Version 058 Exam 4 Mccord (52450) This print-out should have 30 questions.

ns. Multiple-choice questions may continue on the next column or page nd all choices before answering. 001 10.0 points If an individual step in a reaction mechanism is bimolecular, is that step necessarily of second order? 1. Yes correct 2. No Explanation: The number of reactant molecules in an elementary step of a mechanism is the order of that step. 002 10.0 points You need that 2 in the calculation. For the reaction 2A B the concentration of [A] after 15 hours is 0.15 M. How much of compound [A] was initially present if k = 2.16 107 M/s? 1. 1.617 101 M 2. 7.32 102 M 3. 1.733 101 M correct 4. 1.504 101 M Explanation: 5. 1.535 101 M 003 10.0 points 3. 107.9 g 4. 53.9 g 5. 21.58 g 6. 0 g Explanation: This is a 2 electron process. g= Q(molar mass) nF (19.3 103 C)(107.9 g/mol) = (2)(9.65 104 C/mol) = 10.79 g 004 10.0 points

What is the potential in an electrolysis cell formed from the two half reactions below if the sodium ion concentration is 103 M and the aluminum ion concentration is 1M? Half reaction Na+ Na Al3+ Al 1. -1.18V correct 2. -1.0V 3. -0.82V 4. 1.18V 5. 1.0V 6. 0.82V Explanation: E = 1.0V Ecell = E cell 0.05916 log Q Ne [Al3+ ] 0.05916 log = 1.0 3 [Na+ ]3 0.05916 = 1.0 9 3 = 1.18 E 2.7V 1.7V

While electroplating a spoon with silver (molar mass = 107.9 g/mol) from an Ag2+ solution, 19.3 103 C of charge is used. By how much has the mass of the spoon increased? 1. 5.39 g 2. 10.79 g correct

Version 058 Exam 4 Mccord (52450) 005 10.0 points Which statement best describes the action of a catalyst? 1. It releases activation energy for a chemical reaction. 2. It changes the reactants necessary for a chemical reaction. 3. It raises the activation energy for a chemical reaction. 4. It lowers the activation energy for a chemical reaction. correct Explanation: 006 10.0 points 2A+ B 2C [CH4 ]3 rate3 = rate1 [CH4 ]1 y 3 5.0 10 1.0 = 2.5 103 0.5 y=1 007 The reaction 10.0 points

Consider the data below: [CH4 ] [O2 ] initial rate M M M s1 Exp 1 0.5 1.3 2.5 103 Exp 2 0.5 2.6 1.0 102 Exp 3 1.0 1.3 5.0 103 Which of the following is a correct rate law for the reaction? 1. k[CH4 ]1[O2 ]2 2. k[CH4 ][O2 ] correct 3. k[CH4 ] 4. k[CH4 ]1[O2 ] 5. k[CH4 ][O2 ] Explanation: [O2 ]1 rate1 = rate2 [O2 ]2 3 1.3 2.5 10 = 2 1.0 10 2.6 x=2
2

has a negative Hr ; a possible mechanism for this reaction is (1) 2 A D rapid equilibrium, K (2) D + B 2 C slow, k What is the reaction prole diagram for this reaction?

1.

Energy Energy

reactants

products Reaction progress

2.
x

products

reactants Reaction progress

Version 058 Exam 4 Mccord (52450)

3.

Energy

products

must be lower than that of the reactants. The rate-determining step has a higher energy barrier (hump) that the rst step. Since C is the only mode going via step 2, and it is the slowest step, this means that step 2 is the ratedetermining step of the reaction (no available alternative routes to product C).

Energy The reaction

reactants Reaction progress

Energy

reactants

4.

products

products Reaction progress 008 Consider the cell 10.0 points

reactants Reaction progress

In | In3+ (1 M) || Ru3+ (0.1 M) , Ru2+ (1 M)|Pt The potential (E) for this cell will be which of the following?

Energy

1. greater than E 0 reactants 2. Not enough information is given. 3. less than E 0 correct

5.

products Reaction progress

4. the same as E 0 Explanation: Net reaction is: In + 3Ru3+ In3+ + 3Ru2+ All substances are in standard state except the Ru3+ which has been lowered from standard state to 0.1 M. This will raise the value of Q above 1 and therefore LOWER the potential from the standard potential. 009 10.0 points

Energy

6.

reactants

correct

products Reaction progress Explanation: Since the overall reaction has a negative Hr , we know the energy of the products

N2 + 3 H2 2 NH3 is proceeding under conditions that 0.150 moles of NH3 are being formed every 20 sec-

Version 058 Exam 4 Mccord (52450) onds. What is the rate of disappearance of H2 ? 1. 7.5 103 moles/sec 2. 2.25 101 moles/sec 3. The question cannot be answered from the information given; we need to know the volume of the container. 4. 1.125 102 moles/sec correct 5. The question cannot be answered from the information given; we need to know the rate law for the reaction. Explanation: nNH3 = 0.150 mol t = 20 s The rate of appearance of NH3 is 1 [NH3 ] Rate = 2 t We can consider this to be 1 0.150 mol = 0.00375 mol/s 2 20 s 3. PbSO4 (s) 4. PbCl2 (s) 5. Pb-Ni(CO3 )2 (s) 6. PbO2 (s) correct

Explanation: PbO2 has lead in the +4 oxidation state. This will accept 2 electrons and thus be reduced to PbSO4 as the battery discharges. Pb metal is oxidized to PbSO4 . 011 10.0 points The 2 is needed in this calculation. Consider the reaction 2 NOCl(g) 2 NO(g) + Cl2 (g) with rate constant 0.0480 M1 s1 when conducted at 200 C. The initial concentration of NOCl was 0.521 M. What is the concentration of NOCl after 0.535 minutes and at 200 C? 1. 0.0239 M 2. 0.200 M correct 3. 0.508 M 4. 0.112 M 5. 0.289 M Explanation: k = 0.0480 M1 s1 t = 0.535 min [A]0 = 0.521 M The units on k indicates a second order reaction: 1 1 = akt [A]t [A]0 1 1 = +akt [A]t [A]0 1 = 0.521 M +2(0.0480 M1 s1 ) 60.0 s (0.535 min) min

Rate =

The rate of disappearance of H2 is 1 [H2 ] Rate = 3 t 1 [H2 ] 0.00375 mol/s = 3 t [H2 ] = 0.01125 mol/s t Thus H2 disappears at a rate of 1.125102 mol/s. 010 10.0 points Consider the lead storage battery and the chemical reaction that drives it forward on discharge. There are various substances present as reactants and products. Which of the following substances is reduced as the battery discharges. 1. Pb (s) 2. H2 SO4 (aq)

Version 058 Exam 4 Mccord (52450) = 5.00 M1 [A]t = 0.200 M 012 10.0 points A given reaction has an activation energy of 26.57 kJ/mol. At 25 C the half-life is 4 minutes. At what temperature will the half-life be reduced to 20 seconds? 1. 115 C correct 2. 59.9 C 3. 100.C 4. 25.5C 5. 1.19 C 6. 75.0C 7. 57.9C 8. 150 C 9. 125 C Explanation: Use the Arrhenius equation. The 20 second reaction is running 12 times that of the 240 240 reaction. Put that ratio = 12 in for 20 ka the ln term. Remember to use Kelvin kb for the temperatures. 013 10.0 points Consider the cell Pt | H2 (1 atm); H+ (? M) || Hg2 Cl2 (s); Cl (1 M) | Hg + 2 H + 2 e H2 E 0 = 0.00 V Hg2 Cl2 + 2 e 2 Hg + 2 Cl E 0 = 0.268 V If the measured cell potential for the cell is 0.39 volts, what is the pH of the solution? 1. 3.4 2. 4.12 1. k[CH3 Br] [HCl] [CH3 Cl]1 correct 2. k[CH3 Br] [HCl] 3. 2.07 correct 4. less than 1.00 5. 5.45

Explanation: [H+ ] is not known, likely not at 1 M (standard conditions). The second reaction is under standard conditions. So we know that: H2 2 H+ + 2 e E=? Hg2 Cl2 + 2 e 2 Hg + 2 Cl E = +0.268 V Ecell = +0.39 V E for the rst reaction must be 0.122 V. Use the Nernst equation to determine [H+ ]: 0.0592 [Red]y log n [Ox]x 1 0.0592 log 0.122 V = 0 V 2 x2 0.0592 0.0592 0.122 V = log(1) + log x2 2 2 0.0592 log x2 0.122 V = 0 + 2 4.12162 = log x2 x2 = 104.12162 x = 0.00869339 = [H+ ] pH = log[H+ ] = log(0.00869339) = 2.06081 E = E0 014 10.0 points

Consider the reaction mechanism below: Step 1 2 3 overall Reaction CH3 Br CH3 + + Br CH3 + + HCl CH3 Cl + H+ H+ + Br HBr CH3 Br + HCl CH3 Cl + HBr

If step 3 is the slow step what is the rate law?

Version 058 Exam 4 Mccord (52450) terms of the [SF6 ]. 3. k[CH3 Br] [HCl] [Br ] 4. k[CH3 Br] Explanation: The reactants that precede the slowest forward step will appear in the rate law for a reaction. 015 10.0 points For a given single step reaction the activation energy is 40 kJ and H = 60 kJ. The activation energy for the REVERSE reaction is 1. 0 kJ 2. 60 kJ 3. 40 kJ 4. 20 kJ 5. 100 kJ correct Explanation: forward Potential Energy 40 kJ 100 kJ 60 kJ reverse C+D A products
1

2 CH2S + 12 F2 C2 F4 + 4 HF + 2 SF6 [SF6 ] correct 2t [SF6 ] 2. rate = 2t 2[SF6 ] 3. rate = t [SF6 ] 4. rate = t 2[SF6 ] 5. rate = t Explanation: [CH2 S] rate = 2t [F2 ] = 12t [C2 F4 ] = t [HF] = 4t [SF6 ] = 2t 017 10.0 points A reaction 1. rate =

A+B

is observed to obey second-order kinetics. Which of the following choices would give a straight line plot where the slope equals the rate constant? 1 vs t correct [A] 2. [A] vs t 1. 3. [A] vs t 4. [A] vs 1 k

Reaction Coordinate For C and D to become A+B they need at least 60 kJ + 40 kJ = 100 kJ energy. 016 10.0 points

5. ln[A] vs t 6. ln[A] vs 1 k

Express the rate of the following reaction in

Version 058 Exam 4 Mccord (52450) 1 1 7. vs [A] t 8. ln[A] vs 1 t 4. 16 kJ/mol 5. 32 kJ/mol correct Explanation: T1 = 50 C + 273 = 323 K T2 = 70 C + 273 = 343 K ln k2 Ea = k1 R

k2 = 2 k1

9. ln[A] vs k Explanation: The integrated rate equation for a reaction obeying second order kinetics is 1 1 = akt [A] [A]0 1 should give you a straight Thus a plot of [A] line. 018 10.0 points A battery has two terminals labeled positive and negative. As the battery discharges, electrons ow from the ? terminal to the ? terminal through the external circuit and ? reaction occurs at the positive terminal. 1. positive; negative; an acid/base

1 1 T1 T2 k2 R ln k1 Ea = 1 1 T1 T2 (8.314 J/mol K) ln 2 = 1 1 323 K 343 K = 33.5 kJ/mol

020 10.0 points All else being equal, a reaction with a higher activation energy compared to one with a lower activation energy will 1. proceed faster.

2. postive; negative; an oxidation 2. proceed slower. correct 3. negative; positive; an oxidation 3. be more exothermic. 4. negative; positive; a reduction correct 4. be more endothermic. 5. positive; negative; a reduction Explanation: In a voltaic cell electrons ow from the negative to the positive terminals. Reduction occurs at the positive terminal. 019 10.0 points Suppose for some reaction the rate constant doubles in going from T = 50 C to 70 C. What is Ea for this reaction? 1. 40 kJ/mol 2. 24 kJ/mol 3. 8 kJ/mol 1. 0.766071 M 5. not be any dierent. Explanation: The larger the activation energy, the smaller the number of reactant particles that have the necessary energy and the slower the reaction. 021 10.0 points The rst order rate constant for A products is 7.7 s1 . If [A] = 1.8 M at t = 0, what is the value of [A] at t = 0.5 s?

Version 058 Exam 4 Mccord (52450) 2. 9.57588 10

6

k=

ln 2 , so t1/2 ln a (ln 2) t [A]0 = akt = [A]t t1/2 (ln 2)(400 s) = 603 s = 0.459799 [A]0 = 1.58376 [A]t [A]t 100% = 63.1% [A]0

3. 1.91518 105 M 4. 0.00766071 M 5. 0.0383035 M correct Explanation: [A] = 1.8 M t = 0.5 s 1 k = 7.7 s If the reaction is rst order, the integrated rate equation is [A]0 = akt [A] ln[A]0 ln[A] = a k t ln[A] = ln[A]0 a k t = ln(1.8 M) (1) 7.7 s1 (0.5 s) = 3.26221 M [A] = 0.0383035 M ln 022 10.0 points A certain rst-order reaction A products has a half life of 603 seconds. What percent of an initial amount of the reactant will remain unreacted after 400 seconds? 1. 61.1 2. 63.1 3. 66.1 4. 61.9 5. 67.9 6. 34.8 7. 65.1 8. 43.1 9. 58.2 10. 59.5 Correct answer: 63.1%. Explanation: a=1 t = 400 s t1/2 = t1/2 = 603 s =

and

023 10.0 points Yes, youll need that 2 in your calculation. Plus, a year (unit=y) is 365.25 days when you factor in for leap years. Consider the reaction at 25 C 2 NO2 2 NO + O2 The overall rxn rate = k[NO2 ]2 The rate constant, k = 1.4 1010 M1 s1 If 5 moles of NO2 are initially present in a sealed 1.00 liter vessel at 25 C, what is the half-life of the reaction? 1. 32.3348 2. 29.0184 3. 23.0963 4. 22.6343 5. 25.7209 6. 35.3662 7. 40.4185 8. 24.6026 9. 29.782 10. 25.1493 Correct answer: 22.6343 y. Explanation: a=2 k = 1.4 1010 M1 s1 [A]0 = 5 M For a second order reaction 1 1 a k [A]0 1 2 (1.4 1010 M1 s1 ) 1 5M

Version 058 Exam 4 Mccord (52450) = 7.14286 108 s 1y 365.25 d = 22.6343 y 1h 1d 3600 s 24 h

Remember, leap years account for there being 365.25 days in a year for extended years. 024 10.0 points Collision theory states that 1. reactions can occur even at absolute zero. 2. reaction intermediates can accumulate under the right conditions. 3. molecules must collide with sucient energy in order to react. correct 4. transition states are short-lived. Explanation: Collision theory states that molecules must collide with sucient energy and correct orientation in order to react and that both the frequency and energy of the collisions is directly proportional to systems temperature. 025 10.0 points Which of the following is NOT true concerning reaction mechanisms? 1. They can be analyzed mathematically to provide an expression for the overall rate. 2. They can generally be veried absolutely. correct 3. They are a set of elementary reaction steps. 4. They often involve a rate-determining step. 5. They are proposed on the basis of chemical interaction and experimental rate data. Explanation: A reaction mechanism is simply a proposed

series of elementary reactions which, when added together, give the equation for the reaction. It must be consistent with chemical knowledge of the various species and with the experimentally observed overall reaction rate. A rate-determining step may or may not be present. 026 10.0 points Why can the lead-acid batteries used in cars generate electricity for several years before running down (i.e., the battery is dead)? 1. These batteries are used only to generate the electricity that makes the rst spark plug spark. Therefore, they are hardly used at all when a car is started, and never when it is driven. 2. A lead-acid battery is so large that it holds large quantities of the chemicals whose electrochemical interaction creates the electricity. 3. The mechanical motion of the engine drives an alternator that generates electricity to recharge the battery. correct 4. The electrons they generate and not the chemical components provide most all of the electricity. Explanation: Lead-acid batteries are secondary cells. The battery is used when a car is started, which is why it recharges via the alternator when you drive, but it is also sometimes used when your A/C compressor cycles. 027 10.0 points For a reaction that is zero-order overall, 1. the reactant concentration does not change with time. 2. the activation energy is zero. 3. the rate does not change during the reaction. correct

Version 058 Exam 4 Mccord (52450) 4. the rate constant is zero. Explanation: Remember that for a zero order reaction, the reactant is still used up; its concentration will decrease as time passes, but the rate will not be aected. If you double or triple the concentration of that reactant, the rate will not change for a zero order reaction. 028 10.0 points A certain reaction (X Y) is run and the half-life is found to be 3.5 minutes. The same reaction is run again using half the original amount of reactant X and the half-life changed to 7.0 minutes. What is the order of this reaction? 1. You must run one more experiment before you can tell. 2. zero order 3. second order correct 1. 4 4. Half-lives are not indicators of order. 2. 1 5. rst order Explanation: For the rst reaction t1/2 1 = 3.5 min For the second reaction 1 [A]0 = [A]0 t1/2 = 7 min 2 [A]0 [A]01 = First run: t1/2 3.5 1 [A]01 [A]0 [A]0 Second run: = 2 = t1/2 3.5 14 [A]0 For zero order is a constant, so it is t1/2 not zero order. For rst order t1/2 is independent of [A0 ], so it is not rst order. For second order t1/2 [A0 ] is a constant. First run ([A0 ]1 )(t1/2 ) = 3.5[A]0 1 [A]0 (7.0) = 3.5[A]0 Second run 2 Therefore the rate is second order. 3. 5 4. 6 5. 3 6. 2 correct

10

029 10.0 points Which type of widely used battery is NOT rechargeable? 1. lithium-ion 2. lead-acid (storage batteries) 3. nickel-cadmium (NiCad) 4. alkaline correct Explanation: Alkaline batteries were not designed to be rechargeable and do not do so eciently, although there are some websites that disagree. 030 10.0 points When a ruthenium chloride solution was electrolyzed for 500 s with a 120 mA current, 31 mg of ruthenium was deposited. What is the oxidation number of ruthenium in ruthenium chloride?

Explanation: t = 500 s m = 31 mg = 0.031 g I = 120 mA = 0.12 A = 0.12 C/s F = 96485 C Run+ (aq) + n e Ru(s)

The amount of Ru is

nRu = (0.031 g Ru)

1 mol Ru 101.07 g Ru = 0.000306718 mol Ru . q =It

The total charge is

Version 058 Exam 4 Mccord (52450) = (0.12 C/s) (500 s) = 60 C .

11

n = (60 C) e

1 mol e 96485 C = 0.000621858 mol e .

n=

0.000621858 mol e 0.000306718 mol 2.02746 mol charge e . = 1 mol

Therefore, the oxidation number is +2; i.e., Ru2+ (aq) + 2 e Ru(s).