Inorganic Chemistry
Attached in next pages are the Syllabi and tests for
1) CHEM 281 Inorganic Chemistry: introduction and the lab
component.
2) CHEM 281 Advanced Inorganic Chemistry: Advanced study of
inorganic concpets and the lab component.
1
CHEM 281 Syllabus
Louisiana Tech University: Chemistry 281 - Section 001, Winter 2013-14, TR
10:00 AM - 11:15 PM CTH 227
Labs W 2:00-06:15 PM CTH 303
Instructor: Dr. Upali Siriwardane
Office: 311 Carson Taylor Phone: 257-4941
Office hours: MWF 8:00 am - 10:00 am;
E-mail: Upali@latech.edu
Tu,Th 8:30-9:30 a.m. 1:00 - 2:00 pm
Course Homepage: Blackboard: http://moodle.latech.edu/ and Follow menu to CHEM 281(001)
Winter 12
Course objective: This is the first inorganic chemistry course designed primarily for chemistry, science and
engineering majors who have an interest in the inorganic materials as it will be applied to future work in
their professional careers. It attempts to give the student a general appreciation of the field of inorganic
chemistry with a working knowledge of certain of its more important phases as summarized in course
syllabus and course calendar.
Text: Chemistry: The Molecular Science
REQUIRED TEXT: Inorganic Chemistry By Peter Atkins, Tina Overton,
Jon Rourke, Mark Weller, Fraser Armstrong, 5th Edition 2010.
OPTIONAL SUGGESTED TEXTS FOR READING:
Inorganic Chemistry, Huheey and Keiter 1993, 4th Edition.
Basic Inorganic Chemistry, Cotton, Wilkinson and Gaus 1995, 3rd Edition.
Inorganic Chemistry, Bowser 1993.
Inorganic Chemistry, Poterfield 1993, 2nd Edition.
Advanced Inorganic Chemistry, Cotton and Wilkinson 1988, 5th Edition.
Supplements: A full copy of slides, my class lectures, homework, exam review guides and sample questions
and answers are available online:
Blackboard: http://moodle.latech.edu/ and Follow menu to CHEM 281(001)
Course Evaluation: The final course grade will be based on a score of 1000 pts. (NO CURVE).
1.
2.
3.
4.
Three in class Exams:
Comprehensive Final Exam:
15 in Class Quizzes:
Group Activity Assignments:
5. 6 Lab experiments & Reports
40% (@ (400/3) pts. each)
Replace the one lowest of the three exams)
10% (@10 pts. each)
20% (@ 25 pts. each)
400 pts.(40%)
30% (@ 50 pts. each)
300 pts.(30%)
1000 pts.(100%)
Course Total
100 pts.(10%)
200 pts.(20%)
Bonus points: (50 maximum make-up pts.)
1. Bonus assignment:
50 pts.
50 pts.
50 pts.
Bonus Total
Class attendance:
2
You should attend all classes regularly and punctually. Attending classes just to take tests on test
days does not reflect the complete learning/participation/experience provided in this course.
The points you earned for the about 15 in-class quizzes and about 10 group activity assignments
reflect your class attendance/participation/experience. Failure to attend classes without proper
excuses will lead to losing points for the in-class quizzes you missed and that may lead to a lower
grade for you in this course.
Grading Policy:
Grading Scale:
A = 100 - 90% B = 89 - 80% C = 79 - 70% D = 69 - 60%
F = below 60%
Grades will be posted on Blackboard:
Grades will be posted under Course Information for CHEM 281 on Moodle. Graded group
activity can be picked up in class or from the 311 Carson Taylor Hall.
Exams: There will be three hourly exams during the class and an optional comprehensive final
exam. Contact me before an exam at 257-4941 if you will miss an exam due to a University
allowed absence. Only University allowed absences will be eligible for making up an exam,
turning in group activity assignments and lab reports late without penalty or dropping a quiz
[bring dated proof within a week of the missed day(s)].
Hourly Exams: January 5, 2013 Test 1 (Chps. 1&,2), January 31, 2014 Test 2 (Chps. 3 &4),
February 28 , 2014, Test 3 ; (Chps. 5 & 6), Comprehensive Final Make Up Exam: February 20,
2014 (10:00-12:15 AM, CTH 122).
NOTE: For all exams you must bring the following: 1) The text book in case instructor allows
using the tables in the book and 2) a Calculator.
Quizzes: There will be 10-15 in-class quizzes -- about one per lecture – worth 10 points each.
Each quiz will consist of 3 simple questions pertaining to the material we have covered on or
before that day. Quiz sheets with the date will be available at the beginning of each class to be
used. Why a quiz every class? 1) this requires you to come to class where you will learn more
than on your own; 2) this assures me that you will be paying attention in class instead of talking
to your neighbor, reading the newspaper, etc.; 3) how well you do on the quiz lets me know
how well you are learning.
Homework Assignments: There will be about 10 Homework Assignments to be completed as
the materials are introduced in the class. Students can work study groups. NOTE: Each student
in the group must turn in their own hand-written copy of the assignment with their name
printed in the upper right hand corner. Your Homework Assignments handed in late (without
justification) will lose 10% of the points per day past the due date. The due date on the
Homework Assignments means that the assignment is due in class on that day at the end of
3
class 11:15 AM. Blank assignments sheets are available on the webpage under homework:
http://www.chem.latech.edu/~upali/chem281/Group-HW.html
Non-graded text book homework: There will also be nongraded text book homework problems
assigned. It is very important that you do the non-graded text book problems because
questions based on these will also appear on the exams. If after attempting on your own, using
solution manual and with your study group you have any trouble with the graded or non-graded
homework problems, you should see me immediately!
Class Discussion: I will be asking questions in class from. You will be able to discuss the
question with other students for a short period of time and answer as a group so tries to sit
together.
Bonus Essay Assignment: There will be one essay assignment. It will be a 5-10 page typed
essay with at least 5 references (original articles-not web links) or equivalent assignment on
some chemistry topic and it will be worth 40 points. I will give you the topic during the first 3
weeks of classes. It can be handed in anytime before/or on February 14, 2012 1 by 11:15 AM.
Helpful Hints for Learning Inorganic Chemistry:
1. Survey the assigned material for overall concepts before lecture-meaning SKIM READ THE
BOOK!
2. Go back and read the same material for comprehension focusing on unclear areas.
3. Work problems within the chapter during this second reading.
4. Go to lecture and take notes.
5. Reread any remaining unclear areas.
6. Work problems, work problems, work problems within and at the end of the chapter.
Work additional problems again and again until you fully comprehend the concept.
7. If you are still unclear about a concept, ask me but NOT on the day of the exam or the day
before the exam (by then it will be too late for you to truly absorb the material).
Outside Class Assistance:
If you can't meet with me during my office hours, then please contact me by e-mail or make an
appointment with me. A couple of days before the exams, I will hand out a study guide (which
will also be posted on the internet at the beginning of the quarter) and will have a review/help
session during class time. If you get a message on your returned group activity assignments or
exams or by e-mail that says to COME SEE ME IMMEDIATELY, do so immediately so that we can
get you on track for a good grade in this course.
Class Rules:
No talking while I am lecturing. Turn cell phones off before entering class. You are expected to
pay attention to my lecture in order to learn the material presented and to complete group
activity assignments on time. If you fail to do so, you will lose points for group activity and all
4
available BONUS points. Instructor only decides who are worthy of bonus points. Any
academic misconduct, whether premeditated or unpremeditated (as defined in the Code of
Student Conduct), will be reported to the Office of the Dean of Students for appropriate actions.
Chapter
Sections & Titles
Pages
Chapter Sections & Titles
Test 1
Chapter 1. Atomic structure
3
The origin of the elements
3
1.1 The nucleosynthesis of light elements
5
1.2 The nucleosynthesis of heavy elements
6
1.3 The classification of the elements
8
The structures of hydrogenic atoms
10
1.4 Spectroscopic information
10
1.5 Some principles of quantum mechanics
11
1.6 Atomic orbitals
12
Many-electron atoms
18
1.7 Penetration and shielding
18
1.8 The building-up principle
20
1.9 Atomic arameters
23
Chapter 2. Molecular structure and bonding
35
Lewis structures
35
2.1 The octet rule
35
2.2 Structure and bond properties
40
2.3 The VSEPR model
45
Valence-bond theory
48
2.4 The hydrogen molecule
48
2.5 Homonuclear diatomic molecules
49
2.6 Polyatomic molecules
49
Molecular orbital theory
52
2.7 An introduction to the theory
52
2.8 Homonuclear diatomic molecules
55
2.9 Heteronuclear diatomic molecules
58
2.10 Bond properties
60
Test 2
Chapter 3.The structures of simple solids
71
The description of the structures of solids
72
3.1 Unit cells and the description of crystal structures 72
3.2 The close packing of spheres
74
3.3 Holes in close-packed structures
76
The structures of metals and alloys
77
3.4 Polytypism
77
3.5 Non-close-packed structures
78
3.6 Polymorphism of metals
79
3.7 Atomic radii of metals
80
3.8 Alloys page
80
Ionic solids
83
3.9 Characteristic structures of ionic solids
84
3.10 The rationalization of structures
89
5
Pages
Chapter 4. Acids and bases
Brønsted acidity
4.1 Proton transfer equilibria in water
4.2 Solvent levelling
4.3 Characteristics of Brønsted acids
4.4 Simple oxoacids
4.5 Anhydrous oxides
4.6 Polyoxo compound formation
Lewis acidity
4.7 Examples of Lewis acids and bases
4.8 Group characteristics of Lewis acids
Reactions and properties of
Lewis acids and bases
4.9 The fundamental types of reaction
4.10 Hard and soft acids and bases
Test 3
Chapter 5. Oxidation and reduction
Reduction potentials
5.1 Redox half-reactions
5.2 Standard potentials
5.3 Trend in Standard potentials
5.4 The electrochemical series
Chapter 6. Physical techniques in
inorganic chemistry
Diffraction methods
6.1 X-ray diffraction
Absorption spectroscopy
6.3 Ultraviolet—visible spectroscopy
6.4 Infrared and Raman spectroscopy
Resonance techniques
6.5 Nuclear magnetic resonance
6.6 Electron paramagnetic resonance
Chemical analysis
6.10 Atomic absorption spectroscopy
6,11 Elemental analysis
6.12 Thermal methods
Magnetometry
111
111
112
115
118
119
122
123
125
125
126
130
130
132
141
142
142
141
144
146
169
169
169
173
173
175
177
177
181
187
187
188
189
190
Laboratory component:
Seven laboratory experiments are selected from following categories depending on student
interest. Specific instructions will be given during the lab on Wendesday 2:00-6:15 pm.
1. Glassblowing
Students make a test tube, connect two straight glass tubes, bend glass to get U trap and
make a T-joint
2. FTIR Spectroscopy Experiments:
Student prepares samples of metal carbonyl compounds and obtain their IR spectra, Rus
gas samples (NH3 and HCL) and solid KBr samples. Learn about FT-IR techniques and
software.
3. NMR Spectroscopy Experiment:
Student learn how to run NMR spectrometer: sample preparation, locking shimming, data
collection. They will interpret the 1H and 13C data they obtain on organic and
organometallic samples.
4. UV-VIS Spectroscopy Experiments:
Students run UV spectra of Ni (en)32+ and other organometallic compounds and learn the
rage of their absorptions and intensities.
5. X-ray Diffraction Experiments:
Students prepare X-ray powder samples and learn how to run the -2 powder
diffractometer and identify peak positions and search match with PDF data base.
Vacuum line Synthesis and Inert atmosphere handling
Students are exposed to handling air sensitive compounds using vacuum line and dry box.
6. Synthesis of Organometallic Compounds
Students are given the procedure Synthesize of CpFe(CO)2C(O)Ph from [CpFe(CO)2]2 ,
Na/Hg amalgam and benzoyl chloride.
7. High Pressure Synthesis
8. Thermal Analysis Experiments:
Thermal Analysis of metals and hydrates of CuSO4.5H2O. They use Both DTA (tin) and TGA
(CuSO4.5H2O )to analyze their samples
9. Atomic Absorption Experiments:
Students prepare sample of Pb and using a calibration determine the concentration of the
sample.
10. GC Analysis
Students run a gas samples containing CH4 and CO2 and they learn to identify gases in the
stream O2, N2 and the CH4 and CO2.
11. GC/MS Analysis
Students are shown the operation of GC/MS and given the spectra of CpFe(CO)2C(O)Ph
and other compounds. They assign the molecular ion fragments to Mass Spectral peaks.
12. Electrochemistry
They conduct as cyclic voltametic analysis of CpFe(CO)2C(O)Ph and other compounds
(ferrocene).
Important Dates During the Winter 2011-12 Quarter:
November 30
Classes begin
December 20
Christmas holiday Begin at the end of classes
January
4
Christmas holiday Ends classes start 8:00 a.m.
6
January
4
Classes resume, 8:00 a.m.
January
16
ML King Jr., holiday
January
17
Classes resume, 8:00 a.m.
February
3
Last day to drop courses or resign with "W" grades
February 17
Mardi Gras holiday begins at the end of classes
January
23
Mardi Gras holiday Ends classes start 8:00 a.m
February 28
Last day of classes
February 29
Grades for graduating students due on BOSS
March
2
Grades “live” on Student BOSS
March
3
Commencement Day
Changes on this syllabus:
Schedules on this syllabus are not contractual and may be changed by the instructor when it becomes
necessary to do so as determined by the instructor. However, any changes that are deemed necessary
to be made will be communicated orally to the students during lecture. Therefore, it is a requirement
that students attend class on time or make themselves responsible for informing themselves of any
changes made by the instructor during lectures.
Last revised: November 30, 2011, Copyright © 2012, Louisiana Tech University, Department
of Chemistry. All rights reserved.
7
Louisiana Tech University Test 1. CHEM 281 (001). Winter 2011.
Name:___________________
1. Explain how the nucleosynthesis of lighter and heavier chemical elements took place in
the Universe.
2. Using the equations: E = -2.178 x 10-18 J [1/n2f - 1/n2i] J,  = hc/E,
Calculate the wavelength of light that can excite the electron in a ground state hydrogen
atom to n = 7 energy level.
3. Calculate the nuclear binding energy per nucleon (MeV per nucleon) of 208 Pb.
Mass defect (m) = Mass of Nuclide - mass of (p + n +e ) amu
Proton mass: 1.00728 amu
Neutron mass: 1.00867 amu
Electron mass: 5.486 X 10-4 amu
931.5 MeV = 1 amu
8
4. Describe the two components of components of wave function,
y

5. Construct a quantum number tree for the principal quantum number n = 3.
6. Calculate the number of total, radial and angular nodes in 4d orbital
# total nodes: _______
# radial nodes: _______
#angular nodes: _______
7. Which radial electron density function correspond to a 3s electron
8. How is Zeff the nuclear charge felt by an electron in a multielectron atom is calculated?
9. Describe the following applied in obtaining an electronic configuration:
a) The Building Up (Auf Bau) Principle:
b) Pauli Exclusion Principle:
9
c) Hunds Rule:
10. Describe the trend of the following atomic properties in the periodic table:
a) Atomic radii
b) Ionic radii
c) First ionization energies
d) Electron affinities
11. Describe following materials in terms of electrons:
a) diamagnetic;
b) paramagnetic;
c) ferromagnetic;
12. Give electronic configurations in the core format of the following:
a) N :
b) Ca:
c) Fe :
d) Fe2+ :
13. Determine the number of unpaired electrons in atoms
a) O :
b) Cr :
c) Fe3+ :
10
14. Which atom has higher first ionization energy, N or O? Give a brief reason.
15. Describe the difference between following types of radii:
a) Covalent Radii:
b) Van der Waals Radii:
c) Metallic Radii:.
d) Ionic Radii:
16. Using Octet Rule and Lewis dot symbols of elements describe why these three types of
bonding is found in chemical substances:
a) Covalent bonding
b) Ionic bonding
c) Metallic bonding
17. Draw a Lewis structure for PCl3 assuming P is the central atom.
18. Draw a Lewis structure for [POCl2]- ion assuming P is the central atom
11
19. Draw the resonance structures of SO2 and calculate the partial bond order between S and
O atoms.
20. How electronegativity difference between two atoms is is used to distinguish following
types of bonding?
a) Non-polar covalent
b) Polar covalent
c) Ionic
12
Louisiana Tech University : Test 2.CHEM 281 (01) Winter 2011. Chapters 2 and 3.
Name:_______________
1. Draw Lewis structures and predict the hybridization on the central atom:
a) SiCl4
b) BF3
c) SF6
d) [Fe(H2O)6]+3
2. Would you expect Be2 to exist? Use a molecular orbital energy diagram to explain your reasoning.
3. What are there any differences in molecular orbital diagrams of B2, C2, N2, O2 and F2?
4. Draw a molecular orbital diagram for O2 determine the bond order and magnetic properties.
5. Assuming that it has similar molecular orbital energies to those of carbon
monoxide, deduce the bond order of the NO+ ion. (show your work)
6. Assuming that it has similar molecular orbital energies to those of
carbonmonoxide, deduce the bond order of the NO- ion. (show your work)
7. Predict the intermolecular forces in following
a) N2
13
b) CO2
c) CCl4
d) H2O
e) HCl
8. What is a crystalline material, describe the bonding and packing in C(s)-diamond and how it is
different from NaCl(s)?
9. What is the coordination number of a metal atom in a face centered cube(FCC) ?
10. Draw a simple cubic (SC) unit cell and label axes (a,b, c )and angles ()?
11. Give the general unit cell dimensions for following crystal systems:
a) Triclinic:
b) Tetragonal:
c) Hexagonal:
a=
a=
a=
b= 
b = 
b= 



c=
c=
c=






12. What are seven crystal systems?
a)
b)
c)
d)
e)
f)
g)
13. Which would you expect to contain ionic bonds, MgCl2 or SC12? Explain your reasoning.
14. Draw pictures of:
14
a) AAAAA.. lose packing to show how a simple cubic (SC) unit cells are created.
b) Draw pictures of ABABABAB.. lose packing to show how a body centered cubic (BCC) unit cells
are created.
15. How do you calculate the packing efficiency (52%) of cubic (SC) of a metal?
16. Calculate the number of atoms in a cubic unit cell of a metal:
a) Simple cubic (SC):
b) Body-centered cubic (BCC)
c) Cubic closest-packed (CCP-FCC)
17. Give coordination number for both anion and cation of the following ionic lattices.
a. CsCl Structure:
b. Rock Salt Structure:
c. Fluorite Structure:
d. Sphalrite Structure:
Show how many ions are per unit cell and show how it agrees with the
formula of the pervoskite structure material, (1-2-3:Y-Ba-Cu)
15
Louisiana Tech University CHEM 281. TEST 3. Chapters 4 & 5. Winter 2011-2012.
Your Name: __________________
1.
ID #:________
Arrange in the following ions in order of increasing acidity: [Al(OH 2)6]2+, [Fe(OH2)6]3+, [Fe(OH2)6]2+.
Give your reasoning.
2. Figure out the driving force for following reactions.
a) Ca(OH)2 + H2SO4
---> CaSO4 + 2H2O
b) Na2CO3 + 2HCl
---> CO2(g) + H2O + 2NaCl
c) Mg + 2HCl
---> MgCl2 + H2
a) __________________________________________
b) __________________________________________
c) __________________________________________
3. Identify the conjugate acid/base pairs in following reactions.
a) CO32- + H2O  HCO3- + OHb) NH3 + HClO4  NH4+ + ClO4Acid1
Base2
Con-base1
Con-acid2
a)
______ ______ ______ ____________________
b)
______ ______ __________________________
4. For each of the following processes, identify the Lewis acids and bases involved and characterize
the process as complex formation or acid–base displacement.
a) SO3 + H2O → HSO4- + H+
b) CH3[B12] + Hg2+ → [B12]+ + CH3Hg+ (B12 designates the cobalt macrocycle vitamin B12)
c) KCl + SnCl2
→ K+ + [SnCl3]–
d) AsF3 (g) + SbF5 (l) → [AsF2]+[SbF6]– (s)
5. Explain the reaction sequence given below in terms of hard and soft Lewis acid-base behavior:
NaBr
NaCN
AuNO3 ---->
AuBr ---->
[Au(CN)2]6. Explain why Na+ prefers F- to I- where as Cu+ prefers I- to F-.
7. Explain the role of Al2Cl6 as a Lewis acid catalyst in Friedel Craft Acylation of benzene. (show the
steps in the reaction).
8. Explain the Lewis acidity trend observed in the following series:
SiI4 > SiBr4 > SiCl4 > SiF4
9. For the redox reaction answer the following:
2Cr + 6HCl(aq) 2CrCl3 (aq) + 3H2(g)
16
OHR:
RHR:
Oxidizing agent:
Reducing agent:
10. Answer the following for the redox reaction that takes place in basic solution:
Al(s) + MnO4-(aq) ----- MnO2(s) + Al(OH)4-(aq) (basic solution)
OHR:
RHR:
Number of electrons transferred:
Net ionic equation:
Spectator ions:
Molecular equation:
11. Using the E0 values given in the table calculate the Eocell for reactions:
Fe(s) + Cu2+(aq)  Fe2+(aq) + Cu(s)
identify following:
a) Eocell;
b) two half reactions;
b) anode;
c) cathode;
d) direction of electron flow through the external wire.
Use Ellingham diagram given for following reactions:
12. According to the Ellingham diagram, under what conditions might C
be expected to reduce FeO to Fe?
13. According to the Ellingham diagram, under what conditions might
aluminum be expected to reduce MgO?
14. According to Ellinham diagram what temperature C expected to
reduce CaO to Ca?
15. According to Ellinham diagram explain why a potential difference need to be applied reduce
Al2O3 to Al in it had to be accomplished at 1000ºC?
17
Table of Selected Standard Potentials at 25°C
Couple
F2(g) + 2e-  2F-(aq)
Ce4+(aq) + e-  Ce3+(aq)
MnO4-(aq) + 8H+ + 5e-  Mn2+(aq) + 4H2O(l)
Cl2(g) + 2e-  2Cl-(aq)
O2(g) + 4H+ + 2e-  2H2O(aq)
[IrCl6]2-(aq) + e-  [IrCl6]3-(aq)
Fe3+(aq) + e-  Fe2+(aq)
[PtCl4]2-(aq) + 2e-  Pt(s) + 4Cl-(aq)
I3-(aq) + 2e-  3I-(aq)
[Fe(CN)6]3-(aq) + e-  [Fe(CN)6]4-(aq)
Cu2+(aq) + 2e-  Cu(s)
AgCl(s) + e-  Ag(s) + Cl-(aq)
2H+(aq) + 2e-  H2(g)
AgI(s) + e-  Ag(s) + I-(aq)
Ni2+(aq) + 2e-  Ni(s)
Fe2+(aq) + 2e-  Fe(s)
Zn2+(aq) + 2e-  Zn(s)
Al3+(aq) + 3e-  Al(s)
Ca2+(aq) + 2e-  Ca(s)
Li+(aq) + e-  Li(s)
18
E° / V
+3.05
+1.76
+1.51
+1.36
+1.23
+0.87
+0.77
+0.76
+0.54
+0.36
0.34
+0.22
0
-0.15
-0.23
-0.44
-0.76
-1.68
-2.87
-3.04