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chemistry
physical chemistry

Questions and Answers of Physical Chemistry

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
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
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.
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
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
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
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
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 ×
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
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
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?
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,
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
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
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
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
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
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
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
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
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
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
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.
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
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] =
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
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
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
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
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
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
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
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,
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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?
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?
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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

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