Probelm Sets

Conversion Factors
(Exact conversion factors are denoted with an asterisk)

SI Units
1 J = 1 kg m2 s-2 *
1J=1CV*
1 C = 1 J V-1 *
SI English Units
1 lb = 0.4535924 kg
1 in = 2.54 cm *
1 oz = 28.3495 g
Other
16 oz = 1 lb *
5280 feet = 1 mile *
1 J = 4.184 cal *
Physical Constants
Name
Gas Constant
Symbol
R
Faradays Constant
Avogadros Number
NA
Value_________________________
8.314472 J K-1 mol-1
0.0820575 L atm K-1 mol-1
96,485 C
96,485 J V-1
6.022141 x 1023 mol-1
Selected Equations
Arrhenius Equation
Nernst Equation at 25 C
Zero order Integrated Rate Law
Ea
k = Ae RT
0.0592 V
E = E
log ( Q )
n
[ A] = kt + [ A]o
First order Integrated Rate Law
ln [ A] = kt + ln [ A]o
Second Order Integrated Rate Law
1
1
= kt +
[ A]
[ A]o
Problem Set 1
CONCEPTS AND SKILLS
This problem set reviews key background concepts from algebra and from General
Chemistry I.
1-1. Review fundamental calculator skills (multiply, divide, add, subtract, order of operations,
logarithms and exponentials, powers and roots).
1-2. Review fundamental algebra sills (linear equations, quadratic equations, logarithms and
exponentials, powers and roots).
1-3. Review and apply the rules of significant figures.
1-4. Review and perform unit conversions, and express final answers with the correct units.
1-5. Review and perform mass to mole conversions.
1-6. Review and perform solution dilution calculations.
PROBLEMS
1-1.
Calculator Skills. Solve the following problems using your calculator. Consult the
calculators users manual if you run into difficulties with these exercises.
A.
27 x (43 + 2) = __________
( 38 1) = ______
B.
1
1
298 373
C.
log(4.2 x 10-3) = ______
D.
e 32.7 = _______
E.
(1.54 x 10-2)5 = __________
3
F.
634.2 = _________
G.
Write out (and number) the steps required to completely clear and reset the
memory (RAM) of your calculator.
1-2.
Algebra: Linear Equations. Solve the following equations for x.

A.
27 x - 45 = 22
B.
12 x + 27 = 10 x - 6
1-3.
Algebra: Quadratic Equations. Solve the following equations for x.

A.
2x2 = 27 3x
x2
B.
1.0 x 103 =
( 0.010 x )
1-4.
Algebra: Logarithms and Exponentials: Solve the following equations for x.

A.
ln(2x) = -12.7
B.
37 = 10-3.7x
1-5.
Algebra: Powers and Roots: Solve the following equations for x.

A.
36 = x7
2.78 = 3 4 x + 2
B.
1-6.
Significant Figures: Solve the following problems, and express them to the correct
number of significant figures.
A.
27.3 x 3342 x 12 = _________
B.
223.5 + 1.232 + 2.323 x 104 = __________
(298.43 297.64) ( 8.3145 )
C.
= ____________
122.5
1
74231 1
D.
= ________
8.314 323 298
1-7.
Units: Solve the following problems involving unit conversions.

A.
1 inch = 2.54 cm (exactly). There are 5280 feet in a mile. A car is traveling at
60.0 miles per hour. Convert this speed to meters per second.
B.
1 atm = 1.01325 bar. 1 bar = 105 Pa. 1 Pa = 1 N m-2. Pressure is defined as
Force per unit area. If a 101 kg man is standing on a 0.0100 m2 surface what
pressure does he exert on the surface? Express your answer in units of (a) Pa, (b)
bar, and (c) atm. g (acceleration due to gravity) = 9.81 ms-2
1-8
Mass and Moles

A.
How many moles are in 64.9 grams of H2O?
B.
What is the mass of 2.87 moles of H2SO4?
1-9
Dilution
A.
How many mL of 12.0 M HCl are required to make 150.0 mL of 0.100 M HCl?
B.
If 25.0 mL of water is added to 50.0 mL 0.250 M HCl, what is the final HCl
molarity?
Problem Set 2
CONCEPTS AND SKILLS
2-1. Review basic concepts related to solutions and their formation.
2-2. Predict whether a solute will be soluble in a given solvent.
2-3. Discuss the relationship between the partial pressure of a gas and its solubility (Henrys
Law).
2-4. Review and perform molarity, mass, and volume problems.
2-5. Review and perform problems involving the dilution of solutions.
PROBLEMS
2-1.
Review and memorize all terms and their definitions that are defined in this set of lecture
notes.
2-2.
When a certain solid is placed in water, its enthalpy of solution is endothermic.

Hsoln > 0. Will the solid dissolve in water? Explain your answer completely.
2-3.
For each of the following compounds, predict whether it will be more soluble in
ammonia (NH3) or carbon tetrachloride (CCl4). Justify your choices.
A. Water (H2O)
B. Methane (CH4)
C. Methanol (CH3OH)
E. Sodium Chloride (NaCl)
D Hexane (CH3CH2CH2CH2CH2CH3)
2-4.
Henrys Law constant for N2 in water at 20C is 6.9 x 10-4 M atm-1. In the atmosphere,
the partial pressure of N2 is 0.78 atm. What is the concentration of N2 in an open
container containing water at 20C?
2-5.
Henrys Law constant for CO in water at 20C is 1.04 x 10-3 M atm-1. What would the
partial pressure of CO have to be for an open glass of water to have a CO concentration
of 3.0 x 10-5 M? Express your answer in atm and in torr.
2-6.
How many grams of CaCO3 would be required to make 100.0 mL of a 0.250 M solution?
2-7.
You have a concentrated 18.0 M solution of a mineral acid. How much of the
concentrated solution would you need to use to make 1.000 L of a 0.125 M solution?
Problem Set 3
CONCEPTS AND SKILLS
3-1. Define the following six concentration units, and calculate concentrations in each of these
units: molarity, mass percent, parts per million, parts per billion, mole fraction, and
molality.
3-2. Perform conversions between these six units.
3-3. State and explain Raoults Law. Use Raoults Law in calculations involving partial
pressure and mole fraction.
PROBLEMS
3-1.
37.0 g of CaCl2 are dissolved into 37.0 mol of water. The density of the resulting
solution is 1.12 g/mL. Calculate the concentration in each of the following units:
A.
mass percent of CaCl2
B.
parts per million of CaCl2
C.
parts per billion of CaCl2
D.
mole fraction of H2O
E.
mole fraction of CaCl2
F.
molality
G.
molarity
3-2.
An aqueous solution is 0.231 m (molal) in NaCl. If the solution density is 1.034 g/mL,
calculate the concentration in the following units:
A.
mass percent of NaCl
B.
parts per million of NaCl
C.
parts per billion of NaCl
D.
mole fraction of NaCl
E.
F.
molarity
3-3.
An aqueous solution is 0.00150 M (molar) in HCl. If the solution density is 0.999 g/mL,
calculate the concentration in each of the following units:
A.
molality
B.
mass percent of HCl
C.
parts per million of HCl
D.
parts per billion of HCl
E.
mole fraction of HCl
F.
3-4.
At some temperature the equilibrium vapor pressure of pure water is 28.0 torr. Calculate
the partial pressure of water vapor in equilibrium with a 2.00 m aqueous solution. The
solute is nonvolatile.
3-5.
At some temperature the equilibrium vapor pressure of pure water is 28.0 torr. If the
experimental partial pressure of water vapor over a solution containing a nonvolatile
solute is 24.4 torr, calculate the mole fraction of the solute.
Problem Set 4
CONCEPTS AND SKILLS
4-1. Define colligative property. On what do colligative properties depend?
4-2. Perform calculations to determine boiling point elevations, freezing point depressions, or
osmotic pressures.
4-3. Use colligative properties to determine the molar mass of a solute.
PROBLEMS
The following constants may be useful in one or more of the following problems. You
may assume that all solutes are nonvolatile.
Substance
Formula Kb (C/m) Kf (C/m)
water
H2 O
0.51
1.86
benzene
C6H6
2.53
5.12
ethanol
C2H5OH
1.22
1.99
carbon tetrachloride
CCl4
5.02
29.8
chloroform
CHCl3
3.63
4.68
4-1.
The normal freezing temperature of water is 0.000 C. What is the expected freezing
point of a 0.150 m aqueous solution of NaCl?
4-2.
What concentration (m) of Ca(NO3)2 would be required to increase the boiling

temperature of ethanol (solvent) by 2.50 C?
4-3.
If an aqueous solution exerts an osmotic pressure of 2.54 atm at 298 K, what is the
molarity of the nonvolatile solute?
4-4.
Camphor (C10H160) melts at 179.8 C and has a freezing point depression constant, Kf =
40.0 C/m. When 0.300 g of a substance is dissolved in 26.41 g of liquid camphor, the
freezing point of the mixture is measured to be 175.6 C. What is the molar mass of the
solute?
4-5.
10.25 g of polystyrene polymer was dissolved in enough toluene to form 0.500 L of

solution. The osmotic pressure of the solution was found to be 8.96 Torr at 25.0 C.
Calculate the average molar mass of the polystyrene polymer.
Problem Set 5
CONCEPTS AND SKILLS
5-1. Identify the factors that affect reaction rates.
5-2. Given the rate of one species, determine the rate of another.
5-3. Calculate the average rate (of appearance or disappearance) over a specified period of
time, given initial and final concentrations.
PROBLEMS
5-1.
Identify four important factors that can affect reaction rates. In brief sentences, explain
the role of each factor in changing the rate of reaction.
5-2.
Consider the hypothetical reaction, 3A + 2B 4D + F. If A is being used up at the rate

of 3.30 x 10-2 M s-1, determine the following rates.
a. Overall reaction rate; b. rate of disappearance of B; c. rate of appearance of D; d. rate
of appearance of F.
5-3.
Consider the following reaction: C12H24O11 + 25/2 O2 12CO2 + 12H2O. If CO2 is

being produced at a rate of 1.800 x 10-4 M s-1, determine the following rates.
a. Overall rate of reaction; b. rate of disappearance of C12H24O11; c. rate of consumption
of O2; d. rate of appearance of H2O.
5-4.
(a) Define the following terms: average rate; instantaneous rate; initial rate. (b) At what
point in a reaction is the overall rate largest?
For the next two problems, consider the following experimental data, which was
collected for the overall reaction, 2A + B P.
time (s)
0
50
100
150
200
250
300
350
400
[A]/M
0.0100
0.0079
0.0065
0.0055
0.0048
0.0043
0.0038
0.0034
0.0031
5-5.
Calculate the average rate of disappearance of A, and the average rate of reaction for the
first 200 seconds.
5-6.
Calculate the average rate of disappearance of A, and the average rate of reaction for the
last 200 seconds.
Problem Set 6
CONCEPTS AND SKILLS
6-1. Define key terms related to rate laws, and orders of reaction.
6-2. Determine the units associated with the rate constant for a given rate law.
6-3. Given a rate law, determine how the rate will be affected by specific changes in reactant
concentrations.
PROBLEMS
6-1.
(a) What is a rate law? (b) Define the rate constant. (c) For a reaction of the form, 3A +
2 B + C products, what is the assumed rate law? (d) What is the relationship between
the exponents in the rate law and the coefficients of the balanced equation? (e) Under
what conditions will the value of the rate constant change?
6-2.
A reaction, 3A + B C + 2D, has the experimentally-determined rate law, v = k[A]2[B].

What is (a) the order of the reaction in A, (b) the order of reaction in B, and (c) the
overall order of reaction?
6-3.
The reaction, A + B P, is zero order in the reactant B. What does this mean?
6-4.
Given the following units for the rate constant, identify the overall order of reaction: (a)
year-1; (b) M-2 s-1.
6-5.
Determine the correct units for the following orders of reaction, assuming that
concentrations are in molarity (M) and time is in seconds (s): (a) zero order; (b) second
order; (c) fourth order.
6-6.
Consider the rate law, v = k[A][B]2. (a) What happens to the rate of reaction if the
concentration of B is doubled, without changing [A]? (b) What happens to the rate of
reaction if the concentration of A is doubled without changing [B]? (c) What happens to
the rate of the reaction if [A] is doubled and [B] is simultaneously tripled?
6-7.
Consider the rate law, v = k[A][B]3. (a) What happens to the rate of reaction if the
concentration of B is reduced to 1/3 its original value, without changing [A]? (b) What
happens to the rate of reaction of the concentration of A is reduced to 1/3 its original
value without changing [B]? (c) What happens to the rate of reaction if the concentration
of A is halved and the concentration of B is simultaneously doubled?
6-8
(a) The rate of a reaction increases by a factor of 3.06 when the concentration of reactant,
R, is increased by a factor of 1.75. What is the order of reaction in the reactant, R? (b)
For another reaction, the rate increases by a factor of 2.83 when the concentration of
reactant, R, is doubled. What is the order of reaction in the reactant, R?
6-9
Write the rate law expression for each of the following reactions as described. (a) The
overall reaction is first order and only reactant, A, appears in the rate law. (b) The
overall reaction is second order overall, and the rate depends only on the concentration of
reactant, B. (c) The reaction is second order overall, and is first order in both reactant A
and reactant B.
Problem Set 7
CONCEPTS AND SKILLS
7-1. Determine the rate law, given initial rate data.
7-2. Using the same data, determine the value of the rate constant, k.
PROBLEMS
For each of the following problems, an overall chemical reaction is given, with a table of initial
rate (experimental) data. For each of these three problems, complete the following. (a)
Determine the rate law. (b) Determine the value and the units of the rate constant, k. (c)
Predict the initial reaction rate when all initial reactant concentrations are 0.125 M.
7-1.
Overall reaction: 2NO(g) + 2H2(g) N2(g) + 2H2O(g).

Initial rate data:
trial [NO]o/M [H2]o/M vo/(M s-1)
1
0.10
0.10
1.23 x 10-3
2
0.10
0.20
2.46 x 10-3
3
0.20
0.10
4.92 x 10-3
7-2.
Overall reaction: 2A(g) + B(g) X(g) + 2Y(g).

Initial rate data:
trial [A]o/M [B]o/M
1
0.40
0.30
2
0.60
0.30
3
0.60
0.75
vo/(M s-1)
1.00 x 10-4
2.25 x 10-4
1.41 x 10-3
Overall reaction: A(g) + B(g) 2X(g).

Initial rate data:
trial [A]o/M [B]o/M
1
0.25
0.20
2
0.50
0.20
3
0.50
0.40
vo/(M s-1)
1.25 x 10-3
3.54 x 10-3
3.54 x 10-3
7-3.
Problem Set 8
CONCEPTS AND SKILLS
8-1. Calculate [A] or k, using the first-order integrated rate law.
8-2. Identify the characteristics of a first-order reaction plot; determine the half-life or rate
constant from the plot.
8-3. State the relationship between k and t; use the relationship to convert between the two.
8-4.
8-5.
Determine the half-life of a reaction from experimental data.

Given the half-life or rate constant calculate the time required for a reactant to decrease to
a given amount (or fraction).
PROBLEMS
8-1.
A P is a first order reaction. Explain what is meant by this statement, and write the
rate law for this reaction.
8-2.
One form of the integrated rate law for first order reactions is ln[A] = -kt + ln[A]o. (a)
Identify the meaning of each variable in the equation. What units are associated with
each of the four variables? Using algebra, derive the following relationships from the
above equation: (b) ln([A]/[A]o) = -kt; (c) [A] = [A]o e-kt; (d) ([A]/[A]o) = e-kt.
8-3.
2N2O5 2N2O4 + O2 is a first order reaction, with v = k[N2O5]. At some temperature,

the rate constant is experimentally determined to be k = 6.22 x 10-4 s-1. If the reaction is
carried out at the same temperature with an initial N2O5 concentration of 0.100 M, how
long will it take (in minutes) for the N2O5 concentration to drop to 0.0100 M?
8-4.
The decomposition of dimethyl ether, (CH3)2O, at 510 C is a first-order process with a

rate constant of 6.8 x 10-4 s-1.
(CH3)2O(g) CH4(g) + H2(g) + CO(g)
If the initial pressure of (CH3)2O(g) is 135 torr, what is its partial pressure after 1420 s?
8-5.
When sucrose is placed in aqueous solution, it is broken down to glucose by the

following reaction, C12H22O11 + H2O 2C6H12O6. Experimental studies show that the
reaction is first order in sucrose. After 154.2 minutes at 298 K, the original sucrose
concentration of 6.0 g L-1 has decreased to 5.4 g L-1. Calculate the rate constant for this
reaction in units of min-1.
8-6.
The first-order rate constant for the decomposition of N2O5,

N2O5(g) 2NO2(g) + O2(g),
-3 -1
at 70 C is 6.82 x 10 s . Suppose we start with 0.0300 mol of N2O5(g) in a volume of
2.5 L. (a) How many moles of N2O5 will remain after 2.5 minutes? (b) How many
minutes will it take for the quantity of N2O5 to drop to 0.0050 mol? (c) What is the halflife of N2O5 at 70 C?
8-7.
The reaction, 2NO2 2NO + O2, is first order, and has a rate constant of 2.83 x 10-2 s-1.
How long will it take for the concentration of NO2 to decrease to 62.5% of its original
value?
8-8.
(a) Define half life, t . (b) Combine the integrated law and the algebraic expression for
the half-life concentration to derive the relationship between rate constant and half-life
for a first order reaction. (c) What characteristic of the first order half life is different
from the half lives of other order reactions? (d) If the half life of a first order reaction is
25.7 s, what is its rate constant? (e) If the rate constant for a first order reaction is 2.120
x 10-4 yr-1, what is its half life? (f) How many half lives are required for the reactant
concentration to drop to 1/8 of its original value?
8-9.
The thermal decomposition of N2O5(g), N2O5(g) 2NO2(g) + O2(g), is a first-order

reaction. The rate constant for the reaction is 5.1 x 10-4 s-1 at 318 K. What is the half-life
of this reaction at 318 K?
8-10. A P is a first order reaction. (a) Predict the characteristics of the following two plots
based on concentration data: [A] vs. t; ln[A] vs. t. (b) Which of the two plots can be
used to determine the rate constant, k, and the initial concentration, [A]o? How can these
two quantities be determined from the graphical data?
8-11. Consider the following concentration data for A P. (a) What is the half life of this
reaction? (b) Does the data indicate that the reaction is first order? Justify your answer.
time/s [A]/M
0.0 0.880
5.0 0.740
10.0 0.622
15.0 0.523
20.0 0.440
25.0 0.370
30.0 0.311
35.0 0.262
40.0 0.220
45.0 0.185
50.0 0.156
8-12. Consider the following plot of [A] vs. t for a first order reaction, A P. Estimate the
reactions half life and the rate constant.
1.0
0.9
[A] (M)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0
200
400
600
800
1000
time (s)
8-13. Consider the following plot of ln [A] vs. t for A P. Coordinates of the first and last
data points are shown. (a) Is the reaction first order? Justify your answer. (b) Estimate
the reactions rate constant and half life.
-0.5
(0, -0.69)
ln ([A]/M)
-1.0
-1.5
-2.0
-2.5
-3.0
-3.5
-4.0
(1000, -4.16)
-4.5
0
200
400
600
800
1000
t/s
8-14. It takes 2820 s for the concentration of reactant, A, to decrease to 1/3 of its original value
in the first order reaction, A B + C. What is the half-life of this reaction?
8-15. Radium-223 has a first order radioactive decay half life of 11.4 days. What fraction of an
original Ra-223 sample will have decayed after 25.0 days?
8-16. The half life of a first order reaction is 200 s. (a) How long will it take for the reactant A
to decrease to 1/9 of its original concentration? (b) How long will it take for the initial
concentration of 1.000 M to drop to 0.300 M?
8-17. You are studying a chemical reaction, A P, to determine its overall order. In the
laboratory you collect an extensive set of concentration, [A], vs. time data for the
reaction. (a) What two separate tests can you run on your data to determine whether the
reaction is first order? (b) For each of the tests, what results support a first order rate
law?
Problem Set 9
CONCEPTS AND SKILLS
9-1. Identify and discuss the characteristics of alpha, beta, and gamma radiation.
9-2. Balance nuclear equations.
9-3. Solve problems involving the kinetics of radioactive decay.
9-4. Solve problems involving dating methods based on radioactive decay.
PROBLEMS
9-1. Identify and compare the fundamental nature and characteristics of alpha, beta,
and gamma radiation. Discuss (with explanation) which of the three is likely to
be most damaging to living organisms.
9-2.
9-3.
Complete the missing numbers, symbols, or other information in the table below:
name
symbol
A. Thorium-234
B.
14
C.
206
D.
__
6_____
__Pb
-1
Identify the missing reactant or product in each of the following nuclear reaction
equations, and classify the nuclear reaction.
214
4
A.
84Po _____ + 2
B.
______ + 5826Fe 266109Mt + 10n
C.
239
D.
______ + 10n 9038Sr + 14354Xe + 3 10n
94Pu
+ 10n 24095Am + ______
9-4.
Np-239 has a half-life of 2.35 days. Suppose you isolate a 95.0 g sample of pure
Np-239. How much Np-239 remains after exactly 1 week (7.00 days) has passed?
9-5.
A piece of linen cloth found at an ancient burial site is found to have a 14C activity
of 4.8 disintegrations per minute. Determine the age of the cloth. Assume that
the 14C activity of an equal mass of living flax (the plant from which linen is
taken) is 14.8 disintegrations per minute. The half-life of 14C is 5715 years.
9-6.
Uranium-238 decomposes to Pb-206, with an associated half-life of 4.51 x 109

year. The overall process, which takes place in several steps, is summarized by:
238
206
4
0
92U
82Pb + 8 2 + 6 -1.
If it can be assumed that no lead Pb-206 was present when a geological sample
was formed, and that the mineral has not undergone any chemical changes that
would allow the Pb-206 to be physically separated from its parent U-238, it is
possible to estimate the age of geological rocks via the mass ratio of Pb-206 to U238.
A rock is found to contain 5.51 mg of U-238 and 1.63 mg of Pb-206. Determine
the age of the rock.
Problem Set 10
CONCEPTS AND SKILLS
10-1. Identify the features of a Reaction Coordinate Diagram, including the activation energy
and E; use the diagram to make predictions about rates of reaction.
10-2. Identify the properties of a catalyst.
10-3. Discuss the effect of a catalyst on the reaction pathway.
PROBLEMS
10-1. Draw a reaction coordinate diagram for the reaction, R P, when the internal energy of
the reactant is less than the internal energy of the product. Label all of the following on
your diagram: the axes, reactant, product, activated complex, transition state, E for the
reaction, forward activation energy, reverse activation energy.
10-2. (a) Why is the reaction rate so strongly dependent on temperature? (b) Explain why each
of the following can be an important factor in the reaction rate: number of collisions
between molecules; relative orientation between colliding molecules; energies of
colliding molecules.
10-3. Where is the temperature dependence in the rate law, v = k[A]m[B]n?
10-4. The Arrhenius equation is, k = A exp(-Ea/RT). Answer the following, based on your
diagram in 10-1 and/or on the Arrhenius equation. Assume that Ea > 0.
(a) If all other factors are the same, how will the rate of reaction be affected if:
(1) The prefactor, A, is increased?
(2) The activation energy, Ea is increased?
(3) The temperature is increased?
(b) If all other factors are the same, how will the ratio of product to reactant
concentrations at equilibrium be affected by a decrease in the forward activation energy?
(c) Consider two reactions, one which has a large energy of activation and the other a
small energy of activation. Which one of the two will be more sensitive to temperature
changes? Justify your answer.
10-5. (a) Identify the properties of a catalyst. (b) How does a catalyst increase the rate of
reaction? (c) How is the equilibrium ratio of product to reactant concentrations affected
by a catalyst?
Problem Set 11
CONCEPTS AND SKILLS
11-1. Define reactants, products, catalysts and intermediates, and identify them in a reaction
mechanism.
11-2. For a given elementary reaction step, identify its molecularity, and write its rate law.
11-3. Choose a mechanism consistent with a given rate law.
PROBLEMS
11-1. Consider the following mechanism. (a) Write the balanced overall reaction equation. (b)
Identify each species in the reaction as a reactant, product, intermediate, or catalyst. (c)
For each reaction step, state its molecularity and write its elementary rate law.
(i)
Cl2 2Cl
(k1, k-1)
(ii)
Cl + CHCl3 HCl + CCl3
(k2)
(k3)
(iii) Cl + CCl3 CCl4
11-2. For each of the following elementary reaction steps, identify the molecularity, and write
the correct expression for the elementary reaction rate. (Do this for the forward and the
reverse elementary reactions.)
(i)
A* B + C
(k1, k-1)
(ii)
D+EF+G
(k2, k-2)
(iii)
Br + Br + Xe Br2 + Xe*
(k3, k-3)
11-3. Explain what is meant by the rate determining step.
11-4. Consider the overall reaction, NO2(g) + CO(g) NO(g) + CO2(g), whose rate law is
experimentally determined to be v = k[NO2]2. The following two-step mechanism is
proposed:
(1) NO2 + NO2 NO3 + NO
(slow, k1)
(fast, k2)
(2) NO3 + CO NO2 + CO2
(a) Is the mechanism consistent with the overall reaction equation? Explain.
(b) Using the rate determining step principle, determine the rate of reaction from the
mechanism.
(c) Is the mechanism derived in (b) consistent with the laboratory rate law? Explain.
11-5. Consider the overall reaction, 2NO(g) + Br2(g) 2NOBr(g), whose rate law is
experimentally determined to be v = k[NO]2[Br2]. The following two-step mechanism is
proposed:
(1) NO + NO N2O2
(fast, k1, k-1)
(slow, k2)
(2) N2O2 + Br2 2NOBr
(a) Is the mechanism consistent with the overall reaction equation? Explain.
(b) Using the rate determining step principle along with the pre-equilibrium
approximation, determine the rate of reaction from the mechanism. Express your answer
in terms of reactant concentrations and elementary rate constants.
(c) Is the mechanism derived in (b) consistent with the laboratory rate law? Explain.
Problem Set 12
CONCEPTS AND SKILLS
12-1. Identify the factors on which equilibrium depends; determine whether a specified system
is at, or can reach equilibrium.
12-2. For a gas-phase equilibrium, write the correct expression for the equilibrium constant, K.
12-3. Given all concentrations, calculate the value of K for a given reaction.
12-4. From the magnitude of K, deduce whether reactants or products (or neither) are most
abundant at equilibrium.
12-5. Determine the value of K, given K for a related reaction.
PROBLEMS
12-1. Write the correct expression for the equilibrium constant, Kc, for each of the following
gas phase reactions.
a.
2NO2(g) N2O4(g)
b.
2SO2(g) + O2(g) 2SO3(g)
c.
H2(g) + Cl2(g) 2HCl(g)
d.
2HBr(g) + Cl2(g) 2HCl(g) + Br2(g)
12-2. A mixture of pure nitrogen gas is mixed with some pure hydrogen gas in a closed,
otherwise empty 5.00-L container at 773 K. The mixture is analyzed after equilibrium
has been established, and found to contain 3.01 mol N2(g), 2.10 mol H2, and 0.565 mol of
NH3. Calculate the value of the equilibrium constant, Kc, at 773 K for the following
reaction: N2(g) + 3H2(g) 2NH3(g).
12-3. Consider the following three equilibrium reactions and their respective equilibrium
constants. For each reaction, state whether the reactants, products, or neither will have
concentrations that dominate the equilibrium mixture.
Kp = 1.45 x 10-5
a.
N2(g) + 3H2(g) 2NH3(g)
b.
2NO(g) N2(g) + O2(g)
Kc = 1 x 1030
c.
AB(g) + C(g) A(g) + BC(g)
Kc = 1.1
12-4. Consider the following hypothetical equilibrium reactions, with their assigned
equilibrium constants.
Reaction
Kc
K1
A(g) + 2B(g) 2C(g)
2C(g) + D(g) A(g) + 2G(g) K2
Express the equilibrium constant, Kc, of each of the following reactions in terms of K1
and/or K2.
a.
3A(g) + 6B(g) 6C(g)
b.
A(g) + 2G(g) 2C(g) + D(g)
c.
A(g) + G(g) C(g) + D(g)
d.
2B(g) + D(g) 2G(g)
12-5. Consider the following equilibrium reactions, with their associated equilibrium constant
values.
Reaction
Kc
1.0 x 1012
Cl2(g) + Br2(g) 2BrCl(g)
2HBr(g) + Cl2(g) Br2(g) + 2HCl(g) 4.0 x 104
Calculate the value of the equilibrium constant , Kc, for each of the following reactions.
a.
4Cl2(g) + 4Br2(g) 8BrCl(g)
b.
2BrCl(g) Cl2(g) + Br2(g)
c.
4HBr(g) + 2Cl2(g) 2Br2(g) + 4HCl(g)
d.
Br2(g) + 2HCl(g) 2HBr(g) + Cl2(g)
e.
Cl2(g) + HBr(g) BrCl(g) + HCl(g)
Problem Set 13
CONCEPTS AND SKILLS
13-1. Write the correct K expression for heterogeneous equilibria; given equilibrium
concentrations, calculate the value of K.
13-2. Calculate all final concentrations, and the value of K, given all initial concentrations and
one final concentration.
13-3. Determine the concentration (pressure) of one species given K and the equilibrium
concentrations (pressures) of the other substances.
PROBLEMS
13-1. Write the correct equilibrium expression, K, for each of the following reactions.
a.
C6H12O6(s) + 6O2(g) 6CO2(g) + 6H2O(l)
b.
CaCO3(s) CaO(s) + CO2(g)
c.
H2O(l) + H2SO4(aq) H3O+(aq) + HSO4-(aq)
d.
SnO2(s) + 2CO(g) Sn(s) + 2CO2(g)
e.
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
13-2. The reaction below is carried out in a 5.00-L reaction vessel:
CO(g) + H2O(g) CO2(g) + H2(g).
At equilibrium it was found that 0.0200 mol of CO, 0.0215 mol H2O, 0.0700 mol CO2,
and 2.00 mol H2 were present. What is the value of the equilibrium constant, Kc?
13-3. Consider the following equilibrium reaction: N2O4(g) 2NO2(g). A 5.00-L vessel is
filled with 10.0 mol of pure N2O4(g). Once equilibrium has been established, 3.50 moles
of NO2 is found in the container. What is the equilibrium concentration of N2O4(g), and
what is the value of the equilibrium constant, Kc?
13-4. A mixture containing only 1.00 mol NO, 0.500 mol H2, and 1.00 mol of H2O is placed in
a 10.0-L vessel. The following equilibrium is established:
2NO(g) + 2H2(g) N2(g) + 2H2O(g).
At equilibrium the concentration of NO is measured and found to be 0.0620 M.
Calculate the equilibrium concentrations of the other three species, and calculate the
value of Kc.
13-5. At some temperature the equilibrium constant for the reaction,
2NO(g) + Cl2(g) 2NOCl(g),
has a value, Kp = 52.0. At equilibrium, the partial pressures of NO and Cl2 are measured,
and found to be 0.095 atm and 0.171 atm respectively. What is the partial pressure of
NOCl in the equilibrium mixture?
13-6. For the equilibrium, C(s) + CO2(g) 2CO(g), Kp = 167.5 at an elevated temperature. At
this temperature the equilibrium partial pressure of CO is 0.500 atm. What is the partial
pressure of CO2 in the equilibrium mixture?
13-7. Each of the following mixtures was placed in a closed container and allowed to stand.
Which of the mixtures is capable of attaining equilibrium, as expressed by the following
equation: CaCO3(s) CaO(s) + CO2(g). For the solids you may assume that a sufficient
amount is present, if required to reach equilibrium.
a.
pure CaCO3(s).
b.
CaO(s) and a pressure of CO2(g) greater than the value of Kp.
c.
CaCO3(s) and a pressure of CO2(g) greater than the value of Kp.
d.
CaCO3(s) and CaO(s).
e.
pure CO2(g)
f.
CaO(s) and a pressure of CO2(g) less than the value of Kp.
g.
CaCO3(s) and a pressure of CO2(g) less than the value of Kp.
h.
A mixture of CaCO3(s), CaO(s), and CO2(g).
Problem Set 14
CONCEPTS AND SKILLS
14-1. Calculate the reaction quotient, Q, and predict the direction a given reaction composition
must take to reach equilibrium when K is known.
14-2. Given K and all initial concentrations (pressures) of a non-equilibrium composition,
calculate the equilibrium concentrations (pressures) of all species.
PROBLEMS
14-1. Consider the reaction, 2SO2(g) + O2(g) 2SO3(g) for which Kc = 0.154. A system is
prepared by adding 2.00 mol of each gas to an empty 5.00 L container. Calculate the
reaction quotient, Q, and predict the direction of reaction required to reach equilibrium.
14-2. Consider the reaction, 2SO2(g) + O2(g) 2SO3(g) for which Kc = 0.154. A system is
prepared by adding 80.1 g of SO3 to an empty 5.00 L container. Calculate the reaction
quotient, Q, and predict the direction of reaction required to reach equilibrium.
14-3. Consider the reaction, 2SO2(g) + O2(g) 2SO3(g) for which Kp = 4.09 x 10-2. A system
is prepared by adding 0.500 atm of all three gases to an empty 5.00 L container. (a)
Calculate the reaction quotient, Q, and predict the direction of reaction required to reach
equilibrium. (b) Does the total system pressure increase or decrease by the time the
system reaches equilibrium?
14-4. Consider the reaction, A(g) + B(g) P(g) + Q(g), for which Kc = 64.0. 3.00 mol of both
P and Q are added to an empty 10.0 L container. (a) Predict the direction of reaction. (b)
Calculate the concentrations of all four gases at equilibrium. (c) Verify your
concentrations in (b) by using them to calculate the value of Kc.
14-5. Consider the reaction, CO(g) + H2O(g) CO2(g) + H2(g), for which Kc = 4.06. A 10.0-L
container is filled with 2.00 mol each of CO and H2O and with 1.00 mol each of CO2 and
H2. (a) Predict the direction of reaction. (b) Calculate the concentrations of all four gases
at equilibrium. (c) Verify your concentrations in (b) by using them to calculate the value
of Kc.
14-6. Consider the reaction, A(s) B(s) + Q(g), for which Kp = 1.50 at 298.15 K. 2.00 mol
each of A(s, 50.0 g/mol) and B(s, 35.0 g/mol) are placed in an otherwise empty 10.00 L
container. (a) What is the final equilibrium pressure of Q(g)? (b) How many moles of
Q(g) were formed? R = 0.08206 L atm mol-1 K-1 (c) What masses of A(s) and B(s) are
present after equilibrium has been established? (d) Determine the molecular weight of
the gas, Q.
Problem Set 1
SOLUTIONS
1-1.
Calculator Skills. Solve the following problems using your calculator. Consult the
calculators users manual if you run into difficulties with these exercises.
A.
1215
B.
5.5 x 104
C.
-2.38
D.
6 x 10-15
E.
8.66 x 10-10
F.
8.592
G.
See your users manual. It is imperative that you know how to do this if your
calculator is programmable.
1-2.
Algebra: Linear Equations. Solve the following equations for x.

A.
Given:
27 x - 45 = 22
Add 45 to both sides:
27 x = 67
Divide both sides by 27:
x = 2.5
B.
Given:
12 x + 27 = 10 x 6
Subtract 10x from both sides: 2 x + 27 = 6
Subtract 27 from both sides: 2 x = 33
x = -16.5
1-3.
Algebra: Quadratic Equations. Solve the following equations for x.

To solve a quadratic equation, the equation must first be rearranged to the form:
a x2 + b x + c = 0
Once it is in this form, it can be solved one of two ways.
Method 1: Use your programmable calculators polynomial equation solver. (See the
users manual. This method is recommended.
Method 2: Use the quadratic formula. The two roots of a quadratic equation are given by
b b 2 4ac
.
2a
Given:
2x2 = 27 3x
Add 3x to both sides:
2x2 + 3x = 27
Subtract 27 from both sides: 2x2 + 3x - 27 = 0
Identify the coefficients:
a = 2; b = 3; c = -27
x=
A.
Solve (see above): x =

B.
Given:
3 32 4 ( 2 )( 27 )
2 ( 2)
1.0 x 103 =
Multiply both sides by (0.010 x):
3 225 3 15
=
= {4.5 , 3}
4
4
x2
( 0.010 x )
(1.0 x 10 ) ( 0.010 x ) = x
3
Expand the LHS:

1.0 x 105 1.0 x 103 x = x 2
Subtract terms on LHS from both sides: 0 = x 2 + 1.0 x 103 x 1.0 x 105
Identify coefficients: a = 1; b = 10-3; c = -10-5
Solve:
x=
103
(10 )
3
4 (1) 105
2 (1)
103 4.1 x 105

2
103 6.4 x 103

= 3.7 x 103 , 2.7 x 103
x=
2
1-4.
Algebra: Logarithms and Exponentials: Solve the following equations for x.

A.
Given:
ln(2x) = -12.7
Exponentiate both sides:
exp[ln(2x)] = exp[-12.7]
Evaluate both sides:
2x = 3.05 x 10-6
x = 1.5 x 10-6
B.
Given:
37 = 10-3.7x
log[37] = log[10-3.7x]
Take log10 of both sides
Evaluate both sides
1.57 = -3.7 x
Divide both sides by -3.7
x = -0.42
1-5.
Algebra: Powers and Roots: Solve the following equations for x.

A.
Given:
36 = x7
B.
1-6.
Take the seventh root of both sides: 7 36 = 7 x 7

x = 1.67
2.78 = 3 4 x + 2
Given:
Cube both sides:
( 2.78 )

Subtract 2 from both sides:
21.5 = 4x + 2
19.5 = 4x
x = 4.88
4x + 2
Solution. Significant Figures: Solve the following problems, and express them to the
correct number of significant figures.
A.
27.3 x 3342 x 12 = _________
When all operations are multiplication or division, the answer has the same
number of significant figures as the term with the fewest. 12 has only two, so the
answer has two. Answer: 1.1 x 106.
B.
223.5 + 1.232 + 2.323 x 104 = __________
When all operations are addition or subtraction, the answer has the number of
decimals, ones, tens, etc., as the term with the fewest. The best way to visualize
this is to line up the numbers before adding.
223.5
1.232
23230
23454.732
Because the third term has only tens (no ones or decimals), the answer will be
good to the tens place. Answer: 2.345 x 104
C.
D.
(298.43 297.64) ( 8.3145 )
= ____________
122.5
The order of operations is important in this problem. First do the subtraction.
298.43 297.64 = 0.79, which has only two significant digits. The
answer to the remaining multiplication/division problem will therefore have only
two significant digits. Answer: 0.054
1
74231 1
= ________
8.314 323 298
Again, begin by considering the subtraction in parentheses.
1/323 1/298 = 0.003096 0.003356 = -0.00026 (two significant figures).
Therefore the remaining multiplication/division problem has two significant
figures. Answer: -2.3
1-7.
Solution.
A.
1 inch = 2.54 cm (exactly). There are 5280 feet in a mile. A car is traveling at
60.0 miles per hour. Convert this speed to meters per second.
60.0 mi 5280 ft 12 in 2.54 cm m hr min
-1
= 26.8 m s
hr
mi
ft
in
100
cm
60
min
60
s
5
-2
B.
1 atm = 1.01325 bar. 1 bar = 10 Pa. 1 Pa = 1 N m . Pressure is defined as
Force per unit area. If a 101 kg man is standing on a 0.0100 m2 surface what
pressure does he exert on the surface? Express your answer in units of (a) Pa, (b)
bar, and (c) atm. g (acceleration due to gravity) = 9.81 ms-2.
P = F/A. F = mg.
Force of the man = (101 kg)(9.81 m s-2) = 991 kg m s-2 = 991 N (Newtons)
Pressure = F/A = (991 N)/(0.0100 m2) = 9.91 x 104 N m-2 = 9.91 x 104 Pa
In units of bar: (9.91 x 104 Pa) x (1 bar / 105 Pa) = 0.991 bar.
In units of atm: (0.991 bar)(1 atm / 1.01325 bar) = 0.978 atm.
1-8.
Solution.
A.
How many moles are in 64.9 grams of H2O?
MW of H2O is 18.02 g mol-1. n = g/MW = (64.9 g)/(18.02 g mol-1) = 3.60 mol
B.
What is the mass of 2.87 moles of H2SO4?
MW of H2SO4 = 98.08 g mol-1.
m = (n)(MW) = (2.87 mol)(98.08 g mol-1) = 281 g
1-9.
Solution. Dilution. Key concept for dilution problems:

moles of solute before dilution = moles of solute after dilution.
because mol (n) = molarity (M) times volume (V), this leads to
MiVi = MfVf.
A.
How many mL of 12.0 M HCl are required to make 150.0 mL of 0.100 M HCl?
Vi = ???
Mf = 0.100 M
Vf = 150.0 mL
Mi = 12.0 M
Vi = MfVf/Mi = [(0.100 M)( 150.0 mL)]/( 12.0 M) = 1.25 mL
B.
If 25.0 mL of water is added to 50.0 mL 0.250 M HCl, what is the final HCl
molarity?
The final volume of the solution is the sum of the two volumes added:
Vf = 25.0 mL + 50.0 mL = 75.0 mL
Vi = 50.0 mL
Mf = ????
Vf = 75.0 mL
Mi = 0.250 M
Mf = MiVi/Vf = [(0.250 M)( 50.0 mL)]/( 75.0 mL) = 0.167 M
Problem Set 2
SOLUTIONS
2-1.
Review lecture notes.
2-2.
Solution. Because H > 0, more information is required. The solid may be soluble if
H is not too large and the entropy effect (randomization of solute particles in the
solvent) is large enough. If H is large, the solid will not dissolve.
2-3.
Solution. NH3 is polar. CCl4 is nonpolar. Like dissolves like.

A. Water (H2O) is polar: it dissolves in ammonia.
B. Methane (CH4) is nonpolar: it dissolves in carbon tetrachloride.
C. Methanol (CH3OH) is polar: it dissolves in ammonia.
D Hexane (CH3CH2CH2CH2CH2CH3) is nonpolar: carbon tetrachloride.
E. Sodium Chloride (NaCl) is polar: ammonia.
2-4.
Solution. Henrys Law says that the solubility of a gas in a solvent is proportional to its
partial pressure over the solution: Sg = k Pg. In this problem, k = 6.9 x 10-4 M atm-1
(Henrys Law constant), Pg = 0.78 atm (partial pressure of the gas), and the desired
concentration is Sg (solubility of the gas). Substitute and solve:
Sg = (6.9 x 10-4 M atm-1)(0.78 atm) = 5.4 x 10-4 M.
2-5.
Solution. Henrys Law (above) can be rearranged: Pg = Sg / k. Substitute the values

given and solve: Pg = (3.0 x 10-5 M) / (1.04 x 10-3 M atm-1) = 2.9 x 10-2 atm. To convert
to torr, multiply by 760 torr / atm. Pg = (2.9 x 10-2 atm)( 760 torr / atm) = 22 torr.
2-6.
Solution. M = n/V: M = molarity (mol L-1); n = mol; V = volume (L)

Recall that n = m/W where m = mass, and W = molecular weight.
W, the molar mass of CaCO3 = (40.08) + (12.01) + 3(16.00) = 100.09 g mol-1.
V is given: 100.0 L.
M is given: 0.250 mol L-1.
Rearranging the first equation: n = MV
Substituting for n: (m/W) = MV
Multiplying through by W: m = WMV, and watching unit conversions:
m = (100.09 g mol-1)[( 0.250 M)(mol L-1 / M)][(100.0 mL)(1 L / 1000 mL)]
m = 2.50 g
2-7.
Solution. Because the final number of moles of solute must equal the initial number of
moles, and n = MV, MiVi = MfVf. Rearrange the equation to isolate the desired quantity,
Vi: Vi = (MfVf)/( Mi). All quantities on the right side of the equation are given in the
problem and can be substituted directly.
Vi = [(0.125 M)( 1.000 L)]/(18.0 M) = 0.00694 L = 6.94 mL.
Problem Set 3
SOLUTIONS
3-1.
Solution. 37.0 g of CaCl2 are dissolved into 37.0 mol of water. The density of the
resulting solution is 1.12 g/mL.
A.
mass percent of CaCl2.
mol H2O = (m)(MW) = (37.0 mol)(18.02 g mol-1) = 667 g
total mass = 37.0 g + 667 g = 704 g
mass % = [m(CaCl2) / total mass] x 100 = (37.0 g)/(704 g) x 100 = 5.26%
B.
parts per million of CaCl2
ppm = [m(CaCl2) / total mass] x 106 = 5.25 x 104 ppm
C.
parts per billion of CaCl2
ppb = [m(CaCl2) / total mass] x 109 = 5.25 x 107 ppm
D.
MW of CaCl2 = 111.0 g mol-1
mol CaCl2 = (37.0 g)/(111.0 g mol-1) = 0.333 mol
mol fraction of H2O = XH2O [mol (H2O)] / (total mol) = (37.0 mol)/(37.333 mol)
= 0.991
E.
mole fraction of CaCl2
Total mol = (37.0 mol + 0.333 mol) = 37.3 mol
mol fraction of CaCl2 = [mol (CaCl2)]/[total moles]
XCaCl2 = (0.333 mol)/(37.3 mol) = 0.009
Note that the mol fractions add to equal 1.
F.
molality
m = (mol solute / kg solvent)
From above, mass of solvent = 667 g = 0.667 kg.
From above, moles of solute = 0.333 mol
m = (0.333 mol)/(0.667 kg) = 0.499 m
G.
molarity
Total mass of solution = (mass CaCl2 + mass H2O) = 37.0 g + 667 g = 704 g.
Total volume = (mass)/(density) = (704 g)/(1.12 g mL-1) = 629 mL = 0.629 L.
Molarity = (moles solute) / (Liters solution) = (0.333 mol)/(0.629 L) = 0.530 M
3-2.
Solution. An aqueous solution is 0.231 m (molal) in NaCl. The solution density is 1.034
g/mL.
Recall that molality is (moles solute / kg solvent). Because all concentration units are
ratios, it is legitimate and convenient to assume that you have a solution containing
exactly 1 kg of solvent (the units in the denominator) and m (0.231) moles of solute.
A.
mass percent of NaCl
MW of NaCl = 57.44 g mol-1
mass of NaCl = (0.231 mol)(57.44 g mol-1) = 13.5 g
total mass = (13.5 g + 1000.0 g) = 1013.5 g
mass percent of NaCl = (13.5/1013.5) x 100 = 1.33%
B.
parts per million of NaCl
ppm of NaCl = (13.5/1013.5) x 106 = 1.33 x 104
C.
parts per billion of NaCl
ppb of NaCl = (13.5/1013.5) x 109 = 1.33 x 107
D.
mole fraction of NaCl
moles of water = (1000. g)/(18.02 g mol-1) = 55.49 mol
total moles = (55.49 mol + 0.231 mol) = 55.725 mol
mol fraction of NaCl = XNaCl = (0.231 mol)/( 55.725 mol) = 0.00414
E.
XH2O = (55.49 mol)/(55.725 mol) = 0.996
F.
molarity
From above: total mass = 1013.5 g
mol solute = 0.231 mol
Volume = m/d = (1013.5 g)/(1.034 g mL-1) = 980.2 mL = 0.9802 L
Molarity = mol solute / volume solution = (0.231 mol) / (0.9802 L) = 0.236 M.
3-3.
Solution. An aqueous solution is 0.00150 M (molar) in HCl. The solution density is

0.999 g/mL.
Recall that molarity is (moles solute / L solution). Because all concentration units are
ratios, it is legitimate and convenient to assume that you have a solution containing
exactly 1 L of solution (the units in the denominator) and M (0.00150) moles of solute.
molality
Total mass of solution = d V = (1.0000 L)(0.999 g/mL)(1000 mL/L) = 999 g
MW of HCl = 36.46 g mol-1
mass of HCl = (mol HCl)(MW) = (0.00150 mol)(36.46 g mol-1) = 0.0547 g
mass of H2O = mass of solution mass of solute = 999 g 0.0547 g = 998.945 g
molality of HCl = mol HCl / kg H2O = (0.00150 mol)/(0.999 kg) = 1.50 x 10-3 m
B.
mass percent of HCl
mass percent = (0.0547 g)/(999 g) x 100 = 5.48 x 10-3%
C.
parts per million of HCl
ppm = (0.0547 g)/(999 g) x 106 = 54.8 ppm
D.
parts per billion of HCl
ppb = (0.0547 g)/(999 g) x 109 = 5.48 x 104 ppb
E.
F.
mole fraction of HCl

from above: mass water = 998.945 g
mol water = (998.945 g)/(18.02 g mol-1) = 55.435 mol
total moles = (54.435 + 0.00150) = 54.4365
mol fraction HCl = (0.00150)/(54.4365) = 2.76 x 10-5
mol fraction HCl = (55.435)/(54.4365) = 0.99997 = 1.00 to three significant figures.
3-4.
Solution. PA0 = 28.0 torr. Concentration = 2.00 m. Calculate PA.

Raoults law tells us that PA = XA PA0 . We need to convert the concentration to mol
fraction and then substitute into the equation.
Assume 1 kg of H2O (solvent). There will be 2.00 mol of solute.
Mol of H2O = (1000. g)/(18.02 g/mol) = 55.49 mol water
Total moles = 2.00 + 55.49 mol = 57.49 mol
Mol fraction of water = (55.49 / 57.49) = 0.9652
Substituting values into Raoults Law: PA = (0.9652)( 28.0 torr) = 27.0 torr.
3-5.
Solution. PA0 = 28.0 torr. PA = 24.4 torr.

Raoults law tells us that PA = XA PA0 .
Rearrange and solve for the mol fraction of the solvent. XA = PA / PA0.
XA = (24.4 torr)/(28.0 torr) = 0.871.
Because all mole fractions must sum to exactly 1, Xsolute = 1 0.871 = 0.129.
Problem Set 4
SOLUTIONS
4-1.
Solution. The decrease in freezing point is proportional to the molality of solute.

Tf = Kf m. Kf is for the solvent, and is equal to 1.86 C/m (from table).
The effective molality is 0.300 m, because NaCl is a strong electrolyte that dissociates to
form Na+(aq) + Cl-(aq).
Tf = (1.86 C/m)(0.300 m) = 0.558 C.
The new freezing temperature (Tf) is equal to the normal freezing temperature (Tf)
minus the change (Tf). = Tf = Tf - Tf.
Tf = (0.000 C) (0.558 C) = -0.558 C.
4-2.
Solution. The increase in boiling temperature is proportional to the molality of the

solute. Tb = Kb m. Kb is for the solvent, and is equal to 1.22 C/m (from table).
The effective molality is 3 m, where m represents the nominal molality of undissociated
Ca(NO3)2; this is because Ca(NO3)2 is a strong electrolyte that dissociates to form Ca2+(a
+ NO3-. Rearranging the above equation, 3 m = T/Kb. Therefore, m = T/3Kb.
Substitute and solve: m = (2.50 C )/(3)(1.22 C/m) = 0.683 m.
4-3.
Solution. Osmotic pressure is proportional to the molarity (M) and temperature (T) of
the solution. = MRT. R is the gas constant. Rearrange to get M = /RT.
Substitute and solve: M = (2.54 atm)/(0.08206 L atm mol-1 K-1 )(298 K) = 0.104 M.
4-4.
Solution. Freezing point depression: Tf = Kf m.

First solve for the solution molality.
m = Tf / Kf = (179.8 C 175.6 C)/( 40.0 C/m) = 0.105 m
Next, determine the number of moles of solute (n).
m = (mol solute) / (kg solvent): mol/kg
Multiply the molality by the mass of solvent in kg.
n = (0.105 mol/kg)(26.41 g)(1 kg/1000 g) = 2.77 x 10-3 mol
To determine the MM, divide the solute mass by the number of moles. MM = m/n.
MM = (0.300 g) / (2.77 x 10-3 mol) = 108 g mol-1.
4-5.
Solution. Osmotic pressure, = MRT, where M is the solution molarity, R is the gas
constant (0.0821 L atm mol-1 K-1) and T is the absolute temperature (K). First calculate
the molarity of the solution by rearranging the above equation, then substituting and
simplifying. Be sure to convert pressure from Torr to atm.
M = / RT = (8.96 Torr)(1 atm / 760 Torr)/[( 0.0821 L atm mol-1 K-1)(298.15 K)]
Molarity = 4.816 x 10-4 M
Next, calculate number of moles of solvent: Molarity = n / V, so n = MV
Moles: n = (4.816 x 10-4 mol/L)(0.500 L) = 2.408 x 10-4 mol
Finally, use n = m/MM (mass divided by molar mass). Rearrange: MM = m/n.
Substitute and evaluate: MM = (10.25 g)/(2.408 x 10-4 mol) = 4.26 x 104 g mol-1.
Problem Set 5
SOLUTIONS
5-1.
Solution. The four factors that affect reaction rates are concentration, temperature,
catalysts, and surface area. 1. In general, increasing concentrations of the reactants will
increase the reaction rate. 2. Increasing the temperature of reaction increases the rate of
reaction. A temperature increase of 10 K often doubles the rate of reaction. 3. Catalysts
[chemical species that do not appear in the overall reaction equation] can speed a
chemical reaction. 4. The greater the surface area available, the faster the reaction rate.
For the next two problems, the following definitions are applied. For a reaction, aA + bB
pP, the average rate of disappearance of A is given by [A]/t;
the average rate of disappearance of B is given by [B]/t,
and the average rate of appearance of product is given by +[P]/t.
These three rates are related through the overall rate of reaction (v), which is given by
1 [ P ] 1 [ A] 1 [ B ]
v=
=
=
.
p t a t b t
5-2.
Solution. 3A + 2B 4D + F. The rate of disappearance of A is given as 3.30 x 10-2 M

s-1. (a) The overall rate can be written as v = (1/3)(- [A]/T). Substituting the value
given, v = (3.30 x 10-2 M s-1)/3, so v = 1.10 x 10-2 M s-1. (b) The rate of disappearance of
B is related to the overall rate by the equation, v = (1/2) (-[B]/T), so -[B]/T = 2 v =
2.20 x 10-2 M s-1. (c). The rate of appearance of D is related to the overall rate by the
equation, v = (1/4) ([D]/T), so ([D]/T) = 4 v = 4.40 x 10-2 M s-1. (d). The rate of
appearance of F is related to the overall rate by the equation, v = (1/1) ([F]/T), so
([F]/T) = 1 v = 1.10 x 10-2 M s-1.
5-3.
Solution. C12H24O11 + 25/2 O2 12CO2 + 12H2O. The rate of appearance of CO2 is

given as ([CO2]/T) = 1.800 x 10-4 M s-1. (a) The relationship between the overall rate
of reaction and the rate of appearance of CO2 is v = (1/12) ([CO2]/T). Substituting
values in the problems gives v = (1.800 x 10-4 M s-1)/12, so v = 1.500 x 10-5 M. (b) The
rate of disappearance of C12H24O11 is related to the overall rate by the equation, v =
(1/1)(- [ C12H24O11]/T), so (- [ C12H24O11]/T) = 1 v = 1.500 x 10-5 M. (c) The rate
of consumption of O2 is related to the overall reaction rate by the equation, v =
(1/(25/2))(- [ O2]/T), so (-[ O2]/T) = (25/2) v = 1.875 x 10-4 M. (d) The rate of
appearance of H2O is related to the overall rate by the relationship, v =
(1/12)([H2O]/T), so ([ H2O]/T) = 12 v = 1.800 x 10-4 M.
5-4.
Solution. (a) Definitions. Average rate is the average change in the amount of a
chemical species divided by the time over which the change is measured.
Mathematically, the average rate is given by [A]/t, where [A] = [A]f [A]i, and t =
tf ti. Instantaneous rate is the same as the average rate, except that the time interval is
so short that it is nearly zero. In calculus, this is given by the derivative, d[A]/dt. [You
need not know anything about derivatives in this course.] Graphically, the instantaneous
rate is equal to the slope of the line drawn tangent to the concentration vs. time plot,
intersecting that plot at the specific time of interest. The initial rate is the instantaneous
rate at the beginning of the reaction, i.e., at t = 0. (b) The reaction rate is always largest
at the beginning of the reaction (t = 0).
The following concepts apply to the next two problems. The average rate of
disappearance of a reactant is given by [-[A]/t] = -([A]f [A]i)/(tf ti). The initial and
final data points are specified by each problem. The overall reaction rate is given by v =
(1/a) [-[A]/ t]. For the equation given, a = 2, so the reaction rate is the rate of
disappearance of A divided by 2.
5-5.
Solution. Rate of disappearance of A for the first 200 s = [-[A]/ t] = -(0.0048 M

0.0100 M)/(200 s 0 s) = 2.6 x 10-5 M. Average rate of reaction = (1/a) [-[A]/ t] =
(1/2)(2.6 x 10-5 M), so v = 1.3 x 10-5 M.
5-6.
Solution. Rate of disappearance of A for the last 200 s = [-[A]/ t] = -(0.0031 M

0.0048 M)/(400 s 200 s) = 8.5 x 10-6 M. Average rate of reaction = (1/a) [-[A]/ t] =
(1/2)(8.5 x 10-6 M), so v = 4.25 x 10-6 M.
Problem Set 6
SOLUTIONS
6-1.
Solution. (a) A rate law is an algebraic expression that relates the rate of reaction to the
concentrations of reactants and other relevant chemical species. (b) The rate constant is a
proportionality constant in the rate law expression. (c) It is assumed that the rate is
proportional to the concentrations of the reactants, each raised to some power. v =
k[A]m[B]n. (d) There is no logical relationship between the coefficients in the balanced
equation and the exponents in the rate law. (e) The rate constant, k, is constant only at a
fixed temperature. If the temperature changes, the rate law will change.
6-2.
Solution. The order of reaction in a reactant is the exponent on that reactants

concentration in the rate law. The overall order is the sum of all reactant exponents. (a)
Second order in A. (b) First order in B. (c) Third order overall.
6-3.
Solution. Zero order in B implies that [B] does not appear in the rate law, i.e., that the
rate is independent of the concentration of [B]. Thus, v = k[A]n for the reaction. Note,
however, that some of the reactant, B, must be present for the reaction to proceed.
Consider the following concepts for the next two problems.

The rate of a reaction normally has units of concentration / time or pressure / time. For
the sake of this discussion, we will assume the rate is expressed in concentration / time.
(a) For a given order of reaction, the rate law can be written. For example, for a firstorder reaction, v = k[A].
(b) The rate law can be rearranged algebraically to solve for k, the rate constant. For the
previous first order example, k = v/[A].
(c) By substituting appropriate units in the right side of the expression and then
simplifying, the units of the rate constant can be determined. For the same first order
example,
units of k = {units of v}/{units of [A]}
Substituting: units of k = (concentration time-1)/(concentration)
Simplifying: units of k = time-1.
6-4.
Solution. (a) The units, year-1, represent time-1. These are units for a first order reaction,
as illustrated in the example above. (b) Given units: M-2 s-1. These are the units of a
third order reaction. Justification. Third-order reaction equation: v = k[A]3. Rearrange
to solve for k: k = v/[A]3. Substituting units in the RHS gives: (units of k) = (M
s-1)/(M)3. Simplifying gives (units of k) = M-2s-1.
6-5.
Solution. Follow the procedure outlined before the preceding question. (a) Zero order
rate law: v = k. Rearrange: k = v. Substitute and solve: (units of k) = Ms-1. (b) Second
order rate equation: v = k[A]2. Rearrange: k = v/[A]2. Substitute and simplify: (units of
k) = (M s-1)/(M)2 = M-1 s-1. (c) Fourth order rate law: v = k[A]4. Rearrange: k = v/[A]4.
Substitute units and simplify: (units of k) = (M s-1)/(M)4 = M-3s-1.
The next four problems explore how the reaction rate changes when the concentrations of
one or more reactants are changed. The general procedure is relatively straightforward.
The concentration terms and their exponents are the part of the rate law to be considered.
For example, if the rate law were v = k[A]3[B]4, the part to focus on is [A]3[B]4.
Substitute the factor by which a reactant is being multiplied in place of its original
concentration, then evaluate the results. Example: for the rate law above, the ratio of the
new rate to the old is equal to (factor by which original [A] is multiplied)3(factor for
[B])4. Specifically, if [A] were doubled and [B] were tripled, the new rate would be
(2)3(3)4 = 648 times larger the old rate.
6-6.
Solution. Rate law, v = k[A][B]2. In general: new rate / old rate = (A factor)(B factor)2.
(a) [B] is doubled, so the B factor is 2; A factor = 1 because A is unchanged. New rate =
(1)(2)2 = 4 times the old rate. (b) A factor is 2, B factor is 1. New rate = (2)(1)2 = 2 times
the old rate. (c) A factor is 2 and B factor is 3. New rate = (2)(3)2 = 18 times the old rate.
6-7.
Solution. The approach is the same as in the preceding problem. Note that the
multiplicative factors can be fractions. v = k[A][B]3, so new rate = old rate x (A factor) x
(B factor)3. (a) A factor = 1, B factor is 1/3. New rate = (1) x (1/3)3 = 1/27 of the old
rate. [1/27 0.037]. (b) A factor = 1/3, B factor = 1. New rate = (1/3) x (1)3 = 1/3 of the
old rate. (c) A factor is , B factor is 2. New rate = (1/2) x (2)3 = 4 times the old rate.
6-8.
Solution. These are similar to the last three problems, except that the unknown reaction
order is the exponent in the rate law. (a) (increase in rate) = (multiplicative factor)order.
(a) 3.06 = (1.75)x. x = 2. If you cannot solve this by inspection or trial-and-error, take
the logs of both sides: log(3.06) = x log(1.75). Rearrange to get
x = [log(3.06)] /[log(1.75)] = 2. [Round the exponent to the nearest half integer].
(b) (2.83) = (2)x. Solving via the use of logs gives
x = [log(2.83)] /[log(2)] = 3/2. [Round the exponent to the nearest half integer].
In general, the exponents can be 0, whole integers or half integers. They may also be
negative.
6-9.
Solution. (a) v = k[A]. (b) v = k[B]2. (c) v = k[A][B]..
Problem Set 7
SOLUTIONS
7-1.
Solution. (a) Assumed rate law: v = k[NO]m[H2]n. To find m, use trials 1 and 3, where
[H2] is constant: v3/v1 = ([NO]3/[NO]1)m; substituting, (4.92 x 10-3 Ms-1)/( 1.23 x 10-3
Ms-1) = [(0.20 M)/(0.10 M)]m; simplifying, 4 = 2m; solving, m=2. To find n, use lines 1
and 2 where [NO] is constant: v2/v1 = ([H2]2/[H2]1)n; substituting, (2.46 x 10-3 Ms-1)/
(1.23 x 10-3 Ms-1) = [(0.20 M)/(0.10 M)]m; simplifying, 2 = 2n; solving, n=1. Putting the
parts together, the rate law is, v = k[NO]2[H2]. (b) Rearrange the rate law to solve for k.
k = v/([NO]2[H2]). Substitute values from trial 1 to solve for k: k = (1.23 x 10-3 M s-1)/
[( 0.10 M)2( 0.10 M)]; simplifying, k = 1.23 M-2 s-1. Check and verify the answer by
repeating the calculation using data from trial 2: k = (2.46 x 10-3 M s-1)/[( 0.10 M)2( 0.20
M)]; simplifying, k = 1.23 M-2 s-1. (c) Use the rate law from (a) and the rate constant
from (b), and set the initial concentrations to the value given, 0.125 M. v = k[NO]2[H2];
substituting, v = (1.23 M-2 s-1)(0.125 M)2(0.125 M) = 2.40 x 10-3 M s-1.
7-2.
Solution. (a) Rate law: v = k[A]m[B]n. To find m, use trials 1 and 2: v2/v1 =
([A]2/[A]1)m; substituting, (2.25 x 10-4 Ms-1)/( 1.00 x 10-4 Ms-1) = [(0.60 M)/(0.40 M)]m;
simplifying, 2.25 = (1.5)m; solving, m=2. [Solve for m by inspection, trial and error, or
using logs: log(2.25) = m log(1.5), so m = log(2.25) / log(1.5).] To find n, use lines 2
and 3 where [A] is constant: v3/v2 = ([B]3/[B]2)n; substituting, (1.41 x 10-3Ms-1)/ (2.25 x
10-4 Ms-1) = [(0.75 M)/(0.30 M)]m; simplifying, 6.27 = 2.5n; solving, n=2. Putting the
parts together, the rate law is, v = k[A]2[B]2. (b) Rearrange the rate law to solve for k. k
= v/([A]2[B]2). Substitute values from trial 1 to solve for k: k = (1.00 x 10-4 M s-1)/
[( 0.40 M)2( 0.30 M)2]; simplifying, k = 6.94 x 10-3 M-3 s-1. Check and verify by
repeating the calculation using data from trial 2: k = (2.25 x 10-4 M s-1)/[( 0.60 M)2( 0.30
M)2]; simplifying, k = 6.94 x 10-3 M-3 s-1. (c) Use the rate law from (a) and the rate
constant from (b), and set the initial concentrations to the value given, 0.125 M. v =
k[A]2[B]2; substituting, v = (6.94 x 10-3 M-3 s-1)(0.125 M)2(0.125 M)2 = 1.69 x 10-6 M s-1.
7-3.
Solution. (a) Rate law: v = k[A]m[B]n. To find m, use trials 1 and 2: v2/v1 =
([A]2/[A]1)m; substituting, (3.54 x 10-3 Ms-1)/( 1.25 x 10-3 Ms-1) = [(0.50 M)/(0.25 M)]m;
simplifying, 2.83 = (2)m; solving, m = 3/2. [Solve for m by inspection, trial and error, or
using logs: log(2.83) = m log(2), so m = log(2.83) / log(2) = 1.5. Always round to the
nearest half-integer] To find n, use lines 2 and 3 where [A] is constant: v3/v2 =
([B]3/[B]2)n; substituting, (3.54 x 10-3 Ms-1)/ (3.54 x 10-3 Ms-1) = [(0.40 M)/(0.20 M)]m;
simplifying, 1 = 2n; solving, n = 0. [Remember that any number raised to the zero power
is equal to 1.] The reaction is zero order in B, indicating that the rate is independent of
the concentration of B. Putting the parts together, the rate law is, v = k[A]3/2. (b)
Rearrange the rate law to solve for k. k = v/[A]3/2. Substitute values from trial 1 to solve
for k: k = (1.25 x 10-3 M s-1)/( 0.25 M)3/2; simplifying, k = 1.00 x 10-2 M-1/2 s-1. Check
and verify by repeating the calculation using data from trial 2: k = (3.54 x 10-3 M s-1)/
(0.50 M)3/2; simplifying, k = 1.00 x 10-2 M-1/2 s-1. (c) Use the rate law from (a) and the
rate constant from (b), and set the initial concentrations to the value given, 0.125 M. v =
k[A]3/2; substituting, v = (1.00 x 10-2 M-1/2 s-1)(0.125 M)3/2= 4.42 x 10-4 M s-1.
Problem Set 8
SOLUTIONS
8-1.
Solution. The rate of reaction is proportional to the concentration of a single reactant,

raised to the first power. If A is the reactant, the rate law is v = k[A].
8-2.
Solution. (a) [A] is the concentration that corresponds to time, t. k is the rate constant.
[A]o is the initial concentration at t = 0. Typically concentration terms are in M and time
is in s. However, note that the equation applies to pressure, molar, and mass quantities as
well. The general rule is that units for [A] and [A]o must be identical. Time units need
not be in seconds. The units of k for a first-order reaction are time-1, where the time
units must match the units of t. For example, if t is in s, k must be s-1; if t is in yr, k must
be in yr-1. Derivations of the requested equation are as follows.
(b)
(c)
(c)
ln [A] = -kt + ln[A]o

ln [A] ln[A]o = -kt
ln([A]/[A]o) = -kt
ln [A] = -kt + ln[A]o
( kt + ln[ A]0 )
ln A
e [ ] =e
( ln[ A]0 )
ln A
e [ ] = e( kt ) e
Given
Subtract [A]o from both sides
Combine ln terms on LHS: ln(b) ln(a) = ln(b/a)
Given
[ A] = [ A]o e( kt )
[ A] = [ A]o e( kt )
[ A] ( kt )
=e
[ A]
o
Simplify eln(x) = x, rearrange RHS
Exponentiate both sides

Separate RHS: e(a+b) = eaeb
Derived in (c) above
Divide both sides by [A]o
NOTE: You should not need to memorize any of these equations! The first equation,
ln[A] = -kt + ln[A]o is given on exams. The other three can be derived directly from the
given equation.
8-3.
Solution. The most convenient form of the integrated first-order rate law is
Problem 9-2(b)
ln([A]/[A]o) = -kt
Divide both sides by -k
t = -{ln([A]/[A]o)}/k
Substituting values in the problem:
t = -{ln([0.0100 M]/[ 0.100 M]o)}/( 6.22 x 10-4 s-1) = 3701 s
Converting to minutes: (3701 s)(1 min / 60 s) = 61.7 min.
8-4.
Solution. The most convenient form of the integrated rate law is [A] = [A]o e-kt. In this
equation, the pressure, number of moles, or mass (at constant volume) can be used in
place of concentration, p = poe-kt. Substituting values in the problem:
p = (135 torr) exp(-(6.8 x 10-4 s-1)( 1420 s)) = 51.4 torr.
8-5.
Solution. The most convenient form of the integrated first-order rate law is
Problem 9-2(b)
ln([A]/[A]o) = -kt
Divide both sides by -t
k = -{ln([A]/[A]o)}/t
Substituting values in the problem:

k = -{ln([5.4 g L-1]/[ 6.0 g L-1]o)}/( 154.2 min) = 6.83 x 10-4 min-1.
8-6.
Solution. (a) Because V is constant, we can use n = no exp(-kt), in parallel with problem
9-4. Substituting values from the problem:
n = (0.0300 mol) exp(-(6.82 x 10-3 s-1)( 2.5 min x 60 s/min)) = 1.08 x 10-2 mol.
[Note that we converted minutes to seconds to match the units of the rate constant.]
(b) For this part of the problem, the most convenient form of the first order integrated
rate law is ln(n/no) = -kt , so t = -(1/k) ln(n/no) = (-1/(6.82 x 10-3 s-1)) ln((0.0050 mol)/(
0.0300 mol)) = (263 s)(1 min / 60 s) = 4.38 min. (c). The relationship between the rate
constant and half-life for a first-order reaction is ln(2) = kt.
Rearranging, t = ln(2)/k = ln(2)/( 6.82 x 10-3 s-1) = (102 s)(1 min / 60 s) = 1.69 min.
8-7.
Solution. The most convenient form of the integrated rate law is ln([A]/[A]o) = -kt,
which rearranges to give t = -{ln([A]/[A]o)}/k. In the problem, ([A]/[A]o) = 0.625.
Substituting values gives t = -{ln(0.625)}/( 2.83 x 10-2 s-1) = 16.6 s.
8-8.
Solution. (a) The half life of a reactant is defined as the time required for that reactants
concentration to decrease to exactly one-half of its initial value. In algebraic notation,
[A] = [A]o when t = t .
First-order integrated rate law
(b)
ln([A]/[A]o) = -kt
Substitute [A] = [A]o and t = t
ln([[A]o/[A]o) = -kt
ln() = -kt
Simplify argument of ln term
Simplify ln term: ln(1/x) = -ln(x)
-ln(2) = -kt
Multiply both sides by -1.
ln(2) = kt
t = ln(2)/k
Divide both sides by k; rearrange results.
(c) The half life of a first order reaction is independent of concentration, i.e., it is
constant. This is true only for first order reactions. (d) Starting with ln(2) = kt from the
derivation above and dividing both sides by t , we get k = ln(2)/t. Substituting given
values, k = ln(2)/( 25.7 s) = 2.70 x 10-2 s-1. (e) Start with the relationship derived in part
(b): t = ln(2)/k. Substituting the given value of k yields t = ln(2)/( 2.120 x 10-4 yr-1) =
3270. yr. (f) Because 1/8 = ()()() = ()3, it takes three half lives. As an example, if
the half life is 10 s, it would take three half lives, 3(10 s) = 30 s for the reactant
concentration to drop to 1/8 of its original value.
8-9.
Solution. From part (b) of problem 9-8, t = ln(2)/k. Substituting the given value of k,
t = ln(2)/( 5.1 x 10-4 s-1) = 1.4 x 103 s.
8-10. Solution. (a) The plot of [A] vs. t will decrease from its initial value. The plot will be
curved, which is typical of an exponential decay curve. The equation being plotted for a
first order reaction is [A] = [A]o e-kt. A typical concentration vs. time plot is shown in
problem 9-12. The plot of ln[A] vs. t will decrease linearly from its initial value (i.e., it is
a straight line with a negative slope). The equation being plotted is ln[A] = -kt + ln[A]o.
A typical ln[A] vs. t plot for a first order reaction is shown in problem 9-13. (b) The
second plot, ln[A] vs. t can be analyzed to determine both the rate constant and the initial
reactant concentration. The rate constant is determined by calculating the slope of the
ln[A] vs. time plot, and changing the sign. [The slope is equal to k.] The initial reaction
concentration is determined by exponentiating the value of the intercept, [A]o = eintercept.
[The intercept is equal to ln[A]o.]
8-11. Solution. (a) The half life is 20.0 s. Note that the reactant concentration at 20.0 s is
exactly the initial value (at t = 0). (b) Yes the reaction is first order, because there are
multiple pairs of data where the final value is the initial value, and the half-life is
identical for all such sets. The half-life of a first-order reaction is constant, regardless of
the initial concentration. Pairs of times (in s) from the data for which the final
concentration is reduced to the initial value include: (0.0, 20.0), (5.0, 25.0), (10.0,
30.0), (15.0, 35.0), (20.0, 40.0), (25.0, 45.0), and (30.0, 50.0). Together, these confirm
that the half life is constant (t = 20.0 s), within rounding error.
8-12. Solution. t1/2 = 250 s. Because the reaction is first order (given), the half life will be the
same regardless of the initial concentration. The strategy is to choose a (t1, [A]1)
coordinate from the plot. Then look for the coordinate whose concentration is [A]1: (t2,
[A]1). The half life is the time difference, t2 t1. As an example, the two points might
be: initial = (0 s, 1.0 M) and final = (250 s, 0.5 M); the half life is 250 s. The rate
constant is k = ln(2)/t , so k = ln(2)/(250 s) = 2.77 x 10-3 s-1.
8-13. Solution. (a) Yes, the reaction is first order, because the plot of ln[A] vs. t gives a
straight line. When ln[A] vs. t data are plotted for other orders of reaction, the result is
curved (not straight) line. (b) The slope of the plot is m = (ln([A]2/M) ln([A]1/M))/(t2
t1). Using the data points provided, m = (-4.16 (-0.69))/(1000 s 0 s) = -0.00347 s-1.
The rate constant has the same magnitude as the slope but is opposite in sign [see
problem 9-10(b)], so k = 3.47 x 10-3 s-1. t1/2 = ln(2)/k = ln(2)/( 3.47 x 10-3 s-1) = 200. s.
The following three problems require the combination of the first order integrated rate
law [problem 9-2] with the relation between first order rate constant and half-life. The
problems can be solved in two stepsthe first involving conversion between k and t ,
and the second focusing on solving via the integrated law. [The order of these steps
varies with details of the problem.] Alternately, a combined equation can be derived
from each of the four integrated rate law expressions, and the problem solved in a single
step.
The following chart contains the four equivalent integrated rate laws, where [ln(2)](t/t)
has been substituted in place of kt. Do not memorize these equations; instead, derive
them for use as needed.
First-order Integrated Rate Law Equivalent, substituting k = ln(2)/t

ln [ A] = kt + ln [ A]0

t
ln [ A] = ln ( 2 ) + ln [ A]0
t1
2

[ A]
[ A]
ln
t
= kt
ln
=
ln
2
(
)
[ A]
[ A]
t1
0
2
kt
t
[ A] = [ A]0 e
ln ( 2 )
[ A] = [ A]0 e
[ A]
kt
= e
[ A]
0
t
1
2
ln ( 2 )
t
[ A]
1
2
= e
[ A]
0
8-14. Solution.
Solution 1 [two step sequence].
A.
ln([A]/[A]o) = -kt
Integrated first-order rate law
k = -[ ln([A]/[A]o)]/t
Divide both sides by t
k = -[ln(1/3)]/(2820 s)
Substitute values
Simplify
k = 3.896 x 10-4 s-1
Relate t to k
B.
t = ln(2)/k
Substitute value of k
t = ln(2)/( 3.896 x 10-4 s-1)
t = 1779 s
Simplify
Solution 2 [using the modified integrated rate law with t].

[ A]
t
ln
=
ln
2
Integrated rate law with t1/2
( ) t
[ A]
0
12
t1
t1
ln ( 2 )
=
(t )
A
[
]
ln
[ A]
0

ln ( 2 )
=
( 2820 s ) = 1779 s
ln 1
3
( )
Rearrange to isolate t
Substitute and solve
8-15. Solution. Note that the problem asks what fraction of the reactant will have decayed, not
what fraction of the original will remain. ([A]/[A]o) is the fraction that remains. Because
the fraction decayed plus the fraction remaining must equal 1, the fraction that has
decayed is given by: fraction decayed = 1 [A]/[A]o.
The rate constant is k = ln(2)/t = ln(2)/(11.4 days) = 6.08 x 10-2 day-1. The fraction
remaining is given by [A]/[A] o = exp(-kt) = exp[-(6.08 x 10-2 day-1)( 25.0 days)] = 0.219.
Therefore, the amount reacted is 1 0.219 = 0.781. 78% of the original Ra-223 has
reacted, and only 22% remains.
8-16. Solution. The rate constant is k = ln(2)/t . k = ln(2)/(200 s) = 3.466 x 10-3 s-1. For both
parts of the problem, the equation, ln([A]/[A]o) = -kt is rearranged to give
t = -[ ln([A]/[A]o)]/k. Substitutions are shown below.
(a) t = -[ ln(1/9)]/( 3.466 x 10-3 s-1) = 634 s.
(b) t = -[ ln([0.300 M]/[1.000 M])]/( 3.466 x 10-3 s-1) = 347 s.
8-17. Solution. (a) The two tests for first order reaction include: (1) identifying the half life of
the reaction for a series of initial concentrations; and (2) plotting the data in the form,
ln[A] vs. t. (b) (1) The half-life must be constant, regardless of initial concentration. (2)
The plot of ln[A] vs. t must result in a straight line.
Problem Set 9
SOLUTIONS
9-1.
Solution. Alpha radiation involves expulsion of an alpha particle (He-4 nucleus,

4
2) from the atoms nucleus, decreasing the atomic number by 2 and the atomic
mass by 4. Beta radiation involves expulsion of a high-energy electron (0-1)
from the nucleus, increasing the atomic number by 1, but leaving the mass
unchanged. Gamma radiation involves release of high-energy electromagnetic
waves. These are uncharged, and have no direct effect on the mass or atomic
number of the reactants (00). Alpha particles are the heaviest, and alpha radiation
does not penetrate past the skin; the resulting damage is localized on the skin.
However, if the alpha-emission source is ingested, the internal damage can be
quite severe. Gamma particles are the highest in energy, and penetrate all living
tissueresulting in the most extensive damage among the three kinds of particles.
9-2.
Solution.
name
A. Thorium-234
symbol
B. Carbon-14
14
C. Lead-206
206
D. Beta Particle
234
90Th
C
82Pb
-1
(electron)
9-3.
9-4.
Solution.
210
214
4
A.
84Po
82Pb + 2
B.
209
C.
239
D.
235
83Bi
94Pu
92U
Classification
Alpha Emission
+ 5826Fe 266109Mt + 10n

+ 10n 24095Am +
-1
+ 10n 9038Sr + 14354Xe + 3 10n
Nuclear Fusion
Beta Emission
Nuclear Fission
Solution.
The integrated first-order rate law, substituting mass in place of concentration, is:
m = m0 exp(-kt)
Recall the relationship between half life and rate constant for 1st order: k = ln(2) /
t
Combine the two to get: m = m0 exp(-ln(2) t / t)
Substitute and simplify: m = (95.0 g) exp[-ln(2)( 7.00 day)/(2.35 day)]
m = 12.1 g
9-5.
Solution.
The most direct form of the integrated rate law for calculating elapsed time,
substituting activity a for concentration, [A], is: ln(a/ao) = -kt. Substituting k =
ln(2) / t and rearranging the equation gives: t = - t [ln(a/ao)/ln(2)].
Substitute and simplify: t = -(5715 yr) [ln(4.8/14.8)/ln(2)]
t = 9.3 x 103 yr
9-6.
Solution.
The most direct form of the integrated rate law for calculating elapsed time
(substituting moles, n, in place of concentration) is: ln(n/no) = -kt. Substituting k
= ln(2) / t and rearranging the equation gives: t = - t [ln(n/no)/ln(2)] [Eq. 1]. In
this equation, mole values are for the reactant, 23892U. We must calculate the two
mole quantities for U-238.
The current moles of U-238: n = m/AW
n = (5.51 mg)(kg/1000g) / (238 g/mol) = 2.315 x 10-5 mol
The current moles of Pb-206 = (1.63 mg)(kg/1000g) / (206 g/mol) = 7.91 x 10-6
mol
238
206
4
0
92U
82Pb + 8 2 + 6 -1.
Based on the overall equation (above), the initial moles of U-238 is given by the
sum: current moles of U-238 + current moles of Pb-206, because all current Pb206 nuclei are assumed to have disintegrated from what were originally U-238
nuclei.
no = (2.315 x 10-5 mol) + (7.91 x 10-6 mol) = 3.106 x 10-5 mol
Finally, substitute values into Eq. 1 and simplify.
t = - (4.51 x 109 year) [ln((2.315 x 10-5 mol)/( 3.106 x 10-5 mol))/ln(2)]
t = 1.91 x 109 yr
Problem Set 10
SOLUTIONS
10-1. Solution.
10-2. Solution. (a) For a reaction to occur, molecules must collide with energies greater than
the activation energy, Ea. The fraction of molecules with sufficient energy increases
rapidly with increasing temperature, resulting in many more collisions that effect
successful reactions. (b) Reactions result from collisions. More collisions result in an
increased rate of reaction. For many reactions, the relative orientation of colliding
molecules makes a difference as to whether the two molecules will react. Energies of
colliding molecules must exceed the activation energy for the reaction to take place.
10-3. Solution. The temperature dependence is hidden in the rate constant, k. [See the
following problem.] When the temperature changes, so does the value of kresulting in
a changed reaction rate.
10-4. Solution. Arrhenius Equation: k = A exp(-Ea/RT)
(a1) Increasing A increases the rate. (a2) Increasing Ea decreases the rate. (a3)
Increasing T increases the rate. (b) The ratio of product to reactant concentrations at
equilibrium is not affected by a change in the activation energy. The ratio depends only
on the value of E. (c) With a small energy of activation, nearly all molecules have
enough energy to react; changing the temperature does not make a large difference in the
rate. With large Ea, small changes of T result in large (percentage) changes of in the
number of molecules with enough energy to react. As a result, rates of reactions with
large activation energies are much more sensitive to temperature changes.
10-5. Solution. (a) A catalyst is a chemical species that changes (usually increasing) the rate
of a reaction. It does not show up in the overall reaction equation; i.e. its final
concentration in the reaction mixture is identical to its initial concentration. It can either
be in the same phase (homogeneous) or in a different phase (heterogeneous) than the
reactants. (b) A catalyst increases the rate of reaction by changing the reaction pathway.
The new pathway typically has a lower activation energy. The catalyst first acts as a
reactant in an elementary step of the reaction mechanism; it is subsequently regenerated
as a product. (c) The equilibrium ratio of product to reactant concentrations is not
affected by a catalyst, because that ration depends only on E, and not on the activation
energy. The catalysts speeds up both the forward and reverse reactions without affecting
the balance between equilibrium reactant and product concentrations.
Problem Set 11
SOLUTIONS
11-1. Solution. (a) Overall reaction: Cl2 + CHCl3 HCl + CCl4. (b) Reactants: Cl2 and
CHCl3. Products: HCl and CCl4. Intermediates: Cl and CCl3. Catalysts: none. (c)
Reaction Forward/Reverse Molecularity Elementary Rate Law
i
Forward
unimolecular
v1 = k1[Cl2]
i
Reverse
bimolecular
v-1 = k-1[Cl]2
ii
Forward
bimolecular
v2 = k2[Cl][CHCl3]
iii
Forward
bimolecular
v3 = k3[Cl][CCl3]
11-2. Solution. The molecularity indicates the number of atoms or molecules in the
elementary step. The elementary rate law is equal to the elementary rate constant times
the concentration of each reactant, raised to the power equal to its coefficient in the
elementary reaction equation.
Reaction Forward/Reverse Molecularity Elementary Rate Law
i
Forward
unimolecular
v1 = k1[A*]
i
Reverse
bimolecular
v-1 = k-1[B][C]
ii
Forward
bimolecular
v2 = k2[D][E]
ii
Reverse
bimolecular
v-2 = k-2[F][G]
iii
Forward
termolecular
v3 = k3[Br]2[Xe]
iii
Reverse
bimolecular
v-3 = k-3[Br2][Xe*]
11-3. Solution. The rate determining step is the step in the reaction mechanism that is
significantly slower than all other mechanistic steps. When such a step can be identified,
the overall rate of reaction is well approximated by the elementary rate of the slow step.
11-4. Solution.
(1) NO2 + NO2 NO3 + NO

(slow, k1)
(fast, k2)
(2) NO3 + CO NO2 + CO2
(a) Adding the two elementary steps gives NO2 + CO NO + CO2, which is the overall
reaction equation. NO3 is an intermediate in the mechanism. (b) Because the first step is
slow, it is rate determining. As a result the overall rate of reaction is equal to the rate of
the rate determining step. v = v1 = k1[NO2]2. (c) The mechanism is consistent with
experiment because the calculated rate law is consistent with the experimentally observed
rate law, i.e., both rate laws are second order in [NO2] and zero order in [CO]. The
empirical rate constant, k, is equal to k1.
(1) NO + NO N2O2
(fast, k1, k-1)
(slow, k2)
(2) N2O2 + Br2 2NOBr
(a) Yes. Adding the two steps gives 2NO + Br2 2NOBr, the overall reaction.
(b) The second step is rate determining, so the overall reaction rate is equal to the
elementary rate of the second step: v = v2 = k2[N2O2][Br2]. Because N2O2 is an unstable
intermediate this is not the final form of the overall rate law. The pre-equilibrium
approximation tells us that the forward and reverse rates of step 1 are equal.
k1[NO]2 = k-1[N2O2], which can be rearranged to give [N2O2] = (k1/k-1)[NO]2.
Substituting this for [N2O2] in the previous expression gives v2 = (k1k2/k-1)[NO]2[Br2].
11-5. Solution.
(c) This is consistent with the laboratory rate law: both are second order in [NO] and first
order in [Br2]. The experimental rate constant, k, represents a ratio of elementary rate
constants, k1k2/k-1.
Problem Set 12
SOLUTIONS
12-1. Solution. For homogeneous gas phase equilibrium systems, Kc is given by product
concentrations in the numerator, each raised to the corresponding coefficient in the
balanced equation, divided by reactant constants, raised to their balanced equation
coefficient.
a. Kc = [N2O4(g)]/[ NO2(g)]2
b. Kc = [SO3(g)]2/{[ SO2(g)]2[O2(g)]}
c. Kc = [HCl(g)]2/{[ H2(g)][Cl2(g)]}
d. Kc = {[HCl(g)]2[Br2(g)]}/{[HBr(g)]2[Cl2(g)]}
12-2. Solution. The equilibrium constant expression for the reaction given is
Kc = [NH3]2/{[N2][H2]3}.
To use this expression, concentrations must first be calculated by dividing the number of
moles (given) by the volume (given). The resulting concentrations are: [NH3] = 0.113
M, [N2] = 0.602 M, and [H2] = 0.420 M. Substituting these values into the expression
above gives, Kc = (0.113)2/{(0.602)(0.420)3} = 0.286.
12-3. Solution. a. The reactants dominate the reaction mixture because K << 1. b. The
products are predominant because K >> 1. c. Neither. Reactant and product
concentrations are nearly equal, because the value of K is close to 1.
For the next two problems, the following principles apply.

A. When all coefficients of a balanced reaction equation are multiplied by a constant, the
equilibrium constant of the modified equation is equal to the old equilibrium
constant raised to the constant power.
B. When a balanced equation is reversed, the equilibrium constant of the modified
equation is equal to the reciprocal of the original equilibrium constant.
C. When two balanced equations are added to give a third equation, the equilibrium
constant of the third equation is equal to the product of equilibrium constants of
the two original reactions.
12-4. Solution.
Reaction
Kc
K1
1 A(g) + 2B(g) 2C(g)
2 2C(g) + D(g) A(g) + 2G(g) K2
a.
b.
3A(g) + 6B(g) 6C(g).

The coefficients of reaction (1) are multiplied by 3.
The new equilibrium constant is K13.
A(g) + 2G(g) 2C(g) + D(g)
Reaction (2) is reversed.
c.
d.
The new equilibrium constant is 1/K2 = K2-1.

A(g) + G(g) C(g) + D(g)
The coefficients of (b) are multiplied by .
The new equilibrium constant is sqrt(1/K2) = K2- .
2B(g) + D(g) 2G(g)
Equations (1) and (2) are added to give this net reaction.
The new equilibrium constant is K1K2.
12-5. Solution.
Reaction
Kc
1.0 x 1012
Cl2(g) + Br2(g) 2BrCl(g)
2HBr(g) + Cl2(g) Br2(g) + 2HCl(g) 4.0 x 104
Calculate the value of the equilibrium constant , Kc, for each of the following reactions.
a.
4Cl2(g) + 4Br2(g) 8BrCl(g)
The new equilibrium constant is K14 = (1.0 x 1012)4 = 1.0 X 1048.
b.
2BrCl(g) Cl2(g) + Br2(g)
The new equilibrium constant is 1/K1 = 1/(1.0 x 1012) = 1 x 10-12.
c.
4HBr(g) + 2Cl2(g) 2Br2(g) + 4HCl(g)
The new equilibrium constant is K22 = (4.0 x 104)2 = 1.6 x 109.
d.
Br2(g) + 2HCl(g) 2HBr(g) + Cl2(g)
The new equilibrium constant is 1/K2 = 1/(4.0 x 104) = 2.5 x 10-5.
e.
Cl2(g) + HBr(g) BrCl(g) + HCl(g)
Reactions (1) and (2) are added, then the coefficients of the resulting equation are
multiplied by . The new equilibrium constant is (K1K2) = sqrt[(1.0 x 1012)(4.0
x 104)] = 2.0 x 108.
Problem Set 13
SOLUTIONS
13-1. Solution. Remember to omit pure solids, pure liquids, and liquid solvents from the
equilibrium constant expression.
a.
Kc = [CO2]6/[O2]6 or Kp = P6(CO2)/P6(O2) the solid and liquid are omitted
the solids are omitted
b.
Kc = [CO2] or Kp = P(CO2)
the solvent is omitted
c.
K = [H3O+][ HSO42-]/[ H2SO4]
d.
Kc = [CO2]2/[CO]2 or Kp = P2(CO2)/P2(CO) the solids are omitted
the solvent is omitted
e.
K = [Zn2+]P(H2)/[ H+]2
Note also, pressure must be used for the gas in (e) because concentrations are
used to represent solutes in the equilibrium.
13-2. Solution. The equilibrium constant expression is Kc = [CO2][H2]/{[CO][H2O]}.
To use this equation, concentrations of all species must first be calculated by diving the
number of moles by the volume (5 liters). This calculation gives the following
concentrations: [CO] = 0.00400 M; [H2O] = 0.00430 M; [CO2] = 0.0140 M; [H2] = 0.400
M. Substituting these concentrations into the Kc expression gives
Kc = (0.0140)( 0.400)/{( 0.00400)( 0.00430)}= 326.
13-3. Solution. To begin, calculate the initial concentration of N2O4: (10.0 mol)/(5.00 L) =
2.00 M. Set up a chart to organize your work.
N2O4(g) 2NO2(g)
1 Initial Concentration
2.00 M
0
2 Change (in terms of x)
-x
+2x
3 Equilibrium Concentration (in terms of x) 2.00 - x
2x
4 Given value at equilibrium
0.70 M
Line 1: Include all initial concentrations in units of M, as calculated above.
Line 2: Express the change in concentration in terms of unknown x. Observe that the
coefficient of x must match the coefficient in the balanced equation.
Line 3: Add Lines (1) and (2) to obtain the expression for the equilibrium concentrations.
Line 4: Calculate the concentration of NO2 at equilibrium from the data given: [NO2]eq
= (3.50 mol)/(5.00 L) = 0.70 M.
The values / expressions for NO2 in lines (3) and (4) of the chart must be equal. Set them
equal and solve for x: 2x = 0.70 M, so x = 0.35 M.
From line (3) at equilibrium [N2O4] = 2.00 x. Substituting for x, [N2O4] = 1.65 M.
Kc = [NO2]2/[N2O4]. Substituting values gives Kc = (0.70)2/(1.65) = 0.297.
13-4. Solution. The approach is identical to that of the previous problem. Use a table to
organize your work.
N2(g) 2H2O(g)
2NO(g)
2H2(g)
1 Initial Concentration (M)
0.100
0.0500
0
0.100
2 Change (in terms of x)
-2x
-2x
+x
+2x
3 Equil Conc (in terms of x)
0.100 -2x 0.0500 2x
x 0.100 + 2x
4 Given value at equilibrium (M)
0.0620
Line (1) Calculate all initial concentrations in M: divide the number of moles by the
volume.
Line (2) Express the change required to reach equilibrium in terms of an unknown, x.
Line (3) Add lines (1) and (2) to get the equilibrium concentrations in terms of x.
Line (4) Use the data given to calculate the concentration of NO at equilibrium.
For NO, the expression in line (3) must equal the value in line (4) Set the two equal and
solve for x. 0.100 2x = 0.0620; 2x = 0.100 0.0620; 2x = 0.0380,
x = 0.0190 M.
Substitute this value of x into all expressions in line (3) to get equilibrium concentrations.
[H2] = 0.0500 2(0.0190) = 0.0120 M.
[N2] = x = 0.0190 M
[H2O] = 0.100 + 2(0.0190) = 0.138 M.
For the reaction, Kc = [N2][H2O]2/{[NO]2[H2]2}. Substituting the equilibrium
concentrations: Kc = (0.0190)(0.138)2/[(0.0620)2(0.0120)2] = 654.
13-5. Solution. For this reaction, Kp = P2(NOCl)/{P2(NO)P(Cl2)}.
Rearranging: P2(NOCl) = Kp P2(NO) P(Cl2)
Taking square roots: P(NOCl) = sqrt[Kp P2(NO) P(Cl2)] = P(NO) sqrt(Kp P(Cl2))
Check: pressures must be in atmospheres. They are, so no conversion is necessary.
Substituting: P(NOCl) = (0.095 atm) sqrt[(52.0) (0.171)] = 0.283 atm.
13-6. Solution. For the reaction, Kp = P2(CO)/P(CO2). The equation can be rearranged to
solve for P(CO2) = P2(CO)/ Kp. Because the given pressure is in atm, it can be used
without conversion. P(CO2) = (0.500)2/(167.5) = 1.49 x 10-3 atm.
13-7. Solution. CaCO3(s) CaO(s) + CO2(g).
For this problem it is important to note that the equilibrium constant, Kp, is equal to the
equilibrium pressure of CO2(g). The equilibrium condition is: P(CO2) = Kp, with
some of both solids present. If the pressure of CO2 is less than Kp, the reaction must
shift to the right to reach equilibrium. If the CO2 pressure is greater than Kp, the reaction
must shift to the left.
a. Yes. dissociation of CaCO3(s) continues until the system attains equilibrium.
b. Yes. CaO(s) reacts with CO2(g) until equilibrium is attained (i.e., the pressure of
CO2(g) decreases to the value of Kp).
c. No. Because the pressure of carbon dioxide is greater than Kp, equilibrium can only
be attained if the reaction proceeds to the left. But because no CaO(s) is present, reaction
to the left is impossible.
d. Yes. The reaction proceeds to the right until equilibrium is attained.
e. No. Some CaCO3 must be present in the final equilibrium state. But reaction to the
left to form CaCO3 is impossible because no CaO is present to react with CO2 in the
reverse reaction.
f. No. Some amount of CaCO3 has to be present in the final equilibrium state, requiring
the system to shift to the left. Reaction to the left results in a decrease in the pressure of
CO2. Initially P(CO2) < Kp, and reaction to the moves it further away from the
equilibrium condition.
g. Yes. CaCO3 can dissociate until the pressure reaches the value of Kp.
h. Yes. If P(CO2) < Kp, the forward reaction will occur. If P(CO2) > Kp, the reverse
reaction will occur. Either way, equilibrium will be reached when P(CO2) = Kp.
Problem Set 14
SOLUTIONS
14-1. Solution. To evaluate the reaction quotient, we need concentrations in M. (2.00

mol)/(5.00 L) gives 0.400 M as the initial concentration of each gas. Q =
[SO3]2/{[SO2]2[O2]} = (0.400)2/((0.400)2(0.400)} = 2.50. Because Q > K, the reaction
must proceed to the left, increasing the amount of both SO2 and O2, and decreasing the
amount of SO3.
14-2. Solution. To evaluate the reaction quotient, we need concentrations in M. The
molecular weight of SO3 can be calculated as 80.1 g mol-1. The initial concentration is
therefore: (mass/MW)/(Vol) = [(80.1 g)/(80.1 g mol-1)]/(5.00 L) = 0.200 M. Q =
[SO3]2/{[SO2]2[O2]} = (0.200)2/((0)2(0)} = + (undefined). Because Q > K, the reaction
must proceed to the left. Note: whenever a reactant or product is not initially present,
the reaction mixture must always shift to increase that species.
14-3. Solution. (a) Qp = P2(SO3) / {P2(SO2) P(O2)} = (0.500)2/((0.500)2(0.500)} = 2.00.
Because Qp > Kp, the reaction must proceed to the left. (b) From the balanced equation,
a total of 3 molecules of reactants are produced (2 of SO2 and 1 of O2) for every 2
molecules SO3 lost. Because the reaction shifts to the left, the total number of moles
(molecules) in the system increases. This implies that the total pressure must increase,
because the total pressure increases as the total number of moles increases.
14-4. Solution. (a) Calculate the initial concentrations of P and Q: (3.00 mol / 10.0 L) =
0.300 M. Because A and B are initially absent, the reaction must go to the left,
decreasing P and Q, while increasing A and B.
(b) Create a chart to organize all information in the problem.
Q
A B P
1 Initial Conc (M)
0 0
0.300
0.300
2 Change
+x +x
-x
-x
3 Equilibrium conc (M) x x
0.300 - x 0.300 - x
(1) Record initial concentrations.
(2) Write an expression for the change required to reach equilibrium in terms of an
unknown, x. From (a) the reactants increase (+) and the products decrease (-). The
coefficients of x must be the same as the corresponding coefficients in the balanced
equation, which are all 1 in this reaction.
(3) The equilibrium concentration in terms of x is the sum of lines (2) and (3).
Write the equilibrium constant expression: K = [P][Q]/{[A][B]}.
Substitute the value of K (given) and the expressions for the equilibrium concentrations
in terms of x: 64.0 = (0.300 - x)(0.300 - x)/(x)(x) = (0.300 x)2/x2.
Solve for the unknown, x. From above: 64.0 = (0.300 x)2/x2.
Because the RHS of the equation is a perfect square, we can take the square roots
of both sides: 8.00 = (0.300 x)/x.
Multiply both sides by x: 8.00 x = 0.300 x
Add x to both sides: 9.00 x = 0.300
Divide both sides by 9.00: x = (0.300)/(9.00) = 0.03333 M.

Solve for final concentrations by substituting x into the expressions in line 3 of the table.
[A] = [B] = x = 0.03333 M. [P] = [Q] = 0.300 x = 0.2667 M. (3 significant figures.)
(c). Substituting these concentrations into the expression for Kc gives:
Kc = (0.2667)( 0.2667)/[(0.03333)(0.03333)] = 64.0,
which is identical to the value given in the problem.
Note that if you used rounded values (3 significant figures) in your calculation of K, your
result would be 64.3, which contains a rounding error of 0.3. To prevent such rounding
errors in final answers, it is always wise to use unrounded values generated from
intermediate calculations. Only final answers should be rounded to the correct number of
significant digits.
14-5. Solution. (a) Calculate the initial concentrations of all four gases. For CO and H2O, the
concentrations are: (2.00 mol / 10.0 L) = 0.200 M. For both CO2 and H2, initial
concentrations are (1.00 mol / 10.0 L) = 0.100 M. The expression for the reaction
quotient is: Q = [CO2][ H2]/{[ CO][ H2O]} = (0.100)(0.100)/[(0.200)(0.200)] = 0.250.
Because Q < K, the reaction will proceed to the right, decreasing CO and H2O while
increasing CO2 and H2.
(b) Create a chart to organize all information in the problem.
CO2(g)
H2(g)
CO(g)
H2O(g)
1 Initial Conc (M)
0.200
0.200
0.100
0.100
2 Change
-x
-x
+x
+x
3 Equilibrium conc (M) 0.200 - x 0.200 - x
0.100 + x 0.100 + x
(1) Record initial concentrations.
(2) Write an expression for the change required to reach equilibrium in terms of an
unknown, x. From (a) the reactants decrease (-) and the products increase (+). The
coefficients of x must be the same as the corresponding coefficients in the balanced
equation, which are all 1 in this reaction.
(3) The equilibrium concentration in terms of x is the sum of lines (2) and (3).
Write the equilibrium constant expression: K = [CO2][ H2]/{[ CO][ H2O]}.
Substitute the value of K (given) and the expressions for the equilibrium concentrations
in terms of x: 4.06 = (0.100 + x)(0.100 + x)/(0.200 - x)(0.200 - x)
4.06 = (0.100 + x)2/(0.200 - x)2.
Solve for the unknown, x.
Take square root of both sides:
2.015 = (0.100 + x)/(0.200 - x)
Multiply both sides by (0.200 x) 2.015 (0.200 - x) = (0.100 + x)
Expand left side
0.403 2.015 x = 0.100 + x
Add 2.015x, Subtract 0.100
0.303 = 3.015 x
Divide by 3.015
x = 0.1005
Determine equilibrium concentrations by substituting the value of x into line 3
expressions. [CO] = [H2O] = 0.200 x = 0.0995 = 0.100 M. [CO2] = [H2] = 0.100 + x
= 0.2005 = 0.200 M.
(c). Substituting final concentrations in to the equilibrium constant expression:
Kc = (0.2005)(0.2005)/[(0.0995)(0.0995)] = 4.06.
14-6. Solution. (a) For the reaction, Kp = P(Q), because the solids, A and P are left out of the
equilibrium expression. Because no Q is initially present, the gas will be formed until its
pressure is equal to Kp; the equilibrium pressure of Q is 1.50 atm. (b) From the ideal gas
law, n = pV/RT = (1.50 atm)(10.00 K)/[(0.08206 L atm mol-1 K-1)(298.15 K)] = 0.6131 =
0.613 mol. (c) Because all coefficients in the equation are 1, the formation of one mole
of Q must be accompanied by the gain of 1 mol of B and the loss of 1 mole of A. Use
this information to determine the final number of moles. Finally, multiply by the
molecular weight (given) to get the final mass.
Reactant A(s): 2.00 mol 0.6131 mol = (1.3869 mol)(50.0 g/mol) = 69.345 = 69.4 g. This
is a decrease of 30.655 g from the original 100.0 g of A.
Product B(s): 2.00 mol + 0.6131 mol = (2.613 mol)(35.0 g/mol) = 91.4485 = 91.5 g. This
is an increase of 21.4585 g from the original 70.0 g of B.
(d) The mass difference (30.655 21.4585) = 9.1965 g represents the increase in Q. Its
molecular weight is the mass divided by the number of moles.
MW = (9.1965 g)/(0.6131 mol) = 15.00 g mol-1.

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