Answer Key

Chapter 1 2. a) i) 0.714 g/min ii) 0.172 g NO2/min iii) 0.0150 mol

HNO3/min
Page 3, Quick Check b) i) 840. mL ii) 0.450 mol/L
a) Rate of decomposition of SO2Cl2. c)
b) The slope becomes less and less steep. • Δ Conc HNO3 by Titration using Buret, Flasks, Magnetic
c) The rate decreases as the reaction proceeds. Mixer in M HNO3/s to measure Vf and Vi
d) -0.00023 mol/L/s (or +) • Δ Mass Cu by Balance to measure mf and mi in units of
e) Rate is greater at 300 s than at 500 s. g Cu/s
f) Find the slope of a tangent drawn to the curve • Δ Pressure NO2 by Manometer in closed system to
at that time. measure Pf and Pi in units of kPa/s NO2
g) 500 s: 09.2 x 10-5 M/s < 300 s: = 2.1 x 10-4 M/s • Δ Volume NO2 by Eudiometer to measure Vf and Vi in
units of mL/sNO2
Page 6, Practice Problems 1.1.1 • Δ pH by pH meter to measure change in pH of HNO3
1. a) mass of Cu or mass of Ag, [Cu(NO3)2] or [AgNO3], per second
blue colour of Cu(NO3)2 • Δ Mass of NO2 gas by Balance to measure mi and mf in
b) pressure of entire closed system will increase or units of g/s
green colour of chlorine gas • Δ Conc CuNO3 by Titration using buret, etc to find Vf
c) volume or mass of carbon dioxide gas or increased and Vi in M/s
partial pressure of CO2 (in a closed system). 3.a)i) approx 32 mL/min
d) mass of BaSO4 ppt formed, [either reactant], ii) approx 16 mL/min
conductivity as ions are consumed iii) approx 3.3 mL/min
2. Volume change is generally associated with the b) (a) > (b) > (c) As the reaction proceeds there are
formation of a gas. less reactant particles available to collide and react.
3. Concentration change is associated with the Consequently, the rate decreases with time.
formation or use of an aqueous species or a gas, not a 4. a)1.29 x 10-4 mol/s
solid or a liquid (except in the rare case of solid or b) The [HCl] was decreasing. This led to less
liquid mixtures). successful collisions.
c) One of the reactants (either the Sr disk or the HCl
Page 8, Practice Problems 1.1.2 in solution) was completely consumed. Based on
1. a) 0.0292 g/min the reaction rate, the Sr disk was most likely the
b) Rate is greatest at the beginning limiting reagent. The rate implies a reasonably large
c) Rate = 0 g/min in the last increment molarity of HCl.
d) This is because the HCl is all gone (limiting). Excess 5.
Zn left. Time Absorbances Concentration of
2. 2.55 x 10-4 mol/L/s (seconds) (no unit) Copper(II) Ion (mol/L)
0s 0 0 mol/L
Page 9, Practice Problems 1.1.3
20. 0.40 0.017
1. 5.1 x 1025 molecules/L
40. 0.70 0.030
2. 4.02 min
60. 0.90 0.038
3. 52.5 s
80. 1.00 0.042
Page 11, 1.1 Review Questions a) 0.0014M HNO3/s
1. - The distance-time graph involves a vehicle changing b) 0.67 g
position, while the rest of the data in this section c) Cu(s) will decrease in size
involves a property of a chemical changing during a Blue Cu2+(aq) will appear
chemical reaction. Bubbles will be seen as gas forms
- The vehicle accelerates and then decelerates, while This is a very exothermic reaction so heat (and
most reactions start at a maximum rate and decrease potentially some steam) will be given off
rate the entire time. (Colourless NO(g) reacts immediately with oxygen in the
- The vehicle can stop moving entirely and then begin air to form brownish orange NO2(g) or its dimer, N2O4(g)
again. Once a reaction begins, it continues until it is which is also brownish orange.)
finished.

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Page 22, 1.2 Review Questions Page 25, Quick Check
1. Factors affecting heterogeneous and homogeneous 1. Rate = k[C][D]. This means that the rate of the
reactions: reaction is directly related to the product of the
Nature of reactants concentrations of reactants C and D. Furthermore, it
Temperature means the reaction is 1st order with respect to both
Concentration reactants C and D.
Presence of a catalyst (The overall reaction order = 1 + 1 = 2.)
2. Surface Area. You can only increase this area of 2. a) The rate would double. b) The rate would half.
contact for solids and rarely, liquids. 3. If the volume of the container were halved, the
3. a) Platinum in the catalytic converter of a car. concentrations of both A and B would be doubled.
b) Iron is used in the Haber Process to make Hence, the rate would be increased by a factor
ammonia. of 2 x 2 = 4 times.
c) Platinum is used in contact lens disinfectant disks 4. Increased T à Increased Rate. Increased T must cause
to decompose hydrogen peroxide producing oxygen increased rate constant, k.
gas. The bubbling process helps clean the surface of
the lenses. Page 27, Quick Check
d) A Magnesium Complex called Chlorophyll assists in 1. Concentration (Volume of a Gas Sample), Surface
photosynthesis. Area, Temperature
4. CaCO3(s) + 2 HNO3(aq) à Ca(NO3)2(aq) + H2O(l) + 2. Temperature, Presence of a Catalyst
CO2(g) 3. Temperature
a) Increase – more frequent contact between
reactants Page 29, Practice Problems 1.3.1
b) Increase – more surface area leads to more contact 1. a) The added curve should have the same total area
between reactants below it. The area below the curve and to the right of
c) Decrease – less energetic collisions due to lower the vertical line representing Ea should be DOUBLED.
temperature b) The added curve should have the same total area
d) no effect – CO2 is a product so increased contact below it. The area below the curve and to the right of
has no effect on forward rate the vertical line representing Ea should be
5. 3.57 x 10-3 mol HCOOH/min SIGNIFICANTLY INCREASED.
a) Less than half as much time (rxn most rapid a start) c) The added curve should have the same total area
– under 30 seconds. below it. The area below the curve and to the right of
b) Considerably more time – much > 1 minute. the vertical line representing Ea should be INCREASED
c) Approximately half as much time for each 10oC BUT CLEARLY LESS THAN DOUBLE THAT IN CURVE (b).
increase – about 30 seconds.
6. a) i) slow (due to solid C)
ii) fast (ionic species)
iii) slow (due to solid Mg)
Fastest: (ii) > (iii) > (i) Slowest
b) i) surface area of C(s), temperature of system, [O2]
(volume of container) (partial pressure of O2), an
appropriate catalyst
ii) [Pb3+] and [I-], temperature of system, an
appropriate catalyst
iii) [CuCl2], surface area of Mg(s), temperature of
system, an appropriate catalyst
7. c > b > a
The greatest opportunity for contact between
reactant particles is in system c. It appears to have the
highest concentration/greatest partial pressure of
each reactant gas. The next would be system b and
the least opportunity would be system a.

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2.
Temperature 100oC 300oC 6. III > I > II The powdered zinc allows for the greatest
Frequency of 2.00 x 1015 s-1 3.00 x 1015 s-1 contact at the surface and the 1.0M acid has the
Collisions greatest number of particles available for collisions.
Force of Collisions 7. The Cl atoms must be able to contact one another to
(% Possessing Ea) 95.0% 97.0% produce Cl2 and NO2. The particles must be drawn to
Frequency of 1.90 x 1015 s-1 2.91 x 1015 s-1 allow this contact to directly occur.
Collisions 8. a) Low temperatures decrease the frequency of
Possessing Activation collisions and decrease the fraction of collisions
Energy reaching Ea. This keeps the food from spoiling.
a) 97.0% = 1.02X greater b) Fine bits of magnesium in the shavings (more
95.0% surface area) allow more frequent collisions with the
b) 3.00 x 1015 s-1 = 1.50X greater oxygen molecules. This allows a fire to start more
2.00 x 1015 s-1 readily. Its “nature” allows magnesium to react readily
c) 2.91 x 1015 s-1 = 1.53X greater with oxygen with a low Ea.
1.90 x 1015 s-1 c) Pt acts as a catalyst in the conversion of NOx’s into
d) Increased frequency of collisions. N2. This means the collisions required for a successful
e) Extremely forceful collisions may be too forceful to reaction can occur with less energy or at lower
transfer KE of collisions into PE of new bonds. These temperatures.
forceful collisions may be unsuccessful resulting in
reactants that simply bounce off one another. Page 40, Practice Problems 1.4.1
1. Rate = k[NO][O2] Trial 1 = X x 106 l/mol . sec
Page 33, 1.3 Review Questions 2. Rate = k[Y]
1. The frequency of collisions and the fraction of these 𝑘 =  0.0070  𝑠 !!
collisions that succeed. 3. System 1: System 2: System 3:
2. Sufficient energy (Ea) and proper collision geometry.
3. a) Original surface area + 6/6(original surface area) ¢ n n ¢ n n
since six new faces have been exposed. Thus 6.00 cm2 n ¢ ¢
+ 6/6(6.00 cm2) = 12.0 cm2.
b) 6/6 + 6/6 = 12/6 or 2X as many collisions as before.
¢ n ¢ ¢
c) 2 (0.00120 mol Zn/min) = 0.00240 mol Zn/min ¢ n ¢ n¢ n n
d) 242 mL H2 n ¢ n n
4. a) 3 x 0.5 x (3.10 x 10-3 mol/L s) = 4.65 x 10-3 mol/L s ¢ ¢ ¢ ¢ n n
b) 1 x 4 x (3.10 x 10-3 mol/L s) = 1.24 x 10-2 mol/L s
c) The temperature was increased, perhaps by
approximately 10oC. Or a catalyst was added.
¢ n
d) 0.5 x 0.5 (3.10 x 10-3 mol/L s) = 7.75 x 10-4 mol/L s Rate = 0.010 mol/L/s 0.020 mol/L/s 0.080 mol/L/s
(note that both concentrations were halved)
5. a) The greatest concentration of HCl and the greatest Page 42, 1.4 Review Questions
surface area of CaCO3 exists at the beginning of the 1. a) Rate = k[X]2[Y]
reaction. Consequently, the reaction rate is greatest at b) k =  80  L!/mol!/s
the beginning as these circumstances allow for more c) Rate = 0.4 mol/L/s
successful collisions. As the reaction proceeds, there 2. a) Rate = k[NO2][F2]
are less particles and surface available to collide and b) k =  40.0  L/mol/s
so the reaction rate decreases. 3. a) Rate = k[MnO4-]2[H2C2O4]
b) k =  2.0  ×  10!  L!/mol!/
b) If all the concentrations of all three reactants were
doubled, the initial reaction rate would be: (2)2(2)1(2)0
= 8x.
c) If the volume of the reaction system were doubled
by adding distilled water, the reaction rate would be:
(½)2(½)1(½)0 = 1/8x.
4. a) Rate = k[A]2
b) k =  4.00  ×  10!!  L/mol/s
c) Trial 4: Rate = 3.60 × 10-4 mol/L/s
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 b) i) If the initial concentration of NO2 increased, the
5. a) Rate = k[MnO4-]2 reciprocal concentration would decrease, shifting the
b) k =  1.0 × 102  L/mol/min straight line graph down.
c) Rate = 1.0 × 10-5 mol/L/min ii) If the temperature of the decomposition were
d) MnO! ! =  4.8 × 10-4  mol/L elevated further, the slope (k) of the straight line
e) 5.2  ×  10!!  mol/L/min  MnO! ! graph would become steeper (k increases as
6. Rate = k[CH3COCH3] [H+] temperature raises).
k =  0.0038  L/mol/s
Page 56, Practice Problems 1.5.4
Page 48, Practice Problems 1.5.1 1. a) t!/! =  4.6×10!  s           770  min  (13  h)
1. 𝑘 = 2.57  ×  10!! 𝑠 !! b) C =  0.094  mol/L            (0.09  mol/L)
2. C =  0.982  mol/L          (0.98  mol/L) 2. a) k =  5.8  ×  10!!  s !!
3. C =  2.16  ×  10!!  mol/L            (2.2  ×  10!!  mol/L) b) C =  0.038  mol/L          (0.04  mol/L)
c) t = 1.0  ×  10!  s
Page 49, Practice Problems 1.5.2 Page 58, Practice Problems 1.5.5
1. t = 2900  s (48 min) 1. a) t!/! = 126  s
2. Mass =  140  mg !
b) = 39.9  L/mol
3. t = 24  h !
C = 2.51  ×  10!!  mol/L
2. If the half-life of a reaction is independent of the
Page 53, Practice Problems 1.5.3
initial concentration of the reactants, then the
1. Pseudo integrated rate analysis
reaction is first order.
Tim Concentratio ln 1/Concentrati
e (s) n (mol/L) Concentratio on (L/mol)
Page 60, 1.5 Review Questions
n
1.
0 0.100 - 2.30 (- 10.0
a) first b) zero order c) second
2.303)
order order
30 0.074 - 2.6 (- 14
i) rate of Decreases Stays Decreases
2.60)
reaction constant
60 0.055 - 2.9 (- 18
ii) rate Stays Stays Stays
2.90)
constant constant constant constant
90 0.041 - 3.2 (- 24
iii) half life Stays Decreases Increases
3.19)
constant (half the (double the
The substitution reaction is 1st order with respect to
previous) previous)
[(CH3)3CBr].
2. C =  0.222  mol/L          (0.22  mol/L)
𝑘 = 0.0100  s !!
3. C = 0.14  mol/L
2. 2 NO2 (g) à 2 NO (g) + O2 (g)
4. C = 0.41  mol/L
Tim Concentratio ln 1/Concentrati
5. a) k =  0.050  h!!
e (s) n (mol/L) Concentratio on (L/mol)
b) t = 56  h
n
6. k = 0.00212  s !!
0 0.0100 - 4.61 (- 100.
7. t!/! = 7.30  s
4.605)
8. Graphs for a 1st order equation are shown.
50. 0.0079 - 4.8 (- 130
a) decrease in the initial concentration by a factor of
4.84)
½ as evident by examination of the y-axis
100. 0.0065 - 5.6 (- 150
b) decrease in the initial rate: a tangent drawn to the
5.04)
curves in the first graph at time zero now has about
200. 0.0048 - 5.3 (- 210
HALF the SLOPE
5.34)
c) rate constant, k (determined by finding the slope
300. 0.0038 - 5.6 (- 260 of the lnC vs t graph) remains the SAME
5.57) d) temperature has increased. Only a change in
400. 0.0032 - 5.7 (- 310 temperature can change k.
5.75) e) the slope of the initial tangent line (= the rate) has
a) Rate = k[NO2]2 increased and the temperature could increase the
k = 0.54  L/mol/s rate constant

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9. Graphs for a 2nd order equation are shown. Page 66, Quick Check
a) decrease in the initial concentration by a factor of 2. 2 C2H6(g) + 7 O2(g) à 4 CO2(g) + 6 H2O(l) +
½ as evident by examination of the y-axis 2857.0 kJ/molrxn
b) decrease in the initial rate: a tangent drawn to the 2 C2H6(g) + 7 O2(g) à 4 CO2(g) + 6 H2O(l)
curves in the first graph at time zero now has about ΔH = -2857.0 kJ/molrxn
HALF the SLOPE 3. 72.2 kJ/molrxn + 2 HBr(g) à H2(g) + Br2(l)
c) rate constant, k (determined by finding the slope 2 HBr(g) à H2(g) + Br2(l) ΔH = +72.2 kJ/molrxn
of the 1/C vs t graph) remains the SAME
d) temperature has decreased. Only a change in Page 70, Practice Problems 1.6.1
temperature can change k. 1. a) endothermic
e) the slope of the initial tangent line (= the rate) has b) i) 30 kJ/mol
decreased and the temperature could decrease the ii) +20 kJ/mol
rate constant iii) 130 kJ/mol
10. Decomposition of aqueous sucrose to form the iv) 140 kJ/mol
isomers glucose and fructose: 2. I) Activation energy for the forward reaction.
Time [C12H22O11] ln[C12H22O11] 1/[C12H22O11] II) Potential energy for the reactants.
(min) (mol/L) (L/mol) III) Activation energy for the reverse reaction.
0 0.316 - 1.15 (- 1.152) 3.17 IV) Enthalpy change.
39 0.274 - 1.30 (- 1.295) 3.65
80 0.238 - 1.44 (- 1.435) 4.20 Page 72, Quick Check
140 0.190 - 1.66 (- 1.661) 5.26 A) Reverse uncatalyzed activation energy. Ea(Reverse
210 0.146 - 1.92 (- 1.924) 6.85 Uncatalyzed) is #2 in Diagram 2.
a) Rate = k[C12H22O11] B) Forward catalyzed activation energy. #3
b) k = 0.004  s !! . Approximate value from graph C) Decrease in Ea due to catalysis. #4
slope. D) ΔH. #7
c) t!/!  1.13×10!  s           189  min          (3.14  h) . E) Forward uncatalyzed activation energy. #6
Approximate value from graph slope F) Reverse catalyzed activation energy. #1
d) C =  0.166  mol/L          (0.17  mol/L). Approximate (Note that #5 is the PE of the activated complex –
value from graph slope. forward and reverse - uncatalyzed.)
11.
Time [CH3NC] ln[CH3NC] 1/[CH3NC] Page 74, 1.6 Review Questions
(s) (mol/L) (L/mol) 1. a) Fe2O3(s) + 2 Al(s) à Al2O3(s) + 2 Fe(s)
2000 0.0110 - 4.51 (- 4.510) 90.0 ΔH = -852 kJ/molrxn
5000 0.0059 - 5.1 (- 5.13) 170 Fe2O3(s) + 2 Al(s) à Al2O3(s) + 2 Fe(s) + 852
8000 0.0031 - 5.8 (- 5.78) 320 kJ/molrxn
12000 0.0014 - 6.6 (- 6.57) 710 b) Ca(s) + O2(g) + H2(g) à Ca(OH)2(s) ΔH = -
15000 0.0007 - 7 (- 7.3) 1000 986 kJ/molrxn
a) Rate = k[CH3NC] Ca(s) + O2(g) + H2(g) à Ca(OH)2(s) + 986
b) 𝑘 == 0.0002  𝑠 !! . Approximate value from graph kJ/molrxn
slope. c) 2 H2O(l) à 2 H2(g) + O2(g) ΔH = +572
c) 𝑡!/! =    3000  𝑠           50  𝑚𝑖𝑛          (0.9  ℎ) . kJ/molrxn
Approximate value from graph slope. 572 kJ/molrxn + 2 H2O(l) à 2 H2(g) + O2(g)
d) 𝐶 = 2  ×10!!  𝑚𝑜𝑙/𝐿          (10!!  𝑚𝑜𝑙/𝐿). 2. a&b)
Approximate value from graph slope.
12. a) 𝑘 = 0.0105  𝐿/𝑚𝑜𝑙/𝑠
b) 𝑡!/! =  316  𝑠 this is the 1st half life
13. Assume 1.00 mol/L initial sample:
t = 34.2  years
14. a) t!/! =  20   C! s
b) C = 0.13  mol/L
15. t =  75.4  s

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 c) The particles above the Ea line in the first graph
represent the particles whose collisions are
successful (have energy > Ea and have good
geometry).
e) An endothermic reaction has a greater
number of successful collisions than the
corresponding exothermic reaction. This
indicates that the endothermic reaction is much
more sensitive to an increase OR decrease in
temperature’s effect on its reaction rate. (Will blue is PE, red (u-shape) is KE
find in Chapter 2 that an increase in T will always 10. a) exothermic
cause a shift in the ENDO direction.) b) 10 kJ/mol
3. a) Endothermic sketch. c) 25 kJ/mol
b) 60 kJ/mol d) -15 kJ/mol - no change at all when catalyzed.
c) -35 kJ/mol e) 15 kJ/mol lower with a catalyst.
4. a) A = Activation energy for forward catalyzed f) increases the reaction rate.
reaction.
B = ΔH Page 80, Quick Check
C = Reverse uncatalyzed activation energy. 2. a)Bimolecular – Elementary Process
D = Forward uncatalyzed activation energy. b) Unimolecular – Elementary Process
E = Reverse catalyzed activation energy. c) Termolecular – Overall Reaction
b) Exothermic
c) No effect. Page 83, Practice Problems 1.7.1
5. a) -50 kJ/mol
b) Q + S à T + 50 kJ/mol 1. O3(g) à O2(g) + O(g) (slow)
Q + S à T ΔH = -50 kJ/mol
O(g) + O3(g) à 2 O2(g)
c) exothermic
d) 150 kJ/mol (ΔH value for entire reaction = - 284.6 kJ/mol)
6. The energy released as more CO2(g) and H2O(g) is ----------------------------------------------------------------------
formed provides the activation energy needed to 2 O3(g) à 3 O2(g)
continue decomposing the hydrocarbon fuel. There are no catalysts and O is the intermediate.
7. Fill in the blanks for an EXOthermic reaction: The
energy released during bond forming is Overall Ea is shown on the y-axis.
__greater__ than the energy required for bond
__breaking___. As a result, there is a net
___release___ of energy. The bonds formed have
_less_ potential energy than the __reactant__
bonds did.
8. The diagrams would be the same. The potential
bond energy would be the same. The “reaction
coordinate” is NOT a time axis!!
9. As particles approach one another their KE
DECREASES (bond breaking requires energy – KE
à PE). Meanwhile, their PE INCREASES (see
above). Once an activated complex has formed,
the KE INCREASES (bond forming releases energy)
and their PE decreases). The sum of KE and PE
remains constant the entire time. 2. H2(g) + 2 Pd(s) 2 Pd-H(s)
C2H4(g) + Pd-H(s) à C2H5-Pd(s) (slowest
step)
C2H5-Pd(s) + Pd-H(s) à C2H6(g) + 2 Pd(s)
--------------------------------------------------------------------
C2H4(g) + H2(g) à C2H6(g) + 136.9 kJ/mol

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Catalyst is: Pd Intermediates are: Pd-H and C2H5Pd 2. The slowest elementary process in a reaction
mechanism determines the overall reaction rate and
Activation energy is between the dotted lines. is called the RATE-DETERMINING STEP.
3. Chemists determine these models by altering the
concentration of species involved in the mechanism
and examining the effects these alterations produce.
Computer models are also very useful in the pursuit
of mechanisms.
4. a) Hetero b) Homo c) Hetero
5.
1st: H2O2(aq) + I-(aq) à H2O(l) + IO-(l) slow

2nd H2O2(aq) + IO-(aq) à H2O(l) + O2(g) + I-(aq) fast

3.
Cl2(g) à Cl(g) + Cl(g) initiation a) Overall Rxn: 2 H2O2(aq) à 2 H2O(l) + O2(g)
CH4(g) + Cl(g) à CH3Cl(g) + H(g)) x 2 propagation b) Intermediates: IO-
H(g) + H(g) à H2(g) termination c) catalyst is I-
-------------------------------------------------------- 6. NO2 + F2 à NO2F + F (RDS)
2 CH4(g) + Cl2(g) à 2 CH3Cl(g) + H2(g) chain NO2 + F à NO2F
mechanism ------------------------------------
There are no catalysts. LIGHT provides Eafor the reaction. 2 NO2 + F2 à 2 NO2F
Intermediates include H’s and Cl’s (free radicals). 7. a) 3
b) 2nd step (middle step or step C)
c) C
d) B
e) F
f) endothermic
8.
a) Mechanism One:
Step 1:
2 NO2(g) à NO3(g) + NO(g) slow

Step 2:
(The relative heights of the second and third step are not CO + NO3 à CO2 + NO2 fast
actually known from the information provided. The Overall Rxn:
reaction is only slightly exothermic. Though the CO(g) + NO2(g) à CO2(g) + NO(g)
propagation step occurs twice, the reactant and product (Note that this is an example of authocatalysis.
energies are the same, so it is shown only once.) The reactant, NO2, also acts as a catalyst for the
reaction. Some autocatalyzed reactions involve
Page 87, Practice Problems 1.7.2 the formation of the catalyst from the reactants
1. a) intermediates: HOCl, OH-, HIO; catalyst: H2O in an early step.)
b) Rate = k[I-][OCl-]/[OH-]
2. a) Cl2 ↔ 2 Cl Mechanism Two:
Cl + CHCl3 à HCl + CCl3 Step 1:
Cl + CCl3 à CCl4 2 NO2(g) à N2O4(g) fast
Cl2 + CHCl3 à CCl4 + HCl Step 2:
b) intermediates: Cl, CCl3 CO + NsO4 à NO2 + CO2 + NO slow
c) Rate = k[Cl2]1/2[CHCl3] Overall Rxn:
CO(g) + NO2(g) à CO2(g) + NO(g)
Page 91, 1.7 Review Questions
1. A series of steps that may be added together to give b) Mechanism 1 is correct as the CO is NOT in the
an overall chemical reaction. RDS!
9. a) No – too many reactant particles (five) for a
single step.
b) HBr + O2 à HOOBr

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 HBr + HOOBr à 2 HOBr [𝑀]
𝐾!" =
HBr + HOBr à H2O + Br2 𝐴 [𝐵]
HBr + HOBr à H2O + Br2 [M] = Keq[A][B]
4 HBr + O2 à 2 H2O + 2 Br2 Rate = k’Keq[A]2[B]
c) Step One (both HBr and O2 influence reaction Rate = k[A]2[B]
rate). 13. a) Step 1: NO + O2 ↔ NO3
d) Step 2: NO3 + NO à 2 NO2
2 NO + O2 à 2 NO2
b) Rate = k[NO]2[O2]
14. a) NH3 + OBr- ↔ NH2Br + OH-
NH2Br + NH3 à N2H5+ + Br-
N2H5+ + OH- à N2H4 + H2O
2 NH3 + OBr- à N2H4 + Br- + H2O (basic)
b) intermediates: NH2Br, OH-, N2H5+
c) Rate = k[NH3]2[OBr-]/[OH-]
10.

(Note the relative heights of steps one and two don’t

matter, but there must be AT LEAST two steps.)
11. a) intermediate: N2O2
b) Rate = k[NO]2[O2]
12. Starting with each mechanism’s temporary rate law
based upon the slow step:
Mechanism One: inconsistent with the provided rate
law, rate = k[A][B]
Rate = k’[M][A]
𝐶 [𝑀]
𝐾!" =
𝐴 [𝐵]
[M] = Keq[A][B]/[C]
Rate = k’Keq[A]2[B]/[C]
Rate = k[A]2[B] /[C]
N/A: if [M] in the rate law was substituted with the
statement above, non-reactant species are also
included
Mechanism Two: consistent with the provided rate
law, rate = k[A][B]
Rate = k’[M][A]
[𝑀]
𝐾!" =
𝐵
[M] = Keq[B]
Rate = k’Keq[A][B]
Rate = k[A][B]
Mechanism Three: inconsistent with the provided
rate law, rate = k[A][B]
Rate = k’[M][A]

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2016/2017-2