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Edvantage The Ten
Edvantage The Ten
– The Ten –
Development Team
Authors
Cheri Smith
Yale Secondary
School District 34 Abbotsford
Gary Davidson
School District 22 Vernon
Megan Ryan
Walnut Grove Secondary
School District 35 Langley
Chris Toth
St. Thomas More Collegiate
Burnaby, British Columbia
Program Consultant
Lionel Sandner
Edvantage Interactive
m=0 g = 133
y = 100 b = 63
k = 27 Hex = # 00553F
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__________________
Unit 3 Gases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Unit 5: Kinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Unit 6: Thermochemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Unit 7: Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
There are many different AP Chemistry review books available that provide you with thousands of questions.
The design of these books is to give you so many questions that as you solve them you gain a false sense of
confidence that you understand the material.
This book does not do that. This book is created specifically for students of the Edvantage Science program. Their
teachers recognize how to best prepare their students and we are happy to support both teachers and students
where ever we can.
We work with teachers who have consistently supported students to be successful in the AP Chemistry exam. These
same teachers have produced the Edvantage Science AP Chemistry 1 and 2 program. This program is the only
AP Chemistry program written specifically for high school students rather than first year University and College
students. As a result, students using this program tend to well in their current AP Chemistry studies.
The Ten is a summary of these teachers’ collective knowledge around how to best prepare students for an exam.
They have identified key questions in each unit that have traditionally been considered difficult and the type of
question you may expect to encounter on the exam.
After solving each problem, you can check your answer at Edvantagescience.com. Look for the course called
Edvantage Science AP Chemistry Test Prep. This course is organized by units and page number. You will be
able to find the worked solution for every question in The Ten book. There will also be other support tools like
quizzes that will provide you with addtional review.
We realize this is a challenging time and are impressed with your ability to be ready for the exam. It shows your
positive attitute, ability to focus and work hard. You should be proud of your accomplishments as you prepare
to complete this course. Good luck on the exam and in your future academic endeavors.
_______________________________________________________________________________________________________________
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
❑ Describe how radiant energy that is quantized is fundamentally different than radiant energy that travels as waves.
❑ State Bohr’s postulates regarding the behaviour of hydrogen’s electron. Define and use the terms stationary states, quantum
number, ground state, and excited states in your description of Bohr’s model of the atom.
❑ Describe Hydrogen’s bright-line emission spectrum and relate this to the stationary states of Bohr’s atomic model.
❑ Given the relevant equations and constants, solve for:
❑ (i) the energy of the photon released when an electron drops from a higher energy orbit to a lower energy orbit in a hydrogen
atom.
❑ (ii) the wavelength of the light emitted when an electron drops from a higher energy orbit to a lower energy orbit in a hydrogen
atom.
❑ Explain why an electron can have only certain stable orbits.
❑ Use De Broglie’s equation to calculate a particle’s wavelength from its mass and its speed.
❑ State, in general terms, Heisenberg’s uncertainty principle.
❑ Define an atomic orbital and distinguish this from an electron orbit.
❑ Each quantum number (1st, 2nd, 3rd) describes a different feature of an electron’s orbital. Name and provide the orbital feature
described by each quantum number.
❑ Relate the total number of orbitals and the number of different orbital shapes to the first (principal) quantum number.
❑ Name the 4th quantum number, provide its two possible values, and state how it is fundamentally different than the first three
quantum numbers.
❑ State the Pauli exclusion principle.
❑ For multi-electron atoms, the sublevels of each principal quantum number have different energies. Explain why this is the case
and relate a sublevel’s energy to its number of orbitals.
❑ State the Aufbau principle and Hund’s rule.
❑ Provide atoms’ electron configurations and orbital diagrams.
❑ Provide ions’ electron configurations and orbital diagrams.
0
0
0 0
2. Silver has two naturally occurring isotopes. Calculate the percent abundances of silver-107 and silver-109 using the following data:
4. Describe what you would expect to see if hydrogen’s visible emission and absorption spectra were superimposed upon each other.
5. If hydrogen’s electron exists in a spherical orbital, why doesn’t this mean that the electron moves around the nucleus in a circle?
6. What is the difference between a 1s orbital and a 2s orbital? What does that difference indicate about an electron possessing
energy equal to n = 2 as compared to n = 1?
7. Describe the two differences between a 2px orbital and a 3py orbital.
8. The lobes of a p orbital disappear at the nucleus. What does this tell us about electrons in p orbitals?
10. The electron configuration for phosphorus, written in core notation, is [Ne] 3s2 3p3. What two things does Hund’s rule tell us about
the three electrons in the 3p sublevel?
Ge
Zn2+
Sr
Br –
Sn
In3+
[Ne] 3s2
[Xe] 6s2 4f 7
(b) Notice where each of these elements is located on the periodic table. Look at the highest energy sublevel being filled (bold type)
in each of the atoms in the table, and identify the four different sections of the periodic table associated with each of these four
sublevels.
13. Consider the following six stable ions: N 3–, O 2–, F–, Na+, Mg 2+, and Al 3+.
(c) Which neutral atom possesses this electron configuration? What does this suggest about a possible reason for some ion formation?
Alkali Metals Core Notation # Outer Electrons Halogens Core Notation # Outer Electrons
lithium fluorine
sodium chlorine
potassium bromine
rubidium iodine
(b) Consider the numbers of outer electrons present and suggest a reason why elements belonging to the same chemical family
demonstrate similar chemical behavior.
(c) What change occurs in the atoms as we move down each chemical family?
15. (a) On a separate sheet of paper, draw an orbital diagram for an atom of iron with sublevel energy increasing vertically. Arrange
equal energy orbitals in each sublevel horizontally.
(b) Use a highlighter to label the electrons that would be lost when the Fe3+ cation forms.
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
2. Which of the two opposing factors that influence atomic size predominates as we move down a chemical family? What is the
general result?
3. In general, is “effective shielding” most evident going across a period or down a family? How can you tell?
4. Using only the periodic table, rank the following alphabetical list of elements in order of decreasing first ionization energy.
aluminum argon cesium magnesium rubidium silicon sodium sulfu
r
5. Using the periodic table, write the correct number in the space after each statement below:
Members of this chemical family have the highest IE1 in their period. ________
Members of this chemical family have the lowest IE1 in their period. ________
Members of this chemical period have the highest IE1 in their family. ________
Members of this chemical period have the lowest IE1 in their family. ________
7. One of the three properties discussed shows periodic trends when moving across a period or up a family opposite to the other
two properties. Identify this property and the trend observed.
8. Briefly explain why fluorine is a smaller atom than lithium. Consider which factor is predominating across a period.
9. Where are the largest atoms located on the periodic table? Where are the smallest atoms located on the periodic table?
10. The attraction of electrons to the nucleus and repulsion of the electrons between each other both influence the size of an atom or
ion. Use this to complete the following statements.
(a) A cation will always be ________________ (smaller or larger) than its parent neutral atom because of _________________
(increased or decreased) attraction of the outer electrons for the nucleus and _________________ (increased or decreased)
repulsion of the electrons for each other.
(b) An anion will always be ________________ (smaller or larger) than its parent neutral atom because of _________________
(increased or decreased) attraction of the outer electrons for the nucleus and _________________ (increased or decreased)
repulsion of the electrons for each other.
12. Complete the following table by filling in the words “lower left” or “upper right” in the appropriate spaces.
15. Elements with high ionization energies tend to have relatively high electronegativities. What might this indicate about how they
will behave when reacting with low IE and EN elements?
17. Write the electron configuration for nickel and zinc. Use these to explain why an atom of zinc is larger than an atom of nickel.
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
Determine the three-dimensional structures of molecules using Valence Shell Electron Pair Repulsion (VSEPR) Theory.
Determine whether a molecule is polar or non-polar.
Describe, explain, and supply an example of each of the following types of intermolecular forces - dipole-dipole forces, hydrogen
bonds, dispersion forces and ion-dipole forces.
Name and provide examples of hybrid atomic orbitals.
Describe sigma (σ) and pi (π) bonds. Describe single and double bonds in terms of σ and π bonds.
Deduce hybridization, molecular shape and the presence of σ and π bonds from a molecular formula.
Define formal charge and calculate the formal charge of each atom in a species.
Deduce the preferred Lewis structure based on minimizing formal charge.
O
F F
S
F F
(b)
F Xe F
(a) CCl4
(b) PF3
(c) SCl2
c) OF2 d) HCN
e) SF6 f) SOF4
4. State the shape and the central atom hybridization for each of the structures.
7. Assign formal charges to each atom in each of the following six structures for SCO. Predict which structure is favored.
Which is least likely to form?
8. Draw two structures for SO3, one with an expanded octet and one without. You do not need to show resonance
structures for the non-expanded form. Use formal charges to predict which structure is favored. Check the Internet to
see whether you can find any information indicating that the other structure might, in fact, be favored.
H
H C Cl
Cl
dichloromethane
(b)
Cl C Cl
phosgene
(c)
F F
F S F
F F
sulfur hexafluoride
(d)
F
F F
I
F F
iodine pentafluoride
(b) State the shape and the central atom hybridization for each.
(c) Consider the polarity of the bonds in each molecule and then determine whether there is a molecular dipole.
(d) Indicate the number of sigma and/or pi bonds in each molecule or ion.
SCl2 TeF5−
XeF4 CO3−2
IOF5 IF4+
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
Describe how wavelength, wave frequency and photon energy vary across the electromagnetic (EM) spectrum and across the
visible light portion of the EM spectrum.
Describe how nuclear magnetic resonance (NMR) spectroscopy works, e.g. state what each peak in an NMR spectrum represents.
Describe how infrared (IR) spectroscopy works, e.g. state what each inverted peak in an IR spectrum represents.
Describe how the shielding effect influences the effective nuclear charge and how that in turn affects the force of attraction
between a valence electron and the nucleus as described by Coulombs Law.
Describe how ultraviolet-visible (UV-Vis) spectroscopy works, e.g. state what each peak in a UV-Vis spectrum represents.
Describe how the energy required to eject an electron from its atom is calculated in photoelectron spectroscopy (PES).
Describe how PES works, e.g. state what each peak in a PES spectrum represents.
Identify the element represented by a given PES.
Use PE spectra to illustrate periodic trends in binding energy.
0.06
(a)
0.04
Absorbance
(b)
0.02
0.00
300 400 500 600 700 800 900
Wavelength (nm)
.
1. Which sample absorbed more light?
H He
100 10 1 0.1
Binding energy (MJ/mol)
6. Give three points of comparison between the orbital diagram and the PES for boron.
7. Compare and explain the position of the first peak for each of the elements 1 to 5.
8. Compare and explain the heights of the final peak (farthest right) for each of the elements 1 to 5.
9. Examine the figure above. Use the Q values in Coulomb’s law to explain why the energy associated with the first peak is larger in
neon and smaller in oxygen. Do the same for the third peak referring to both the Q and r values.
10. Examine the figure above. Why are the first and second peaks the same height for all three elements while the third peak heights
vary?
UV/Visible
X-rays
12. The first ionization energies for selected elements from the second period of the periodic table are as follows:
700 nm to 400 nm
400 nm to 10 nm
10 to 0.01 nm
(a) (b)
Relative number of electrons
127 125 9 7 5 2 0
400 200 30 10 3 1
Ionization energy (MJ/mol)
Ionization energy (MJ/mol)
(c) (d)
Relative number of electrons
Relative number of electrons
(c) Sketch the PES spectrum for the atom having 8 fewer protons than this atom. Label the axes clearly and show the approximate
energies.
(d) If photons of wavelength 1.25 x 10–8 m bombarded the original element, which, if any, of the electrons could be emitted?
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
Use Boyle’s Law to calculate the effect of changing the volume of a gas on its pressure or vice-versa (at a constant temperature).
Use Charles’ Law to calculate the effect of changing the temperature of a gas on its volume (at a constant pressure).
Use Guy Lussac’s Law to calculate the effect of changing the temperature of a gas on its pressure (at a constant volume).
Use the Combined Gas Law to calculate a gas’ new temperature, pressure, or volume when the other two are changed.
State the conditions of Standard Temperature and Pressure (STP).
Use the Ideal Gas Law to calculate the temperature, pressure, moles, or volume of a gas when the other three are given.
Derive the other gas laws and the “kitty cat equation” from the Ideal Gas Law.
Define a substance’s boiling point in terms of the substance’s vapour pressure.
Describe and explain the effect of altitude on boiling point.
Describe the effect of intermolecular forces on vapour pressure and boiling point.
State Dalton’s Law of Partial Pressures.
Calculate the partial pressure of a gas collected over water by correcting for the water vapour present.
State 4 postulates of Kinetic Molecular Theory (KMT) pertaining to gases.
Calculate the average kinetic energy and the root mean square velocity of a gas particle, given its temperature.
Define diffusion and effusion.
Use Graham’s law to calculate two gases’ relative rates of diffusion or effusion.
Provide two reasons why gases do not exhibit ideal behaviour.
Describe and explain the effect of pressure and temperature on gases’ deviation from ideal behaviour.
Calculate the partial pressure of a gas from its mole fraction.
2. Jo Bob collects a sample of gas from the exhaust pipe of his sister’s car. The sample contains 1.21 x 1023 molecules of gas at a
pressure of 775 mm Hg and a temperature of 38°C. What is the volume of the gas sample?
3. A 44.8 L sample of gas weighs 128.2 g at a temperature of 273 K and a pressure of 760.0 torr. What is the molar mass of this gas?
4. A 7.50 g sample of lithium metal is dropped into 25.0 mL of 1.5 M hydrochloric acid. What volume of hydrogen gas would be
evolved once the limiting reactant has been consumed? (The reaction is performed at SATP conditions; hence the temperature is
25.0°C and the pressure is 101.3 kPa.)
6. Bonzo lives on the planet X, which has an atmospheric pressure of 164 kPa. A nice day on planet X has a temperature of –36°C. If
Bonzo exhales 11.0 g of carbon dioxide, what is the volume of gas?
7. For an unknown gaseous element, 3.23 g occupy 5.60 L at 153°C and 101.3 kPa.
(a) What is the molar mass of the element?
H2SO4 (aq)
H2
Zinc
9. Nitrogen gas is collected over water at 25.0°C and 14.7 psi. Given that the vapor pressure of water is 23.8 mm Hg at this
temperature, what total volume of gas must be collected to obtain 4.10 g of nitrogen?
10. A mixture of 0.50 mol of hydrogen and 0.25 mol of oxygen in a sealed flask has a total pressure of
6.0 × 101 kPa. Calculate the partial pressure exerted by each of the two gases.
11. A mixture of gases contains 5.00 × 1023 molecules of CO2, 6.00 g of CH4, and 0.300 mol of NH3. The total pressure exerted by the
gases is 80.0 kPa. What is the partial pressure of each gas? Hint: First change all the quantities given into moles.
13. The following system is equilibrated with an atmospheric pressure of 1.00 atm in all parts. A thin layer of catalyst near the opened
valve causes the gases to react to form ammonia. Give the partial pressures of each gas and the total pressure in the system when
the reaction is complete.
2.00 L H2 1.00 L N2
14. The penny coin was removed from circulation in Canada In February of 2014. The United States may soon do the same. The major
reason for this move was the rising value of copper metal. When copper’s value increased, pennies were produced as a zinc slug
with a thin layer of copper plated over top. Zinc reacts readily with hydrochloric acid, while copper does not. A triangular file is
used to nick the edge of a penny to expose the zinc slug below the layer of copper. The zinc reacts with the acid releasing bubbles
from the nicked area until nothing remains but a thin shell of copper. If 0.948 L of hydrogen gas is collected over water at 20.0°C
and a total pressure of 752 mm Hg, determine the percentage by mass of the copper in the 2.586 g penny.
(b) A 3.239 mg sample of the drug is combusted in air to produce 8.785 mg of CO2(g) and 2.160 mg of water vapor. Determine
the percent by mass of carbon and hydrogen in the sample. Assume that any remaining element is oxygen and calculate the
empirical formula.
16. Deep sea scuba divers breathe a gas mixture called heliox. Under very high pressures, the nitrogen in air enters the blood stream
and causes a drunken type of state called nitrogen narcosis. The lack of nitrogen allows divers to descend to very deep depths
without worrying about nitrogen toxicity. A 12.5 L scuba tank contains a helium-oxygen mixture containing 250.0 g of helium and
47.5 g of oxygen at 25°C. Calculate the partial pressure of each of the gases in the tank and determine the total pressure exerted
by the heliox.
18. Explain the general pattern for the values of a and b moving down the noble gas family. (A simple statement of the trend is not an
adequate answer.)
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
Describe what “like dissolves like” means and provide several examples.
List 3 criteria required for a substance to dissolve.
Explain why vitamin A is fat-soluble and vitamin C is water-soluble.
Describe how soaps work.
Calculate the concentration of a solution after it is diluted.
Write dissociation equations for ionic solids.
When an ionic solid is dissolved, relate the concentrations of the dissolved ions to each other and to the concentration of their
parent compound.
Calculate the resulting ion concentrations when solutions are mixed.
Define electrolyte, non-electrolyte, strong electrolyte, and weak electrolyte.
Describe and explain the electrical conductivity of soluble salts, salts with low solubility, weak acids and bases, and strong acids
and bases.
Define a titration.
Perform a titration calculation, e.g. calculate a base’s concentration by knowing the volume and concentration of an acid required
to react completely with a given volume of the base.
Label the burette, the standardized solution (or titrant), the Erlenmeyer flask, the solution of unknown concentration (or analyte)
and the indicator on a diagram of a titration apparatus.
The interactions of solutes and solvents create solutions with a wide range of
useful properties.
2. Explain why water molecules will not surround I2 molecules? What forces must be overcome between each water molecule?
3. Would you expect NaCl to dissolve in oil, which is a non-polar solvent? Explain.
4. Predict whether NaCl would dissolve in NH3 liquid. Draw a diagram to show the forces acting within the solute, the solvent, and
the resulting mixture.
8. Octanol has the formula C8H17OH. Explain why octanol does not dissolve in water.
10. Mothballs are made of naphthalene, C10H8. Will a mothball dissolve better in water or paint thinner? Explain.
11. A student places 10 mL of water and 10 mL of CCl4 into a beaker. Solid iodine is added to the beaker. Explain what you would see
and sketch a diagram of it.
12. Why can a molecule of CCl4 not come between water molecules?
13. Explain why NH3 is very soluble in water, but NCl3 is not.
14. When I2 is added to water, it does not dissolve. However, if I2 is added to an aqueous solution of KI, it will dissolve. Use the
following reaction, and your understanding of intermolecular forces to explain the above observations.
I2(s) + I-(aq) ➝ I3-(aq)
H H H
H C C C H
O O O
H H H
Glycerin
17. Ethylene glycol is commonly used as antifreeze. Underline the solvent in which it would be most soluble in each pair below.
H
OH
H C
C H
HO
H
Ethylene glycol
18. List the intermolecular forces present between the following solutes and solvents:
(c) N2 in C8H18
H O H
H C C C H
H H
Acetone
20. A student titrated 10.00 mL HCl with 0.050 M Sr(OH)2. The table below shows the data collected. Calculate the [HCl].
21. A 25.00 mL sample of 0.20 M H2CO3 was titrated with 0.50 M NaOH. What volume of NaOH was required to reach the
equivalence point?
23. In order to standardize a solution of NaOH, 0.18 g of oxalic acid, H2C2O4· 2H2O, was dissolved to make 250.00 mL of solution. A
25.00 mL sample of this solution was titrated against 15.25 mL NaOH. Calculate the [NaOH].
24. Aspirin has the formula C9H8O4. Only one of the H atoms is released when it acts as an acid. An aspirin tablet with a mass of 0.50
g was dissolved in water, and titrated with 18.30 mL of 0.10 M NaOH. Calculate the mass of aspirin in the tablet, and then the
percent by mass of aspirin in the tablet.
25. A 250.00 mL sample of Ca(OH)2 was titrated with 7.25 mL 0.10 M HCl. Calculate the mass of Ca(OH)2 present in the solution.
26. A student dissolved 0.1915 g of an unknown acid HA in 10.00 mL of water. This solution was then titrated with 0.100 M NaOH.
The table below shows the data collected. Calculate the molar mass of the acid HA.
Unit 5: Kinetics
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
40
30
20
10
0
0 1 2 3 4
Time (min)
Recall the discussion of the instantaneous rate earlier in this section.
(ii) 1 min
(iv) 4 min
(b) How do these rates compare? What do you suppose causes this pattern?
2. The following systems represent gaseous reactants A (symbolized by ¢) and B (symbolized by n) at a fixed temperature and
volume. The equation for the reaction is A(g) + B(g) → C(g).
Assume the rate law for the reaction is: rate = k[A][B]3
System 1 represents a reaction with a rate of 0.010 mol/L/s. Complete the diagrams for the other systems as follows:
(a) Adding enough particles of A ¢) to System 2 to represent a system that would react with an initial rate of 0.020 mol/L/s.
(b) Adding enough particles of B (n) to System 3 to represent a system that would react with an initial rate of 0.080 mol/L/s.
System 1 System 2 System 3
(a) Calculate the average rate of reaction in moles of HCl consumed/second over the first 50.0 s.
(b) Calculate the mass of strontium consumed in this 50.0 s period.
(c) Why did the volume of gas collected decrease in each increment until 50.0 s?
(d) Why did the volume of gas remain unchanged from 50.0 s to 60.0 s?
1.2
calibration curve
1.0
0.8
Digital
Output of 0.6
Absorbance
0.4
visible
light 0.2
source
filter or coloured photocell 0.0
mirrors, diffraction solution 0.00 0.01 0.02 0.03 0.04 0.05 0.06
lenses grating Concentration of Cu(NO3)2(mol/L)
and slit
A simpli�ed diagram of a colorimeter
A copper sample was reacted with 250 mL of nitric acid by the following reaction:
As the reaction proceeded, small aliquots were removed and placed in a cuvette (the special test tube used to hold a sample in
the spectrophotometer). The cuvettes were then placed in the instrument and the absorbances were recorded as follows:
0 0 0 mol/L
20. 0.40
40. 0.70
60. 0.90
80. 1.00
Find the absorbances on the standard graph and record the corresponding concentrations of the copper(II) ions (equal to the
concentration of Cu(NO3)2) in the table.
(a) Calculate the average rate of the reaction from time 0 s to 80. s in units of M of HNO3(aq)/s.
Continued
(c) What will you observe in the main reaction flask as the reaction proceeds?
5.Use the information in the table below to write the rate-law expression for the reaction, and explain how you obtained your
answer. Determine the rate constant with units.
2 NO(g) + O2(g) → 2 NO2(g)
6. Consider an imaginary reaction: 2 X + Y → Z. Determine the rate law and the rate constant, with units, from the experimental data
in the table below.
Draw graphs of [(CH3)3CBr] vs. time, ln [(CH3)3CBr] vs. time, and 1/[(CH3)3CBr] vs. time. Is the substitution reaction zero, first, or
second order with respect to (CH3)3CBr? What is the value of the pseudo rate constant with units?
1/Concentration (L/mol)
Concentration (mol/L)
ln Concentration
8. The rate constant for the first order conversion of cyclopropane to propene in a laboratory is 9.0 x 10–4 min–1.
(a) What is the half-life of the reaction?
(b) Assuming the initial concentration of the cyclopropane is 1.50 mol/L, what concentration will remain after 51.2 h?
(a) Draw three graphs and determine the rate law expression and the rate constant with units for the decomposition of nitrogen
dioxide.
1/Concentration (L/mol)
Concentration (mol/L)
ln Concentration
(b) How would the straight-line graph change (in general) if:
(i) the initial concentration of the nitrogen dioxide were increased?
10. The half-life for the decomposition of N2O5 under laboratory conditions is 2.0 min.
(a) What is the rate constant for the reaction under these conditions?
(b) What is the concentration of N2O5 270 s after the reaction starts, assuming an initial concentration of 0.180 mol/L?
(c) How much time does it take for the concentration of N2O5 to drop from 0.180 mol/L to 0.100 mol/L?
O(g) + O3(g) → 2 O2(g) (∆H value for entire reaction = –284.6 kJ/mol)
12. The reaction of the iodide ion and the hypochlorite ion is an oxidation-reduction reaction occurring in basic solution:
I–(aq) + OCl–(aq) → IO–(aq) + Cl–(aq) (basic)
The three-step mechanism is represented as follows:
(a) Show how the above steps combine mathematically to give the overall reaction. Identify all intermediates and catalysts.
(Show work directly on the mechanism provided.)
(b) Show that the mechanism provided gives the rate law: rate = k[I–][OCl–][OH–]–1
(Note: Because this redox reaction is occurring in a basic solution, [OH–] can appear in the rate law expression.)
Unit 6: Thermodynamics
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
Differentiate between, and provide examples of, state functions and pathway dependent functions.
State the first law of thermodynamics.
Calculate the change of internal energy (ΔE) of a system from the heat (q) absorbed or released by the system and the work (w)
performed by or on the system.
For a chemical system at constant pressure, calculate ΔE from ΔH and values that allow you to calculate pressure-volume work (w).
State standard state conditions.
Derive a reaction’s ΔH using Hess’ Law of Heat Summation.
Derive a reaction’s ΔH using Standard Enthalpies of Formation.
Derive a reaction’s ΔH using Average Bond Energies.
Define temperature, heat, and specific heat.
Name and describe 3 types of intermolecular forces (IMF’s).
Define heat of fusion, heat of solidification, heat of vaporization, and heat of condensation.
Calculate the heat required to raise the temperature and/or change the state of a given amount of a substance.
Calculate the final temperature when a hotter material and a colder material are combined.
Calculate the heat released or absorbed in a calorimeter when provided with the calorimetric data.
Discuss some advantages and disadvantages of fossil fuels and cite some alternative energy sources.
Define entropy.
Describe some factors that influence a particle’s or compound’s entropy.
Predict whether entropy increases or decreases during certain reactions by using factors that commonly govern entropy change.
Cite the two thermodynamic “drives” that determine an equilibrium’s position (far left, somewhat centered, far right)
Predict an equilibrium’s position from its thermodynamics and vice-versa.
Define a spontaneous process and relate that to chemical equilibrium
2. Polyvinyl chloride is commonly referred to as PVC. It is a polymer produced from a monomer formed by the addition of ethylene
and chlorine gas. Use the following reactions and their enthalpy changes to determine the overall enthalpy change for the PVC
monomer reaction:
H2(g) + Cl2(g) ➝ 2 HCl(g) ΔHf = –184.6 kJ/molrxn
Use the values in the Table Examples of Heats of Formation above to solve the practice problems below:
5. Use the following information along with the tabular data to calculate the molar enthalpy of formation of ZnS(s).
2 ZnS(s) + 3 O2(g) ➝ 2 ZnO(s) + 2 SO2(g) ΔH of= – 878.2 kJ/molrxn
Use the Table Average Bond Energy (KJ/mol) to produce a full thermochemical equation for each of the molecular representations below.
6.
+ ➔ +
H Cl
7. H H H
H—C—C—C—H + 5 O==O 3 O==C==O + 4 H—O—H
H H H
8. H O
H H
H—C—O—H + 1½ O= O O=C=O +
(g) (g) (g) O (g)
H H H
10. A piece of iron metal initially at a room temperature of 21.5°C is left on the window ledge in the lab on a sunny day. It absorbs
862.4 J of heat and warms to 32.5°C. What is the mass of the iron? See Table 4.6.1.
11. A 75.45 g sample of silicon initially at 20.5°C absorbs 1326 J of heat. What is the final temperature of the sample? See Table 4.6.1.
12. Calculate the heat required to change a 55.00 g ice cube at –15.0°C into steam at 125.0°C. (Hint: There should be five different q
values in your calculation.)
13. A 29.65 g solid gold earring at 33.5°C falls from your ear into a thermally isolated 245.0 mL cup of 65.5°C coffee. Use information
from the Table 4.6.1 to determine the final temperature of the earring and the coffee when they reach the same temperature
(thermal equilibrium). Assume the specific heat capacity and the density of the coffee is the same as those of water and that the
final temperature will be between the initial temperatures.
15. What is the final temperature when a 348.00 g block of ice at –44.5°C is added to 95.00 g of steam at 125.5°C in an insulated
system? Assume the final result will be liquid water.
16. When 500.0 mL of 2.00 mol/L Ba(NO3)2 solution at 22.50°C is combined in a coffee cup calorimeter with 500.0 mL of 2.00 mol/L
Na2SO4 solution also at 22.50°C, a white precipitate forms and the temperature of the mixture rises to 25.60°C. Assume the
calorimeter materials absorb only a negligible quantity of heat and the final solution’s density and specific heat capacity are
identical to those of water. Calculate the molar enthalpy of precipitation of BaSO4(s).
17. A coffee cup calorimeter contains 50.00 g of water at 20.73°C. When 2.13 g of NH4NO3 pellets are stirred into the water, the
temperature falls to 17.41°C. Assume the heat capacity of the resulting solution is the same as that of water and that no energy is
absorbed or released from or to the surroundings. Calculate the molar enthalpy of dissolution of ammonium nitrate, a chemical
commonly used in the production of cold packs.
18. Given: 2 HCl(aq) + Ba(OH)2(aq) ➝ BaCl2(aq) + 2 H2O(l) + 118 kJ/molrxn. Calculate the heat released when 300.0 mL of
0.500 mol/L hydrochloric acid is combined with 100.0 mL of 1.00 mol/L of barium hydroxide. Assume that the temperature of
both solutions is initially 21.55°C. The final mixture has a mass of 400.0 g and a heat capacity the same as that of water with
negligible heat “leakage” to or from the system. What is the final temperature of the mixture?
20. Toluene, C7H8 may be tri-substituted with nitro groups, –NO2, to form the explosive, trinitrotoluene or TNT.
A 750.0 mg sample of toluene liquid was placed in a bomb calorimeter with excess oxygen. The heat capacity of the calorimeter
was 22.53 kJ/°C. When the calorimeter was fired, the combustion of the toluene caused the temperature to increase from 23.002°C
to 24.415°C. Calculate ΔH for the reaction:
C7H8(l) + 9 O2(g) ➝ 7 CO2(g) + 4 H2O(l).
21. (a) A standard calibration reaction is used to determine the heat capacity, C, of a bomb calorimeter. The temperature increases
1.275°C because of the input of 14 580 J of energy. What is the heat capacity of the calorimeter?
(b) Use the data in the table of heats of formation (Table 4.5.1) to calculate the ΔHcombustion of methane, CH4(g).
(c) A sample of 1.754 g of methane is combusted in the calorimeter calibrated in part (a). If the initial temperature of the
calorimeter is 20.754°C, what final temperature should be attained?
23. State whether each of the following reactions will achieve equilibrium with a reasonable amount of reactants and products, go
almost to completion, or virtually not occur.
(a) 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g) ΔH = –907.2 kJ/mol
24. For the following reaction, state whether the forward reaction is endothermic or exothermic, given that the two thermodynamic
drives are opposed to each other. Explain your reasoning.
CaCO3(s) CaO(s) + CO2(g)
25. Describe the thermodynamics of a reaction that establishes equilibrium so far toward reactants that it is said to virtually not
occur.
26. The following equilibrium has a reasonable proportion of reactants and products. State
whether entropy is increasing or decreasing during the forward reaction. Explain your
reasoning.
CO2(g) + NO(g) NO2(g) + CO(g) ΔH = +82 kJ/mol
Unit 7: Equilibrium
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
Use Le Chatelier’s principle to describe how an equilibrium system will respond to changing its volume.
Explain in terms of forward and reverse reaction rates how an equilibrium system will respond to changing its volume.
Use Le Chatelier’s principle to describe how an equilibrium system will respond to changing its temperature.
Explain in terms of forward and reverse reaction rates how an equilibrium shifts in response to changing temperature.
Describe the Haber-Bosch Process and discuss how chemists regulate its reacting conditions to optimize its production rate.
State the equilibrium law and determine a reaction’s equilibrium constant (Keq) from its equilibrium concentrations.
Relate a reaction’s equilibrium constant to its equilibrium position.
State the only change of conditions that will change a chemical equation’s equilibrium constant.
Determine the equilibrium expression for a chemical equation.
Determine the equilibrium constant for a chemical equation given the equilibrium constant for the reverse equation or the same
equation with different coefficients.
Determine the direction a system will proceed to achieve equilibrium, given its reactant and product concentrations and its Keq.
Recognize equilibria that do not strictly abide by Le Chatelier’s principle.
Calculate a reaction’s equilibrium constant, given the initial concentrations of the reactants and any one reactant’s or product’s
equilibrium concentration.
Calculate a reaction’s equilibrium concentrations, given its equilibrium constant and the initial concentrations of its reactants.
Calculate a reaction’s initial concentrations, given its equilibrium constant and any one reactant’s or product’s equilibrium
concentration.
Calculate Kp for a gaseous equilibrium, given the partial pressures of its reactants and products at equilibrium or given its Kc.
When the number of shoppers travelling between the two floors on the escalators is equal, the crowd has reached
equilibrium.
1.0
[NO2]
0.8
0.6
[N2O4] 0.4
0.2
0.0
t1 t2
Time
2. Show how the forward and reverse reaction rates respond to a sudden increase in the temperature of the system below at t1. Use
a solid line for the forward rate and a dotted line for the reverse rate. The system restores equilibrium at t2. The arrow diagram on
the right is another way of depicting the same information. You may use it to do your rough work.
Ni(s) + 4 CO(g) Ni(CO)4(g) ΔH = –603 kJ/mol
Ei
Rate
Ef
t1 t2
Time
A flask containing the above equilibrium turns from purple to pink when cooled. State whether the forward reaction is
endothermic or exothermic. Explain how you arrived at your answer.
5. Why is an equilibrium’s endothermic direction more sensitive to temperature changes than its exothermic direction?
6. What conditions of temperature and pressure favor products in the following reaction:
PCl5(g) PCl3(g) + Cl2(g) ΔH = 238 kJ/mol
7. Briefly describe the conflicting factors that chemists face when choosing a temperature to perform the Haber-Bosch process.
8. Consider the system below. When equilibrium is restored, how will the number of each type of molecule and the concentration
of each substance compare to those before the stress was introduced? Complete the following table using the words “decrease,”
“same,” or “increase.”
2 NH3(g) N2(g) + 3 H2(g) ΔH = 92.4 kJ/mol
Decrease Decrease
Volume Temperature
N2
Equilibrium
H2
concentration
NH3
N2
Equilibrium
H2
number
NH3
rf
rr
0
0 5 10 15 20 25 30
Time (s)
10. Nitric acid is produced commercially by the Ostwald process. The first step of the Ostwald process is:
4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g) + energy
In which direction will the above system shift in the following situations:
(a) Some NO is added.
11. A piston supported by gas trapped in a cylinder is a fixed pressure apparatus. As long as the
gas in the cylinder is supporting the same piston then its pressure must be constant because
it is exerting the same force over the same bottom surface of the piston. If the piston weighs
more, then the fixed pressure is greater. Consider the following equilibrium system trapped
in a cylinder:
PCl5(g) PCl3(g) + Cl2(g)
(a) In which direction will the system shift when some weight is added to the piston?
Remove N2 rf decreases
Decrease volume
net forward rx
(compress)
13. Holding the temperature and pressure constant when a reactant or product is added to an equilibrium system is easier said than
done. Some SO3 is added to the following system. Its temperature and pressure are not fixed.
2 SO2(g) + O2(g) 2 SO3(g) + 198 kJ/mol
(a) In which direction will the system shift in response to the added SO3?
(b) In which direction will the system shift in response to the small change in pressure resulting from the added SO3?
(c) In which direction will the system shift in response to the small change in temperature resulting from the increased
pressure?
(d) In which direction will the system's shift in response to the change in temperature resulting from the system’s shift to the
added SO3?
AB
Concentration
B
A
t1 t2
Time
(b) Decrease the volume of the reaction vessel (at a constant temperature)?
17. Can you infer that reactants are favored in the reaction below because Keq < 1? Explain.
C(s) + H2O(g) CO(g) + H2(g) Keq = 0.16
20. Equal volumes of 1.60 M Ag+ and 2.60 M S2O32− were mixed. The [Ag(S2O3)23−] at equilibrium was 0.35 M. Complete the ICE table
below and determine Keq. (Reminder: Whenever you mix aqueous solutions, there is a dilution effect. Mixing equal volumes
doubles the solution’s volume and halves the concentration of both solutes.)
21. A sample of 6.0 g of carbon was placed in a 1.0 L flask containing 1.4 mol O2. When equilibrium is established, 1.2 g of carbon
remains. Determine Keq. (Note: Because carbon is a solid it is crossed out in the ICE table but the moles of carbon consumed must
be calculated — outside the ICE table — to determine the equilibrium concentrations of O2 and CO.)
23. As part of an experiment, 4.00 mol H2, 4.00 mol C2N2, and 8.00 mol HCN are injected into a 2.00 L flask where they establish
equilibrium. What is the [C2N2] when equilibrium is achieved? Keq = 5.00
24. The table below shows the molarity of three gases at equilibrium. The concentration of HCl is then decreased as shown. What is
the [HCl] when equilibrium is re-established?
Ef
26. Some HI is pumped into a flask. At equilibrium, the [HI] = 0.60 mol/L. What was the initial [HI]? Keq = 0.25
27. Some SO2 and O2 are injected into a flask. At equilibrium, the [SO2] = 0.050 M and the [O2] = 0.040 M. What was the
initial [O2]? Keq = 100
Unit 7: Equilibrium.
Upon completion of the questions in this section and checking the worked solutions at edvantagescience.com, you should be able to:
Use the Solubility Table to determine whether an ionic solid is soluble or has low solubility.
Write the formula equation, complete ionic equation, and net ionic equation for a precipitation reaction.
State 3 techniques for identifying ions in solution. Identify what ions might be present in a solution from the results of
precipitation trials, e.g. precipitates with SO42− but not with OH−.
Devise a selective precipitation scheme to separate different types of ions from solution (e.g. SO42− from S2−) by precipitating
them one at a time.
Describe a technique that may be used to identify precipitates.
Describe possible causes of, harms of, and treatments for hard water.
Define the solubility product constant (Ksp).
Determine the Ksp of a compound from its solubility.
Determine the solubility of a compound from its Ksp.
Determine whether a precipitate will form from a solution’s ion concentrations.
Calculate the maximum concentration of any ion that can coexist in a solution containing known concentrations of other ions.
Describe and explain the common ion effect.
Calculate the solubility of a compound in a solution containing a common ion.
A patient must ingest a solution of barium sulfate for the large intestine
(shown here) to be visible on an X-ray. The small solubility product, or Ksp , of
BaSO4 means humans can safely ingest the suspension.
2. Describe a process to individually remove the ions Br−, SO42–, and S2– from a solution. Be sure to list the compounds that you add
in order, and the method of removing the precipitate.
3. Describe a process to individually remove the ions OH−, PO43–, and S2– from a solution. Be sure to
list the compounds that you add in order, and the method of removing the precipitate.
4. Consider a solution that may contain Pb2+, Ag+, and Cu2+. Devise a qualitative analysis scheme to confirm the presence of each ion
in solution. Remove each ion individually from solution.
5. A solution contains carbonate and phosphate ions. How could you remove these two ions individually from solution?
7. A student prepares a saturated solution by dissolving 5.5 × 10–5 mol of Mg(OH)2 in 500. mL of solution.
Calculate the Ksp of Mg(OH)2.
8. A student evaporated 150. mL of a saturated solution of MgC2O4. If 0.16 g of solute remains, calculate the Ksp.
10. What is the concentration of hydroxide in a saturated solution of iron(III) hydroxide? Hint: Write out the dissociation equation
and Ksp expression first. This example is different than the ones shown.
12. Will a precipitate form when 8.5 mL of 6.3 × 10–2 M lead(II) nitrate is added to 1.0 L of 1.2 × 10–3 M sodium iodate?
13. Will a precipitate form when 1.5 mL of 4.5 × 10–3 M ammonium bromate is added to 120.5 mL of 2.5 × 10–3 M silver nitrate?
15. Calculate the maximum [Sr2+] that can exist in solutions of the following:
(a) 0.045 M sodium fluoride (Remember to consider the source of the fluoride ion.)
16. Sodium carbonate may be added to hard water to remove the Mg2+ ions. What mass of sodium carbonate is required
to soften 10.0 L of hard water containing 3.2 × 10–3 M Mg2+? (Assume no volume change occurs.)
17. What is the maximum [Ag+] that can exist in a saturated solution of PbI2?
19. List two substances that would decrease the solubility of Mg(OH)2. Use Le Châtelier’s principle to explain each.
20. List two substances that would increase the solubility of Mg(OH)2. Use Le Châtelier’s principle and a Ksp expression to explain each.
21. Calculate the molar solubility of silver iodate in 0.12 M sodium iodate.
23. Calculate the solubility (in g/L) of barium sulfate in 0.050 M barium nitrate.