 1.00 mol H2O2 at 25oC and 740 mmHg after 20.0 min.
Hydrogen peroxide in aqueous solution decomposes by a first-order reaction to water and oxygen. The rate constant for this decomposition is 7.40 × 104/s. What quantity of heat energy is initially liberated per second from 2.00 L of solution that is 1.50 M H2O2? See Appendix C for data.
Nitrogen dioxide reacts with carbon monoxide by the overall equation NO2(g)+ CO(g) → NO(g) + CO2(g) At a particular temperature, the reaction is second order in NO2 and zero order in CO. The rate constant is 0.515 L/(mols). How much heat energy evolves per second initially from 3.50 L of
Nitrogen monoxide reacts with oxygen to give nitrogen dioxide. 2NO(g)+O2(g) → 2NO2(g) The rate law is Δ[NO]/ Δt = k[NO]2[O2], where the rate constant is 1.16 × 105 L2/(mol2∙s) at 339oC. A vessel contains NO and O2 at 339oC. The initial partial pressures of NO and O2 are 155 mmHg and 345
Nitrogen monoxide reacts with hydrogen as follows: 2NO(g)+ H2(g) → N2O(g) + H2O(g) The rate law is Δ[H2]/ Δt = k[NO]2[H2], where k is 1.10 × 107 L2/(mol2∙s) at 826oC. A vessel contains NO and H2 at 826oC. The partial pressures of NO and H2 are 144 mmHg and 324 mmHg, respectively. What is
By means of an example, explain what is meant by the term reaction intermediate.
Why is it generally impossible to predict the rate law for a reaction on the basis of the chemical equation only?
The rate law for the reaction 2NO2Cl(g) → 2NO2(g)+ Cl2(g) (overall equation) is first order in nitryl chloride, NO2Cl. Rate = k[NO2Cl] Explain why the mechanism for this reaction cannot be the single elementary reaction 2NO2Cl → 2NO2 + Cl2 (elementary reaction)
There is often one step in a reaction mechanism that is rate-determining. What characteristic of such a step makes it rate-determining? Explain.
The dissociation of N2O4 into NO2,is believed to occur in one step. Obtain the concentration of N2O4 in terms of the concentration of NO2 and the rate constants for the forward and reverse reactions, when the reactions have come to equilibrium.
Define the rate of reaction of HBr in the following reaction. How is this related to the rate of formation of Br2? 4HBr(g) + O2(g) → 2Br2(g) + 2H2O(g)
How does a catalyst speed up a reaction? How can a catalyst be involved in a reaction without being consumed by it?
Describe the steps in the catalytic hydrogenation of ethylene.
Consider the reaction E + F †’ G + H, which has the following reaction coordinate diagram.Which one of the following statements is true? a. The activation energy is greatest for the forward reaction. b. The reactants are at a lower energy than the products. c. The reaction is
Consider the hypothetical reaction A(g) + 2B(g) †’ C(g). The four containers below represent this reaction being run with different initial amounts of A and B. Assume that the volume of each container is 1.0 L. The reaction is second order with respect to A and first order with respect to
You and a friend are working together in order to obtain as much kinetic information as possible about the reaction A(g) †’ B(g) + C(g). One thing you know before performing the experiments is that the reaction is zero order, first order, or second order with respect to A. Your friend
Consider the reaction 3A → 2B + C. a. One rate expression for the reaction is Rate of formation of C = + Δ[C] / Δt Write two other rate expressions for this reaction in this form b. Using your two rate expressions, if you calculated the average rate of the reaction over the same time interval,
Give at least two physical properties that might be used to determine the rate of a reaction.
The reaction 2A(g) †’A2(g) is being run in each of thefollowing containers. The reaction is found to be second-orderwith respect to A.a. Write the rate law for the reaction. b. Which reaction container will have a greater reaction rate? c. In which container will the reaction have a
When viewed from a molecular perspective, a particular reaction is written asa. If the reaction is first-order with a half-life of 10 seconds, complete the following pictures after 10 and 20 seconds have elapsed. b. How would the pictures from part a change if the reaction were second-order with
You perform some experiments for the reaction A → B + C and determine the rate law has the form Rate = k[A]x Calculate the value of exponent x for each of the following. a. [A] is tripled and you observe no rate change. b. [A] is doubled and the rate doubles. c. [A] is tripled and the rate goes
A friend of yours runs a reaction and generates the following plot. She explains that in following the reaction, she measured the concentration of a compound that she calls €œE.€a. Your friend tells you that E is either a reactant or a product. Which is it and why? b. Is the
Given the hypothetical plot shown here for the concentration of compound Y versus time, answer the following questions.a. In which region of the curve does the rate have a constant value (A, B, or C)? b. In which region of the curve is the rate the fastest (A, B, or C)?
You are running the reaction 2A + B †’ C + 3D. Your lab partner has conducted the first two experiments to determine the rate law for the reaction. He has recorded the initial rates for these experiments in another data table. Come up with some reactant concentrations for Experiment 3
The chemical reaction A → B + C has a rate constant that obeys the Arrhenius equation. Predict what happens to both the rate constant k and the rate of the reaction if the following were to occur. a. a decrease in temperature b. an increase in the activation energy of the forward and reverse
Relate the rate of decomposition of NO2 to the rate of formation of O2 for the following reaction: 2NO2(g) → 2NO(g) + O2(g)
A rate of reaction depends on four variables (Question 13.1). Explain by means of an example how the rate law deals with each of these variables.
For the reaction of hydrogen with iodine H2(g)+ I2(g)→ 2HI(g) relate the rate of disappearance of hydrogen gas to the rate of formation of hydrogen iodide.
To obtain the rate of the reaction 5Br(aq) + BrO3 (aq) + 6H+(aq) → 3Br2(aq) + 3H2O(l) you might follow the Brconcentration or the BrO3 concentration. How are the rates in terms of these species related?
To obtain the rate of the reaction 3I(aq) + H3AsO4(aq) + 2H+(aq) → I3(aq) + H3AsO3(aq) + H2O(l ) you might follow the I concentration or the I3 concentration. How are the rates in terms of these species related?
Ammonium nitrite, NH4NO2, decomposes in solution, as shown here. NH4NO2(aq) → N2(g) + 2H2O(l ) The concentration of NH4+ ion at the beginning of an experiment was 0.500 M. After 3.00 hours, it was 0.432 M. What is the average rate of decomposition of NH4NO2 in this time interval?
Iron(III) chloride is reduced by tin(II) chloride. 2FeCl3(aq) + SnCl2(aq) →2FeCl2(aq) + SnCl4(aq) The concentration of Fe3+ ion at the beginning of an experiment was 0.03586 M. After 4.00 min, it was 0.02638 M. What is the average rate of reaction of FeCl3 in this time interval?
Azomethane, CH3NNCH3, decomposes according to the following equation: CH3NNCH3(g) → C2H6(g)+ N2(g) The initial concentration of azomethane was 1.50 × 102 mol/L. After 7.00 min, this concentration decreased to 1.01 × 102 mol/L. Obtain the average rate of reaction during this time interval.
Nitrogen dioxide, NO2, decomposes upon heating to form nitric oxide and oxygen according to the following equation: 2NO2(g) → 2NO(g) + O2(g) At the beginning of an experiment, the concentration of nitrogen dioxide in a reaction vessel was 0.1103 mol/L. After 60.0 s, the concentration decreased to
Hydrogen sulfide is oxidized by chlorine in aqueous solution. H2S(aq) + Cl2(aq) → S(s) + 2HCl(aq) The experimental rate law is Rate = k[H2S][Cl2] What is the reaction order with respect to H2S? with respect to Cl2? What is the overall order?
For the reaction of nitrogen monoxide, NO, with chlorine, Cl2, 2NO(g) + Cl2(g) → 2NOCl(g) the observed rate law is Rate = k[NO]2[Cl2] What is the reaction order with respect to nitrogen monoxide? with respect to Cl2? What is the overall order?
Oxalic acid, H2C2O4, is oxidized by permanganate ion to CO2 and H2O. 2MnO4 (aq) + 5H2C2O4(aq) + 6H+(aq) → 2Mn2+(aq) + 10CO2(g) + 8H2O(l ) The rate law is Rate = k[MnO4 ][H2C2O4] What is the order with respect to each reactant? What is the overall order?
The exponents in a rate law have no relationship to the coefficients in the overall balanced equation for the reaction. Give an example of a balanced equation and the rate law for a reaction that clearly demonstrates this.
Iron(II) ion is oxidized by hydrogen peroxide in acidic
In experiments on the decomposition of azomethane,CH3NNCH3(g) †’ C2H6(g) + N2(g) the following data were obtained: What is the rate law? What is the value of the rate constant?
Ethylene oxide, C2H4O, decomposes when heated to give methane and carbon monoxide.C2H4O(g) †’ CH4(g) + CO(g) The following kinetic data were observed for the reaction at 688 K: Find the rate law and the value of the rate constant for this reaction.
Nitrogen monoxide, NO, reacts with hydrogen to give nitrous oxide, N2O, and water.2NO(g) + H2(g) †’ N2O(g) + H2O(g)In a series of experiments, the following initial rates of disappearance of NO were obtained:Find the rate law and the value of the rate constant for the reaction of NO.
In a kinetic study of the reaction2NO(g) + O2(g) †’ 2NO2(g)the following data were obtained for the initial rates of disappearance of NO:Obtain the rate law. What is the value of the rate constant?
Chlorine dioxide, ClO2, is a reddish-yellow gas that is soluble in water. In basic solution it gives ClO3 and ClO2 ions. 2ClO2(aq) 2OH(aq) → ClO3(aq) + ClO2 (aq) + H2O To obtain the rate law for this reaction, the following experiments were run and, for each, the initial rate of reaction
Iodide ion is oxidized to hypoiodite ion, IO, by hypochlorite ion, ClO, in basic solution. The equation is The following initial-rate experiments were run and, for each, the initial rate of formation of IO was determined. Find the rate law and the value of the rate constant.
Sulfuryl chloride, SO2Cl2, decomposes when heated. SO2Cl2(g) → SO2(g) + Cl2(g) In an experiment, the initial concentration of SO2Cl2 was 0.0248 mol/L. If the rate constant is 2.2 × 105/s, what is the concentration of SO2Cl2 after 2.0 hr? The reaction is first order.
Cyclopropane, C3H6, is converted to its isomer propylene, CH2PCHCH3, when heated. The rate law is first order in cyclopropane, and the rate constant is 6.0 × 104/s at 500oC. If the initial concentration of cyclopropane is 0.0226 mol/L, what is the concentration after 899 s?
A reaction of the form aA → Products is second-order with a rate constant of 0.225 L/(mol∙s). If the initial concentration of A is 0.293 mol/L, what is the molar concentration of A after 35.4 s?
The reaction 3I(aq) + H3AsO4(aq) + 2H+(aq) → I3(aq) + H3AsO3(aq) + H2O(l) is found to be first order with respect to each of the reactants. Write the rate law. What is the overall order?
A reaction of the form aA → Products is second order with a rate constant of 0.169 L/(mol∙s). If the initial concentration of A is 0.159 mol/L, how many seconds would it take for the concentration of A to decrease to 6.07 × 103 mol/L?
Ethyl chloride, CH3CH2Cl, used to produce tetraethyllead gasoline additive, decomposes, when heated, to give ethylene and hydrogen chloride.CH3CH2Cl(g) †’ C2H4(g) + HCl(g) The reaction is first order. In an experiment, the initial concentration of ethyl chloride was 0.00100 M. After
Cyclobutane, C4H8, consisting of molecules in which four carbon atoms form a ring, decomposes, when heated, to give ethylene.C4H8(g) †’ 2C2H4(g) The reaction is first order. In an experiment, the initial concentration of cyclobutane was 0.00150 M. After heating at 450oC for 455 s, this
Methyl isocyanide, CH3NC, isomerizes, when heated, to give acetonitrile (methyl cyanide), CH3CN. CH3NC(g) → CH3CN(g) The reaction is first order. At 230oC, the rate constant for the isomerization is 6.3 × 104/s. What is the half-life? How long would it take for the concentration of CH3NC to
Dinitrogen pentoxide, N2O5, decomposes when heated in carbon tetrachloride solvent. N2O5 → 2NO2 + 1/2 O2(g) If the rate constant for the decomposition of N2O5 is 6.2 × 104/min, what is the half-life? (The rate law is first order in N2O5.) How long would it take for the concentration of N2O5 to
In the presence of excess thiocyanate ion, SCN, the following reaction is first order in chromium(III) ion, Cr3+; the rate constant is 2.0 × 106/s. Cr3+(aq) + SCN(aq) → Cr(SCN)2+(aq) What is the half-life in hours? How many hours would be required for the initial concentration of Cr3+ to
In the presence of excess thiocyanate ion, SCN, the following reaction is first order in iron(III) ion, Fe3+; the rate constant is 1.27/s. Fe3+(aq) + SCN(aq) → Fe(SCN)2+(aq) What is the half-life in seconds? How many seconds would be required for the initial concentration of Fe3+ to decrease to
A reaction of the form aA → Products is second order with a rate constant of 0.413 L/(mol∙s). What is the half-life, in seconds, of the reaction if the initial concentration of A is 5.25 × 103 mol/L?

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