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CHAPTER ONE

Chemistry and Measurement


Matter and Energy - Vocabulary
Chemistry
 Science that describes matter – its properties, the
changes it undergoes, and the energy changes that
accompany those processes
Matter
 Anything that has mass and occupies space.
Energy
 The capacity to do work or transfer heat.
Scientific (natural) law
 A general statement based the observed behavior of
matter to which no exceptions are known.

2
Natural Laws
Law of Conservation of Mass – total
amount of mass remains constant
during a chemical change
Law of Definite Proportions – in a given
chemical compound, the elements are
always combined in the same
proportions by mass

3
Scientific Method
Observation - statement that accurately describes
something seen, heard, tasted, felt, or smelled

Hypothesis - tentative explanations for what we observed


Experimentation - testing of the hypothesis
Data – empirical facts collected during experimentation
*Observation or experiment
Theory - tested explanation of the behavior of nature
Conclusion – statement that is based on what is thought
about a series of observations
Law - generalization based upon the results of many
experiments
4
Three States of Matter

5
Phase Diagram

6
Chemical and Physical Properties
Chemical Properties - chemical changes
 rusting or oxidation
 chemical reactions
Physical Properties - physical changes
 changes of state
 density, color, solubility
Extensive Properties - depend on quantity; i.e.,
volume
Intensive Properties - do not depend on
quantity; i.e., color, temperature, density

7
8
Mixtures, Substances,
Compounds, and Elements

Pure Substance
 matter in which all samples have identical
composition and properties
 Compounds: substances composed of atoms
of two or more elements chemically united in
fixed proportions
 Elements: substances that cannot be
decomposed into simpler substances via
chemical reactions

9
Mixtures, Substances,
Compounds, and Elements
Compounds
 substances composed of two or more
elements in a definite ratio by mass
 can be decomposed into the constituent
elements
 Water is a compound that can be decomposed
into simpler substances – hydrogen and oxygen
 2 H2 O  2 H2 + O 2

10
Mixtures, Substances,
Compounds, and Elements

Mixtures
 composed of two or more substances
 homogeneous mixtures - possess the same
properties throughout the mixture
 heterogeneous mixtures - consists of two
or more regions that differ in properties

11
Rounding
Rules
Off Numbers
Example
1. If the next digit is less than 5, 1.294  1.29
then the previous digit remains the same

2. If the next digit is greater than 5 or 5 followed 1.325001  1.33


by non-zeroes, then the previous digit is 0.999  1.00
increased by one

3. If the next digit is 5 or 5 followed by ALL zeroes, 1.285  1.28


Then the previous digit remains the same if it is even 1.22500  1.22

4. If the next digit is 5 or 5 followed by ALL zeroes, 1.295  1.30


Then the previous digits is increased if it is odd 1.375  1.38
Scientific Notation

Coefficient (any number that’s from ± 1-9)


Exponent (any non-decimal
number)

N. x 10x

General Formula

13
To convert numbers into Scientific
Notation

As you move the decimal point to the left (i.e.,


make the coefficient smaller) the power of ten
(i.e., the exponent) must increase by the same
amount
1750.0 = 1750.0 x 100 = 1.7500 x 103

As you move the decimal point to the right (i.e.,


make the coefficient larger) the power of ten (i.e.,
the exponent) must decrease by the same amount
0.0500 = 0.0500 x 100 = 5.00 x 10-2
14
Significant Digits
Significant digits indicate how accurately
measurements have been made
To find how many significant digits a number
has:
1. Locate the first nonzero digit (start from left to
right), then starting with that digit, count the
number of digits that follow
0.02500

2. zeros at the end of a number that has no decimal


point are not significant 15
Significant Figures
•Any digit that is not zero is significant
1.234 kg 4 significant figures
•Zeros between nonzero digits are significant
606 m 3 significant figures
•Zeros to the left of the first nonzero digit are not significant
0.08 L 1 significant figure
•If a number is greater than 1, then all zeros to the right of
the decimal point are significant
2.0 mg 2 significant figures
•If a number is less than 1, then only the zeros that are at the
end and in the middle of the number are significant
0.00420 g 3 significant figures (4.20 mg)
16
Manipulating Powers of Ten
When multiplying powers of ten, the exponents
are added.
105 x 10-4 = 10 (5+ -4) = 10 1
When dividing powers of ten, the exponents are
subtracted.
104÷ 10-4 = 10 (4- -4) = 108
When raising powers of ten to an exponent, the
exponents are multiplied.
(104)3 = 10 (4x3) = 1012
17
Adding and Subtracting Numbers
When adding or subtracting numbers, your final
answer should have the same number of decimal
places as the number from the problem with the
fewest decimal places
1.7
0. 33
+13.190
15.2 20  15.2
18
Significant Figures
Addition or Subtraction
The answer cannot have more digits to the right of the decimal
point than any of the original numbers.
89.332
+1.1 one significant figure after decimal point
90.432 round off to 90.4

3.70 two significant figures after decimal point


-2.9133
0.7867 round off to 0.79

19
Multiplying and Dividing Numbers
When multiplying or dividing numbers, your final
answer should have the same number of
significant digits as number from the calculation
with the fewest significant digits

1.768 x 1.23 = 2.17464 = 2.17

3.689 ÷ 1.3 = 2.8 3769 = 2.8

20
Significant Figures
Multiplication or Division
The number of significant figures in the result is set by the
original number that has the smallest number of significant
figures
4.51 x 3.6666 = 16.536366= 16.5

3 sig figs round to


3 sig figs

6.8 ÷ 112.04 = 0.0606926= 0.061

2 sig figs round to


2 sig figs
21
Significant Figures
Exact Numbers
Numbers from definitions or numbers of objects are considered
to have an infinite number of significant figures

The average of three measured lengths; 6.64, 6.68 and 6.70?

6.64 + 6.68 + 6.70


= 6.67333 = 6.67= 7
3

Because 3 is an exact number

22
Mixing addition/subtraction with
multiplication and division
Complete all of the addition/subtraction first, then
complete the multiplication/division (round after the
add/sub and after the mult/divs)

1.3456778 +2.8765
1.8

4.2222 = 2.345666 = 2.3


1.8
23
Powers of ten with addition/subtraction
and/or multiplication/division

7.54 x 10-5 (99. x 10200 + 1.25 x 10201)


(1.75x 10-3)3

7.54 x 10-5 (9.9 x 10201 + 1.25 x 10201)


(1.75x 10-3)3

7.54 x 10-5 (11.2 x 10201)


(1.75x 10-3)3
24
Powers of ten with addition/subtraction
and/or multiplication/division

7.54 x 10-5 (11.2 x 10201)


5.36 x 10-9

7.54 x 11.2 x 10-5 x 10201


5.36 10-9

15.755 x 10205

1.58 x 10206
25
SI Base Units
Quantity Unit
Symbol
length meter m
mass kilogram kg
time second s
current ampere
A
temperature Kelvin K
amt. substance mole mol
26
Derived SI Units
Quantity Definition of Quantity SI unit
Area Length squared m2

Volume Length cubed m3

Density Mass per unit volume kg/m3

Speed Distance traveled per unit time m/s

Acceleration Speed changed per unit time m/s2

Force Mass times acceleration of object kg * m/s2


( =newton, N)
Pressure Force per unit area kg/(ms2)
( = pascal,
Pa)
Energy Force times distance traveled kg * m2/s27
2
SI Prefixes (Metric)
Name Symbol Multiplier
mega M 10 6
kilo k 10 3
deka da 10
deci d 10-1
centi c 10-2
milli m 10-3
• micro  10-6
• nano n 10-9
• pico p 10-12
• femto f 10-15

28
Relationships of Some U.S. and Metric
Units

Length
 1 m = 39.37 inches

 2.54 cm = 1 inch

 1 mile = 5280 ft

Volume
 1 liter = 1.06 qt

 1 qt = 0.946 liter

 4 qt = 1 gal

See Table 1.5 for more conversion factors


29
Use of Numbers
Exact numbers
 1 dozen = 12 things for example
Accuracy
 how closely measured values agree with
the correct value
Precision
 how closely individual measurements agree
with each other
30
Accuracy – how close a measurement is to the true value
Precision – how close a set of measurements are to each other

accurate precise not accurate


& but &
precise not accurate not precise

31
The speed of sound in air is about 343 m/s. What is
this speed in miles per hour?

meters to miles
seconds to hours

1 mi = 1609 m 1 min = 60 s 1 hour = 60 min

m 1 mi 60 s 60 min mi
343 x x x = 767
s 1609 m 1 min 1 hour hour

32
The Factor Label Method

9.32 yd  ? mm
3ft 12in 2.54cm 10mm
9.32 yd x x x x  8.52 10 3 mm
1yd 1ft 1in 1cm

33
The Factor Label Method
Express 627 milliliters in gallons.

1L 1.06qt 1gal
627 mL x x x  0.16615 5
1000 mL 1L 4qt
 0.166 gal

34
The Factor Label Method
Express 3.50 (short) tons in grams.

 2000 lb  454 g 
3.50 tons     3178000 g
 ton  lb 
 3.18 x 10 6 g

35
The Factor Label Method
Express 2.61 x 104 cm2 in ft2.

1in 2 1ft
? ft  2.61 10 cm (
2 4 2
) ( ) 2

2.54 cm 12in
 28.0938061 9 ft 2  28.1 ft 2

36
The Factor Label Method
Express 2.61 ft3 in cm3.

12 in 3 2.54 cm 3
? cm  2.61 ft (
3 3
) ( )
1 ft 1 in
 73906.9696 cm  7.39 10 cm
3 4 3

37
Density and Specific Gravity
density = mass
volume
m
d v

Specific gravity = densitysubstance


densitywater

Specific gravity = how dense your substance is


relative to water
38
Density and Specific Gravity
Calculate the density of a substance if
742 grams of it occupies 97.3 cm3.

1 cm  1 mL  97.3 cm  97 .3 mL
3 3

density  m
V

39
Density and Specific Gravity
Calculate the density of a substance if
742 grams of it occupies 97.3 cm3.

1 cm  1 mL  97.3 cm  97 .3 mL
3 3

density  m
V
density  742 g
97.3 mL
density  7.63 g/mL
40
Density and Specific Gravity
Suppose you need 125 g of a corrosive
liquid for a reaction. What volume do
you need?
 liquid’s density = 1.32 g/mL
m m
density  V 
V density
125 g
V  94.7 mL
1.32 g mL 41
Density and Specific Gravity
A 31.10 gram piece of chromium is dipped into a
graduated cylinder that contains 5.00 mL of
water. The water level rises to 9.32 mL. What is
the specific gravity of chromium?
31.10 g
density of Cr 
4.32 mL
 7.19907 g  7.20 g
mL mL
7.20 g mL
Specific Gravity of Cr  g
 7.20
1.00 mL
42
Heat and Temperature
Heat and Temperature
are not the same thing
T is a measure of the
intensity of heat in a
body
3 common temperature
scales - all use water as
a reference

43
Relationships of the Three
Temperature Scales
Kelvin and Centigrade Relationsh ips
K  C  273
o

or
o
C  K  273

44
Relationships of the Three
Temperature Scales
Fahrenheit and Centigrade Relationsh ips
180 18 9
   1.8
100 10 5
o
F  1.8  o C  32
or
F  32
o
o
C
1.8
45
Convert 172.9 0F to degrees Celsius.
0F = (1.8 x 0C) + 32

0F – 32 = (1.8 x 0C)

(0F – 32) = 0C
1.8

0C = (172.9 – 32) = 78.3


1.8

46
Chapter 2
Atoms, Molecules, and Ions
Periodic Table: Elements
Atomic number =
the number of protons
6
Atomic mass =
Weight relative to C
one mole
12.011 Chemical symbol
Isotopes
– atoms whose nuclei have the same atomic number
but different mass numbers
Mass number =
Protons +neutrons
50

Cr
24
Atomic number

52 53 54

Cr Cr Cr
24 24 24
Calculating Average Atomic Mass
Mass number Isotope Mass
%Abundance
50 49.9461
4.35%
52 51.9405
83.79%
53 52.9407
9.50%
49.9461 x 0.0435 = 2.17
54 53.9389
51.9405 x 0.8379 =43.52
2.36%
52.9407 x 0.0950 = 5.03
53.9389 x 0.0236 = 1.27
51.99
• Essentially all elements combine to form
compounds
• Compounds are of two types:
– Molecular, which involve shared electrons and consist
of electrically neutral, discrete particles called
molecules
– Ionic compounds, which involve electron transfer and
charged particles called ions
• Chemical formulas are collections of
chemical symbols that are used to describe
elements and compounds
– Free elements are not combined with other elements in
a compound
• Examples: Fe (iron), Na (sodium), and K
(potassium)
– Many nonmetals occur as diatomic molecules
A molecule is an aggregate of two or more atoms in a definite
arrangement held together by chemical bonds

H2 H2O NH3 CH4

A diatomic molecule contains only two atoms

H2, N2, O2, F2, Cl2, Br2, I2

A polyatomic molecule contains more than two atoms


O3, H2O, NH3, CH4
• Chemical formulas specify the composition
of a substance
• NaCl is composed of the elements sodium and
chlorine in a one-to-one (atom) ratio
• Fe2O3 is composed of the elements iron and oxygen
in a two-to-three ratio
• CO(NH2)2 is composed of the elements carbon,
oxygen, nitrogen, and hydrogen
• Hydrates are crystals that contain water molecules,
for example plaster: CaSO4 • 2H2O
– When all the water is removed (by heating), the solid that
remains is said to be anhydrous (without water)
Counting Atoms in formulas
How many atoms of each element are represented by
The formulas (a) Al2(SO4)3 and (b) CoCl2 •6H2O

2 atoms of Al 1 atom Co
2 atoms Cl
3 atoms of S
12 atoms H
12 atoms of O
6 atom O
• Chemical equations describe what happens
in a chemical reactions
• Hydrogen and oxygen combine to form
water
• Hydrogen and oxygen are called reactants
• Water is called the product
• Reactants are separated from products with “”
– 2 H 2 + O2  2 H 2 O
• Note that the “” is like an equal sign because both
sides of the equation have the same number of each
type of atom
• This can be represented as:
Note: Mass is conserved because the
number of atoms of each type remains
the same on each side of the arrow.
(Both sides of the arrow show 4 H and
2 O atoms.) This equation is said to be
balanced.

The “2” in front of formulas H2 and H2O are called


coefficients. They indicate the number of molecules of each
type and can change when balancing a chemical equation.
The “2” in the formulas H2 and H2O indicate atom ratios for
the compound and must not change.
To balance the equation, you select coefficients
that will make the numbers of atoms of each
element equal on both sides of the equation

C3H8 + O2  CO2 + H2O

Reactant Side Product


Side
C=3 C=1
H=8 H=2
O=2 O=3
• It is sometimes useful to include the
physical state of reactants and products
• For solids use s, liquids use l, gases use g, and for
aqueous solutions use aq.
• For example, the reaction between stomach
acid (an aqueous solution of HCl) and
sodium carbonate (an antacid) can be
written
2 HCl(aq) + CaCO3(s)  CaCl2(aq) + H2O(l) +CO2(g)

Note: You can verify this equation is balanced by checking for


mass balance: each side shows 1 Ca, 1 C, 2 Cl, 2 H, and 3 O.
• As a general rule, molecular compounds are
formed when nonmetallic elements combine
• Many molecular compounds contain
hydrogen:
• Group Noble
Period IVA VA VIA VIIA Gas
• 2 CH4 NH3 H2O HF Ne
3 SiH4 PH3 H2S HCl Ar
• 4 GeH4 AsH3 H2Se HBr Kr
• 5 SbH3 H2Te HI Xe

• Note: The number of hydrogens that combined with the nonmetal


equals the number of spaces to the right we have to move to get to
the noble gas
• Organic chemistry is a major specialty that
deals with compounds containing mostly
carbon and hydrogen
• Hydrocarbons contain only hydrogen and
carbon and are organic compounds
• Alkanes are the simplest hydrocarbons
– General formula is CnH2n+2

Space-filling models:
Black atoms = carbon
White atoms = hydrogen
• Other classes of hydrocarbons exist
• Different classes of organic compounds are
derived from hydrocarbons by replacing
hydrogen
• For example alcohols result when a H is
replaced by OH in a hydrocarbon
Methanol (wood alcohol),
CH3OH, is related to methane,
CH4, by replacing one H with
OH.
An ion is an atom, or group of atoms, that has a net positive
or negative charge.

cation – ion with a positive charge


If a neutral atom loses one or more electrons
it becomes a cation.

11 protons 11 protons
Na Na+
11 electrons 10 electrons

anion – ion with a negative charge


If a neutral atom gains one or more electrons
it becomes an anion.

17 protons 17 protons
Cl Cl-
17 electrons 18 electrons
Ions

Magnesium (Mg) has 12 protons


+p +p +p +p +p +p +p +p +p +p +p +p

-e -e -e -e -e -e
-e -e -e -e -e -e

Magnesium has a tendency to form an ion with a


positive charge indicating that electrons have been loss

Mg 2+
A monatomic ion contains only one atom
Na+, Cl-, Ca2+, O2-, Al3+, N3-

A polyatomic ion contains more than one atom

OH-, CN-, NH4+, NO3-


Rules for Nomenclature
Ionic Compounds
(1) Name the metal first with it’s original

name
(2) Name the nonmetal with the suffix “–
ide”
Chemical Nomenclature

Examples

BaCl2 barium chloride

K2O potassium oxide

Mg(OH)2 magnesium hydroxide

KNO3 potassium nitrate


Rules for Nomenclature
Covalent/Molecular Compounds
Name the first element in the formula
(1)

with it’s original name


Name the second element in the
(2)

formula with the suffix “-ide”


Use greek prefixes to denote how
(3)

many of each element are present


• The number of each type of atom is
specified with Greek prefixes
Greek Prefixes
mono- = 1 (often omitted) hexa- =6
di- =2 hepta- =7
tri- =3 octa- = 8
tetra- = 4 nona- = 9
penta- = 5 deca- = 10

Examples: Note: many


PF5 = phosphorus pentafluoride compounds have
CO2 = carbon dioxide common names, like
N2O5 = dinitrogen pentoxide water for H2O.
• Ions formed by transition metals (Group
IIIB – VIIIB) and post-transition metals:
• Transition Metals
Chromium Cr2+, Cr3+ Zinc Zn2+
Manganese Mn2+, Mn3+ Silver Ag+
Iron Fe2+, Fe3+ Cadmium Cd2+
Cobalt Co2+, Co3+ Gold Au+, Au3+
Nickel Ni2+ Mercury Hg22+, Hg2+
Copper Cu+, Cu2+
Post-transition Metals
Tin Sn2+, Sn4+
Lead Pb2+, Pb4+
Bismuth Bi3+
• Some polyatomic ions (ions with two or
more atoms):
• Ion + Name Ion Name
NH4 ammonium ion CO32- carbonate ion
• OH- hydroxide ion H3O+ hydronium ion
NO2- nitrite ion SO32- sulfite ion
NO3- nitrate ion SO42- sulfate ion
ClO2- chlorite ion CrO42- chromate ion
ClO3- chlorate ion Cr2O72- dichromate ion
PO43- phosphate ion
• To name a compound, you can use this
flowchart:
+1 0

+2 +3 ±4 -3 -2 -1

Ionic Charges
Transition metal ionic compounds
 indicate charge on metal with Roman numerals

FeCl2 iron(II) chloride

FeCl3 iron(III) chloride

Cr2S3 chromium(III) sulfide


Formula of Ionic Compounds
Al3+ O2-

Al2O3

Ca2+ Br-

CaBr2

Na+ CO32-

Na2CO3
Some Polyatomic Ions
NH4+ ammonium SO42- sulfate
CO32- carbonate SO32- sulfite
- -
HCO3 bicarbonate NO3 nitrate
ClO3- chlorate NO2- nitrite
Cr2O72- dichromate SCN- thiocyanate
2- -
CrO4 chromate OH hydroxide
Problems
Name the following compounds:

LiF

NH4NO3

MgCl2

FeO

NaOH

Al2(SO4)3
Problems
Give the correct chemical formula for
the following compounds

Calcium bromide
Strontium phosphide

Potassium sulfate

Carbon tetrachloride

Lithium selenide
Molecular Compounds

HI

NF3

SO2

N2Cl4

NO2

N2O
An acid can be defined as a substance that yields
hydrogen ions (H+) when dissolved in water.

HCl
•Pure substance, hydrogen chloride
•Dissolved in water (H+ Cl-), hydrochloric acid

An oxoacid is an acid that contains hydrogen, oxygen, and


another element.

HNO3 nitric acid

H2CO3 carbonic acid

H2SO4 sulfuric acid


Naming Acids
Acids that contain a monatomic anion
receive the prefix “hydro-” and the
suffix “-ic”
HCl (aq) hydrochloric
HBr (aq) hydrobromic
HI (aq) hydroiodic
Naming Acids Cont’d
Acids that contain a polyatomic anion
ending in “-ite” receives the suffix “-
ous”
H2SO3 (aq) sulfurous
H3PO3 (aq) phosphorous
HNO2 (aq) nitrous
Naming Acids Cont’d
Acids that contain polyatomic anions
that end in “-ate” receive the suffix “-ic”
H2SO4 (aq) sulfuric
H3PO4 (aq) phosphoric
HNO3 (aq) nitric
A base can be defined as a substance that yields
hydroxide ions (OH-) when dissolved in water.

NaOH sodium hydroxide

KOH potassium hydroxide

Ba(OH)2 barium hydroxide


CHAPTER 3
Calculations with Chemical
Formulas and Equations

89
Atomic Weights
Weighted average of the
masses of the constituent
isotopes if an element.
 Tells us the atomic masses of
every known element.
 Lower number on periodic
chart.

90
The Mole
A number of atoms, ions, or molecules
that is large enough to see and handle.
A mole = number of things
 Just like a dozen = 12 things
 One mole = 6.022 x 1023 things
Avogadro’s number = 6.022 x 1023
 Symbol for Avogadro’s number is NA.

91
The Mole

Molar mass - mass in grams numerically


equal to the atomic weight of the element in
grams.
H has an atomic weight of 1.00794 g
 1.00794 g of H atoms = 6.022 x 1023 H atoms
Mg has an atomic weight of 24.3050 g
 24.3050 g of Mg atoms = 6.022 x 1023 Mg atoms

92
Mole and Avogadro’s Number
1 mol Na = 6.02 x 10 23 Na atoms
1 mol H2 = 6.02 x 10 23 H2 molecules
1 mole NaCl = 6.02 x 10 23 NaCl Formula Units
1 mole Na+1 = 6.02 x 10 23 Na+1 ions

93
The Mole
Example: Calculate the mass of a single
Mg atom, in grams, to 3 significant
figures.
 1 mol Mg atoms 
? g Mg  1 Mg atom   
 6.022  10 23
Mg atoms 
 24.30gMg 
   4.04 10  23 g Mg
 1 mol Mg atoms 

94
The Mole
Example: How many atoms are
contained in 1.67 moles of Mg?
 6.022 10 23 Mg atoms 
? Mg atoms  1.67 mol Mg  
 1 mol Mg 
 1.0110 24 Mg atoms

95
The Mole
Example: How many moles of Mg atoms are
present in 73.4 g of Mg?
You do it!

96
The Mole
Example 2-4: How many moles of Mg atoms
are present in 73.4 g of Mg?

 1 mol Mg atoms 
? mol Mg  73.4 g Mg  
 24.30 g Mg 
 3.02 mol Mg
IT IS IMPERATIVE THAT YOU KNOW
HOW TO DO THESE PROBLEMS
97
Formula Weights, Molecular
Weights, and Moles
How do we calculate the molar mass of
a compound?
 add atomic weights of each atom
The molar mass of propane, C3H8, is:
3  C  3  12.01 amu  36.03 amu
8  H  8  1.01 amu  8.08 amu
Molar mass  44.11 amu

98
Formula Weights, Molecular
Weights, and Moles

1 Ca  1 40.08 amu  40.08 amu


2  N  2 14.01 amu  28.02 amu
6  O  6 16.00 amu  96.00 amu
Molar mass  164.10 amu

99
Formula Weights, Molecular
Weights, and Moles
Example: Calculate the number of C3H8
molecules in 74.6 g of propane.
? C3 H 8 molecules  74.6 g C3 H 8 
 1 mole C3 H 8  6.022 10 23 C3 H 8 molecules 
   
 44.11 g C3 H 8  44.11 g C3 H 8 
1.02  10 molecules
24

100
Percent Composition and
Formulas of Compounds
% composition = mass of an individual
element in a compound divided by the
total mass of the compound x 100%
Determine the percent composition of C
in C3H8.
mass C
%C 100%
mass C3 H 8
3 12.01 g
 100%
44.11 g
 81.68% 101
Percent Composition and
Formulas of Compounds
Example: Calculate the percent
composition of Fe2(SO4)3 to 3 significant
figures.
You do it!

102
Percent Composition and
Formulas of Compounds
Example: Calculate the percent
composition of Fe2(SO4)3 to 3 sig. fig.
2  Fe 2  55.8 g
% Fe  100%  100%  27.9% Fe
Fe 2 (SO 4 ) 3 399.9 g
3 S 3  32.1 g
%S  100%  100%  24.1% S
Fe 2 (SO 4 ) 3 399.9 g
12  O 12 16.0 g
% O  100%  100%  48.0% O
Fe 2 (SO 4 ) 3 399.9 g
Total  100%
103
Derivation of Formulas from
Elemental Composition
Empirical Formula - smallest whole-number ratio of
atoms present in a compound
 CH2 is the empirical formula for alkenes
 No alkene exists that has 1 C and 2 H’s
Molecular Formula - actual numbers of atoms of each
element present in a molecule of the compound
 Ethene – C2H4
 Pentene – C5H10
We determine the empirical and molecular formulas of a
compound from the percent composition of the
compound.
 percent composition is determined experimentally

104
Derivation of Formulas from
Elemental Composition
Example: A compound contains 24.74% K,
34.76% Mn, and 40.50% O by mass. What is
its empirical formula?
Make the simplifying assumption that we
have 100.0 g of compound.
In 100.0 g of compound there are:
 24.74 g of K
 34.76 g of Mn
 40.50 g of O

105
Derivation of Formulas from
Elemental Composition
1 mol K
? mol K  24.74 g K   0.6327 mol K
39.10 g K
1 mol Mn
? mol Mn  34.76 g Mn   0.6327 mol Mn
54.94 g Mn
1mol O
? mol O  40.50 g O   2.531 mol O
16.00 g O
obtain smallest whole number ratio

106
Derivation of Formulas from
Elemental Composition
1 mol K
? mol K  24.74 g K   0.6327 mol K
39.10 g K
1 mol Mn
? mol Mn  34.76 g Mn   0.6327 mol Mn
54.94 g Mn
1mol O
? mol O  40.50 g O   2.531 mol O
16.00 g O
obtain smallest whole number ratio
0.6327 0.6327
for K  1K for Mn   1 Mn
0.6327 0.6327

107
Derivation of Formulas from
Elemental Composition
1 mol K
? mol K  24.74 g K   0.6327 mol K
39.10 g K
1 mol Mn
? mol Mn  34.76 g Mn   0.6327 mol Mn
54.94 g Mn
1mol O
? mol O  40.50 g O   2.531 mol O
16.00 g O
obtain smallest whole number ratio
0.6327 0.6327
for K  1K for Mn   1 Mn
0.6327 0.6327
2.531
for O  4O
0.6327
thus the chemical formula is KMnO 4
108
Derivation of Formulas from
Elemental Composition
Example: A sample of a compound
contains 6.541g of Co and 2.368g of O.
What is empirical formula for this
compound?
You do it!

109
Derivation of Formulas from
Elemental Composition
Example: A sample of a compound
contains 6.541g of Co and 2.368g of O.
What is empirical formula for this
compound?
1 mol Co
? mol Co  6.541 g Co   0.1110 mol Co
58.93 gCo
1mol O
? mol O  2.368 g O   0.1480 mol O
16.00 g O
find smallest whole number ratio
110
Derivation of Formulas from
Elemental Composition
Example: A sample of a compound
contains 6.541g of Co and 2.368g of O.
What is empirical formula for this
compound?
0.1110 0.1480
for Co   1 Co for O   1.333O
0.1110 0.1110
multipy both by 3 to turn fraction to whole number
1 Co  3  3 Co 1.333 O  3  4 O
Thus the compound' s formula is :
Co3O 4
111
Some Other Interpretations of
Chemical Formulas
Example: What mass of ammonium
phosphate, (NH4)3PO4, would contain
15.0 g of N?

molar mass of (NH 4 )3 PO 4  149.0 g/mol


1 mol N
? mol N  15.0 g of N   1.07 mol N
14.0 g N

112
Some Other Interpretations of
Chemical Formulas
Example: What mass of ammonium
phosphate, (NH4)3PO4, would contain
15.0 g of N?
molar mass of (NH 4 )3 PO 4  149.0 g/mol
1 mol N
? mol N  15.0 g of N   1.07 mol N
14.0 g N
1 mol (NH 4 ) 3 PO 4
1.07 mol N   0.357 mol (NH 4 ) 3 PO 4
3 mol N

113
Some Other Interpretations of
Chemical Formulas
Example: What mass of ammonium
phosphate, (NH4)3PO4, would contain
15.0 g of N?
molar mass of (NH 4 )3 PO 4  149.0 g/mol
1 mol N
? mol N  15.0 g of N   1.07 mol N
14.0 g N
1 mol (NH 4 )3 PO 4
1.07 mol N   0.357 mol (NH 4 )3 PO 4
3 mol N
149.0 g (NH 4 )3 PO 4
0.357 mol (NH 4 )3 PO 4   53.2 g (NH 4 )3 PO 4
1 mol (NH 4 )3 PO 4
114
Purity of Samples
The percent purity of a sample of a
substance is always represented as
mass of pure substance
% purity = 100%
mass of sample
mass of sample includes impurities

115
Purity of Samples
Example 2-18: A bottle of sodium
phosphate, Na3PO4, is 98.3% pure Na3PO4.
What are the masses of Na3PO4 and
impurities in 250.0 g of this sample of
Na3PO4?
98.3 g Na 3 PO 4
unit factor
100.0 g sample

116
Purity of Samples
Example 2-18: A bottle of sodium
phosphate, Na3PO4, is 98.3% pure Na3PO4.
What are the masses of Na3PO4 and
impurities in 250.0 g of this sample of
Na3PO4?
98.3 g Na 3PO 4
unit factor
100.0 g sample
98.3 g Na 3 PO 4
? g Na 3 PO 4  250.0 g sample 
100.0 g sample
= 246 g Na 3PO 4
117
Purity of Samples
Example: A bottle of sodium phosphate,
Na3PO4, is 98.3% pure Na3PO4. What are
the masses of Na3PO4 and impurities in
250.0 g of this sample of Na3PO4?
98.3 g Na 3 PO 4
unit factor
100.0 g sample
98.3 g Na 3 PO 4
? g Na 3 PO 4  250.0 g sample 
100.0 g sample
= 246 g Na 3 PO 4
? g impurities = 250.0 g sample - 246 g Na 3 PO 4
118
= 4.00 g impurities
Reaction Stoichiometry
Given the following balanced equation, how
many moles of O2 are required to react with 6.0
moles C6H6?

2 C6H6 +15 O2 12 CO2 +6 H2O

6.0 moles C6H6 x 15 moles O2 = 45 moles O2


2 moles C6H6

119
Reaction Stoichiometry
Given the following balanced equation, how
many grams of O2 are required to react with 6.0
moles C6H6?

2 C6H6 +15 O2 12 CO2 +6 H2O

6.0 moles C6H6 x 15 moles O2 x 32.0 g O2 =1.4 x 103 g O2


2 moles C6H6 1 mole

120
Reaction Stoichiometry
Given the following balanced equation, how
many grams of O2 are required to react with 0.50
grams C6H6?

2 C6H6 +15 O2 12 CO2 +6 H2O

0.50 g C6H6 x 1 mol C6H6 x 15 mol O2 x 32.0 g O2 =1.5 g O2


78.0 g 2 mol C6H6 1 mol

121
Limiting Reactant
Given the following balanced equation, how
many grams of H2O are required to react with
0.50 g C6H6 and 0.50 g O2?

2 C6H6 +15 O2 12 CO2 +6 H2O

0.50g C6H6 x 1 mol C6H6x 6 mol H2O x 18.0 g H2O = 0.35 g


78.0 g 2 mol C6H6 1 mole

0.50g O2 x 1 mol O2 x 6 mol H2O x 18.0 g H2O =0.11g


32.0 g 15 mol O2 1 mol
122
End of Chapter 3
The mole concept and basic
stoichiometry ideas introduced in this
chapter are essential components for
the remainder of this course.

123
Reactions in Aqueous
Solution
Chapter 4
A solution is a homogenous mixture of 2 or more
substances

The solute is(are) the substance(s) present in the


smaller amount(s)

The solvent is the substance present in the larger


amount

Solution Solvent Solute


Soft drink (l) H2O Sugar, CO2
Air (g) N2 O2, Ar, CH4
Soft Solder (s) Pb Sn
An electrolyte is a substance that, when dissolved in
water, results in a solution that can conduct electricity.
A nonelectrolyte is a substance that, when dissolved,
results in a solution that does not conduct electricity.

nonelectrolyte weak electrolyte strong electrolyte


Ionic compounds that dissolve in water
always produce solutions that are strong
electrolytes.

Molecular compounds that dissolve in


water may produce nonelectrolytes,
weak electrolytes (weak acids or bases),
or strong electrolytes (strong acids).
Conduct electricity in solution?

Cations (+) and Anions (-)

Strong Electrolyte – 100% dissociation

NaCl (s) H2O Na+ (aq) + Cl- (aq)

Weak Electrolyte – not completely dissociated

CH3COOH CH3COO- (aq) + H+ (aq)


Reversible reaction - Chemical equilibrium
r
Nonelectrolyte does not conduct electricity?

No cations (+) and anions (-) in solution

H2O
C6H12O6 (s) C6H12O6 (aq)

Strong Electrolyte Weak Electrolyte Nonelectrolyte


HCl CH3COOH (NH2)2CO
HNO3 HF CH3OH
HClO4 HNO2 C2H5OH
NaOH H2O C12H22O11
All Ionic
Compounds
Water’s power as an ionizing
solvent results from the
distribution of its electrons and
its overall shape.
A polar molecule is one that has a
+ end and a - end. Water is one
of the most polar molecules.
Hydration is the process in which an ion is surrounded
by water molecules arranged in a specific manner.

d

d
H2O
The Solubility of Ionic Compounds in Water
The solubility of ionic compounds in water depends upon the relative
strengths of the electrical forces between ions in the ionic compound
and the attractive forces between the ions and water molecules in the
solvent. There is a tremendous range in the solubility of ionic
compounds in water! The solubility of so called “insoluble” compounds
may be several orders of magnitude less than ones that are called
“soluble” in water, for example:

Solubility of NaCl in water at 20oC = 365 g/L


Solubility of MgCl2 in water at 20oC = 542.5 g/L
Solubility of AlCl3 in water at 20oC = 699 g/L
Solubility of PbCl2 in water at 20oC = 9.9 g/L
Solubility of AgCl in water at 20oC = 0.009 g/L
Solubility of CuCl in water at 20oC = 0.0062 g/L
Precipitation Reactions
Precipitate – insoluble solid that separates from solution
precipitate

Pb(NO3)2 (aq) + 2NaI (aq) PbI2 (s) + 2NaNO3 (a


molecular equation

Pb2+ + 2NO3- + 2Na+ + 2I- PbI2 (s) + 2Na+ + 2NO


ionic equation

Pb2+ + 2I- PbI2 (s)


PbI2
net ionic equation
Na+ and NO3- are spectator ions
Writing Net Ionic Equations
1. Write the balanced molecular equation.
2. Determine precipitate from solubility rules
3. Write the ionic equation showing the soluble strong
electrolytes as ions.
4. Cancel the spectator ions on both sides of the ionic equation
Write the net ionic equation for the reaction of silver
nitrate solution with sodium chloride solution.

AgNO3 (aq) + NaCl (aq) AgCl (s) + NaNO3 (aq)

Ag+ + NO3- + Na+ + Cl- AgCl (s) + Na+ + NO3-

Ag+ + Cl- AgCl (s)


Molecular Equation: reactants and products are
written as if they were undissociated compounds.

Total Ionic Equation: all soluble ionic substances


(strong electrolytes) are dissociated into ions.

Net Ionic Equation: Eliminate spectator ions.


(These are ions which are unchanged in the
chemical reaction.)
Acids

Have a sour taste. Vinegar owes its taste to acetic acid. Citrus
fruits contain citric acid.
React with certain metals to produce hydrogen gas.
React with carbonates and bicarbonates to produce carbon
dioxide gas

Bases
Have a bitter taste.

Feel slippery. Many soaps contain bases.


Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water


A Brønsted acid is a proton donor
A Brønsted base is a proton acceptor

base acid acid base

A Brønsted acid must contain at least one


ionizable proton!
Monoprotic acids
HCl H+ + Cl- Strong electrolyte, strong ac
HNO3 H+ + NO3- Strong electrolyte, strong ac
CH3COOH H+ + CH3COO- Weak electrolyte, weak acid

Diprotic acids
H2SO4 H+ + HSO4- Strong electrolyte, strong ac
HSO4- H+ + SO42- Weak electrolyte, weak acid

Triprotic acids
H3PO4 H+ + H2PO4- Weak electrolyte, weak acid
H2PO4- H+ + HPO42- Weak electrolyte, weak acid
HPO42- H+ + PO43- Weak electrolyte, weak acid
Neutralization Reaction

acid + base salt + water

HCl (aq) + NaOH (aq) NaCl (aq) + H2O


H+ + Cl- + Na+ + OH- Na+ + Cl- + H2O
H+ + OH- H2O
Writing Balanced Equations for
Neutralization Reactions
Problem: Write balanced chemical equations (molecular,
total ionic, and net ionic) for the following
chemical reactions:
a) barium hydroxide(aq) and hydroiodic acid(aq)
b) lithium hydroxide(aq) and nitric acid(aq)
c) sodium hydroxide(aq) and sulfuric acid(aq)
Oxidation-Reduction (redox)
reactions involve a transfer of
electrons.

oxidation: loss of electrons


reduction: gain of electrons
reducing agent: substance oxidized
oxidizing agent: substance reduced
Oxidation-Reduction Reactions
(electron transfer reactions)

2Mg (s) + O2 (g) 2MgO (s)

2Mg 2Mg2+ + 4e- Oxidation half-reaction (lose e-)

O2 + 4e- 2O2- Reduction half-reaction (gain e-

2Mg + O2 + 4e- 2Mg2+ + 2O2- + 4e-

2Mg + O2 2MgO
Oxidation number: the charge an
atom would have if the shared
electrons were transferred
completely to the atom with the
greater attraction for the
electrons.

An increase in oxidation number


indicates oxidation.

A decrease in oxidation number


indicates reduction.
Oxidation number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.

1. Free elements (uncombined state) have an oxidation


number of zero.

Na, Be, K, Pb, H2, O2, P4 = 0


2. In monatomic ions, the oxidation number is equal to
the charge on the ion.

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2


3. The oxidation number of oxygen is usually –2. In H2O2
and O22- it is –1.
4. The oxidation number of hydrogen is +1 except when
it is bonded to metals in binary compounds. In these
cases, its oxidation number is –1.

5. Group 1 metals are +1, group 2 metals are +2 and


fluorine is always –1.

6. The sum of the oxidation numbers of all the atoms in


a molecule or ion is equal to the charge on the
molecule or ion.

Oxidation numbers of all the elements in


HCO3-, HNO3, Na3PO4, IF7, KIO3, K2Cr2O7,
SO42- ?
Types of Oxidation-Reduction Reactions

Combination Reaction
A+B C
0 0 +4 -2
S + O2 SO2
Oxidized? Reduced? Oxidizing agent? Reducing agent?
Decomposition Reaction
C A+B

+1+5 -2 +1 -1 0
2KClO3 2KCl + 3O2
Types of Oxidation-Reduction Reactions

(Single) Displacement Reaction


A + BC AC + B
0 +1 +2 0
Sr + 2H2O Sr(OH)2 + H2 Hydrogen Displacement
+4 0 0 +2
TiCl4 + 2Mg Ti + 2MgCl2 Metal Displacement
0 -1 -1 0
Cl2 + 2KBr 2KCl + Br2 Halogen Displacement
Oxidized? Reduced? Oxidizing agent? Reducing agent?
The Activity Series for Metals
(Single) Displacement
Reaction

M + BC MC + B
Reaction will occur only
if M is above B.

Ca + 2H2O Ca(OH)2 + H2
Pb + 2H2O Pb(OH)2 + H2
Zn (s) + CuSO4 (aq) ZnSO4 (aq) + Cu (s)
Zn Zn2+ + 2e- Zn is oxidized Zn is the reducing agent

Cu2+ + 2e- Cu Cu2+ is reduced Cu2+ is the oxidizing agent

Nickel wire reacts with silver nitrate to form silver metal.


What is the oxidizing agent in the reaction?

Ni (s) + 2AgNO3 (aq) Ni(NO3)2 (aq) + 2Ag (s)


Ni Ni2+ + 2e-Ni is oxidized Ni is the reducing
agent.
Ag+ + 1e- Ag Ag+ is reduced Ag+ is the oxidizing agent
Types of Oxidation-Reduction Reactions
Disproportionation Reaction

Element is simultaneously oxidized and reduced.


0 +1 -1
Cl2 + 2OH- ClO- + Cl- + H2O

Chlorine Chemistry
Classify the following reactions.

Ca2+ + CO32- CaCO3(s) Precipitation

NH3 + H+ NH4+ Acid-Base

Zn + 2HCl ZnCl2 + H2 Redox (H2 Displacement)

Ca + F2 CaF2 Redox (Combination)


Solution Stoichiometry
The concentration of a solution is the amount of
solute present in a given quantity of solvent or solution.
moles of solute
M = molarity =
liters of solution

What mass of KI is required to make 500. mL of


a 2.80 M KI solution?
M KI M KI
volume KI moles KI grams KI

1L 2.80 mol KI166 g KI


500. mLx x x = 232 g KI
1000 mL 1 L soln 1 mol KI
Dilution is the procedure for preparing a less concentrated
solution from a more concentrated solution.

Dilution
Add Solvent

Moles of solute Moles of solute


before dilution (i) = after dilution (f)

MiVi = MfVf
How would you prepare 60.0 mL of 0.20 M
HNO3 from a stock solution of 4.00 M HNO3?

MiVi = MfVf

Mi = 4.00 Mf = 0.20 Vf = 0.06 L Vi = ? L

MfVf 0.20 M x 60.0 mL


Vi = = = 3.0 mL
Mi 4.00 M

3.0 mL of acid to 60 mL of solution


Gravimetric Analysis
1. Dissolve unknown substance in water
2. React unknown with known substance to form a precipitate
3. Filter and dry precipitate
4. Weigh precipitate
5. Use chemical formula and mass of precipitate to determine
amount of unknown ion
Volumetric Analysis - Titrations
In a titration a solution of accurately known concentration is
added gradually added to another solution of unknown
concentration until the chemical reaction between the two
solutions is complete.

Equivalence point – the point at which the reaction is complete


Indicator – substance that changes color at (or near) the
equivalence point

Slowly add base


to unknown acid
UNTIL
the indicator
changes color
What volume of a 1.420 M NaOH solution is
Required to titrate 25.00 mL of a 4.50 M H2SO4
solution?

WRITE THE CHEMICAL EQUATION!

H2SO4 + 2NaOH 2H2O + Na2SO4


M rx M
volume acid moles acid moles base volume base
acid coef. base

4.50 mol H2SO4 2 mol NaOH 1000 ml soln


25.00 mLx x x = 158 mL
1000 mL soln 1 mol H2SO4 1.420 mol NaOH
Chapter 5: Properties of Gases
Gases have a number of properties
that are very different from liquids and
solids:
1) Gases are compressible
2) Gases exert a pressure
3) Gas pressure depends on the amount of
confined gas
4) Gases fill their container
5) Gases mix freely with each other
6) Gas pressure increases with temperature
The height of the mercury column
varies with altitude
The average pressure at sea level or
the standard atmosphere (atm) was
defined as the pressure needed to
support a column of mercury 760 mm
high measures at 0oC
The SI unit1ofN pressure 2
is the pascal
(Pa) 1 Pa  2
 1 N m
1m
1 atm  101,325 Pa (exactly)
You may encounter a number of
pressure units
The standard atmosphere is
o
760 mm Hg (measured at 0 C)
760 torr
101,325 Pa  101.325 kPa
1.013 bar  1013 mb
14.7 lb in  2
Chemical reactions often involve gases
A manometer is used to measure the
pressure inside closed containers

Open-end manometer. (a) The pressure of the trapped


gas, Pgas equals the atmospheric pressure, Patm. Trapped
gas pressure (b) higher and (c) lower than atmospheric
pressure.
A closed-end manometer for
measuring gas pressures less
than 1 atm. When constructed
(a) the tube is fully evacuated
and mercury is allowed to enter
and fill the closed arm
completely. (a) Mercury flows
out of the closed arm when the
bulb contains gas at low
pressure. The difference in
mercury levels, PHg, is the
pressure of the confined gas,
Pgas.
There are four variables that affect the
properties of a gas: pressure, volume,
temperature, and the amount of the
gas
Simple experiments can be conducted
that relate how these variables change
The gas laws summarize these
experiments
Compressing a gas
increases its
pressure. A
molecular view of
what happens when
a gas is squeezed
into a smaller
volume. The number
of collisions with a
given area of the
walls increases which
causes the pressure
to rise.
Robert Boyle studied how the volume of a fixed
amount of gas varies with pressure at constant
temperature. (a) Air trapped in a J-tube by mercury.
(b) As more mercury is added, the pressure of the
trapped gas increases and the volume decreases.
(a) A typical graph of volume versus pressure showing
volume decreasing as pressure increases. (b) A straight
line is obtained when volume is plotted against (1/P),
which shows that 1
V
P
The relationship between volume and
pressure is called Boyle’s law or the
pressure-volume law
 The volume of a given amount of gas held
at constant temperature varies inversely
with the applied pressure
The proportionality can be removed by
introducing a proportionally constant, C
1
V   C or PV  C (constant amount and temperatu re)
P
Boyle’s Law : P - V Relationship
Pressure is inversely proportional to volume
Or pressure is directly proportional to 1/V
P =k or kV = or
PV=k V P
If n (number of moles) and T are constant
P1V1 = k P2V2 = k

Then : P1V1 = P2V2


A sample of chlorine gas occupies a volume of 946 mL
at a pressure of 726 mmHg. What is the pressure of
the gas (in mmHg) if the volume is reduced at constant
temperature to 154 mL?

P1 x V1 = P2 x V2
P1 = 726 mmHg P2 = ?
V1 = 946 mL V2 = 154 mL

P1 x V1 726 mmHg x 946 mL


P2 = = = 4460 mmHg
V2 154 mL
Boyle’s law is remarkably successful,
especially for common laboratory
conditions
However, no real gas obeys Boyle’s law
exactly over a wide range of
temperatures and pressures
The hypothetical gas that does
exactly obey Boyle’s law is called an
ideal gas
Real gases act more like ideal gases as
their pressures decrease and
temperatures increase
Jacques Alexander Charles studied how
the volume of a gas sample varied with
temperature Charles’ law
plots. Each line
shows how the
gas volume
changes with
temperature for
different sized
samples of the
same gas.
When extrapolated to zero volume all
the samples have the same
temperature:
 273.15 Co

This temperature is called absolute


zero and is the basis of the Kelvin
TK  T scale:
temperature o
C
 273 .15

Charles’ law or the temperature-volume


law can be expressed mathematically
V T or V  C'T (constant amount and pressure)
Joseph Louis Gay-Lussac studied how
the pressure and temperature of a fixed
amount of gas at constant volume are
related
Gay-Lussacs’ law or the pressure-
temperature law states:
 The pressure of a fixed amount of gas held
at constant volume is directly proportional
to the Kelvin temperature
Mathematically this is
P  T or P  C"T (constant amount and volume)

The three gas laws are often used in a


single equation called the combined
gas law
PV P1V1 P2V2
 constant or  (fixed amount)
T T1 T2

When using this equation the


temperature must always be in kelvins
Alternate forms of the previous gas
laws result when certain variables
cancel
Boyle' s Law :
P1V1  P2V2 (when T1  T2 )
Charles' Law :
V1 / T1  V2 / T2 (when P1  P2 )
Gay - Lussac' s Law :
P1 / T1  P2 / T2 (when V1  V2 )

Problems involving the gas laws are


important
Example: What will be the the final pressure
of a sample of oxygen with a volume of
850 m3 at 655 torr and 25.0oC if it is
heated to 80.0oC and given a final volume
of 1066 m3?
ANALYSIS: Use the combined gas law with
temperature in kelvins.
SOLUTION: V1 T2
P2  P1  
V2 T1
850 m 3 (80 .0  273 .2)K
 655 torr  
1066 m (25.0  273.2)K
3

 619 torr
Amedeo Avogadro studied this and devised Avogadro’s
principle:
 When measured at the same temperature and
pressure, equals volumes of gases contain equal
number of moles
 The volume of a gas is directly proportional to its
number of moles, n
V n (at constant T and P)

Thus, the volume of one mole of any gas at


standard temperature and pressure (STP) or
0oC and 1 atm is 22.4 L (a constant for all ideal
gases)
This is called the standard molar volume of a
Ammonia burns in oxygen to form nitric oxide (NO)
and water vapor. How many liters of NO are obtained
from 10 liters of ammonia at the same temperature
and pressure? How many liters of oxygen are
required?
4NH3 + 5O2 4NO + 6H2O

1 mole NH3 1 mole NO

At constant T and P

1 volume NH3 1 volume NO


The combined gas law can be
generalized to include changes in the
number of moles of sample
The ideal gas law is
PV  nRT
R  universal gas constant
atm L
 0.0821
mol K
What is the volume (in liters) occupied by 49.8 g of HCl
at STP?
T = 0 0C = 273.15 K

P = 1 atm
PV = nRT
1 mol HCl
nRT n = 49.8 g x = 1.37 mol
V= 36.45 g HCl
P
L•atm
1.37 mol x 0.0821 mol•K
x 273.15 K
V=
1 atm

V = 30.6 L
Argon is an inert gas used in lightbulbs to retard the
vaporization of the filament. A certain lightbulb
containing argon at 1.20 atm and 18 0C is heated to
85 0C at constant volume. What is the final pressure of
argon in the lightbulb (in atm)?

PV = nRT n, V and R are constant


nR P
= = constant P1 = 1.20 atm P2 = ?
V T
T1 = 291 K T2 = 358 K
P1 P2
=
T1 T2
T2
P2 = P1 x = 1.20 atm x 358 K = 1.48 atm
T1 291 K
The molecular mass is obtained by
taking the ratio of mass to moles, which
could be determined using the ideal gas
law
Gas densities (d), a ratio of gas mass
to volume, can be calculated by taking
the ratio of the molar mass to molar
volume
 Example: The
dO 2  molar
32.0 massof
g/mol oxygen
1.42 g L1 is
32.0 g/mol. What
22.4 isL/mol
the density of oxygen
at STP?
One mole of each
gas occupies 22.4
at STP. Carbon
dioxide is more
dense that oxygen
due to molar mass
We now need to consider mixtures of
differences.
gases
One useful way to describe a
composition of a mixture is in terms of
its mole fractions
The mole fraction is the ratio of the
number of moles of a given component
to the total moles of all components
For a mixture of A, B, … substances,
the mole fraction of substance i (Xi) is
nA
XA  , ni  moles of i
nA  nB  ...  nZ
This provides a convenient way to
`partition’ the total pressure of a
mixture of gases
Dalton’s law of partial pressures
states: the total pressure of a mixture
of gases is the sum of their individual
partial pressures
For a system of only gases, mole
fractions and partial pressure partition
the total pressure in the same fashion
PTotal  PA  PB  ....
 PTotal X A  PTotal X B  ....
1  X A  X B  ...
Gases are often collected over water in
the laboratory
These (collected) gases are saturated
with water
The space above any liquid contains
some of the liquid’s vapor
The pressure this vapor exerts is called
the vapor pressure

As the gas bubbles through the water, water vapor gets


into the gas so the total pressure inside the bottle
includes the partial pressure of the water vapor.
Temperatur e ( o C) Vapor Pressure (torr)
0 4.579
Vapor
20 17.54
pressure of
30 31.82 water at
40 55.32 various
100 760.0 temperatures
.
The total pressure is the pressure of the
gas plus the vapor pressure of water
Ptotal  Pgas  Pwater vapor or
Pgas  Ptotal  Pwater vapor
Example: A sample of oxygen is collected
over water at 20oC and a pressure of 738
torr. What is the partial pressure of
oxygen?
ANALYSIS: The partial pressure of oxygen is
less than the total pressure. Get the vapor
pressure of water from table 11.2 (page
478).
Pwater vapor  17 .54 torr (from Table 11.2)
SOLUTION:
Pgas  (738  17 .54 ) torr  720. torr

Partial pressures can be used to


calculate mole fractions
This is possible because the number of
moles of each gas is directly
proportional to its partial pressure
Using the ideal gas equation for each
gas PAV
nA 
RT

For a given mixture of gases, the


volume and temperature is the same for
all gases
Using C=V/RT gives
PAC
XA 
PAC  PB C    PZ C
PA PA
 
PA  PB    PZ Ptotal
The partial pressure of a gas can be
calculated using the total pressure and
mole fraction
PA  X A Ptotal
Diffusion is the spontaneous
intermingling of the molecules of one
gas with another
Effusion is the movement of gas
molecules through a tiny hole into a
vacuum
The rates of both diffusion and effusion
depend on the speed of the gas
molecules
The faster the molecules, the faster
diffusion and effusion occur
He found that the effusion rate of a gas
was inversely proportional to the square
root of the density (d)
This is known as Graham’s law
1
effusion rate  (constant P and T )
d
effusion rate ( A) dB MB
 
effusion rate ( B ) dA MA
Where Mi is the molar mass of species i
Postulates of the Kinetic Theory of Gases
1) A gas consists of a large number of tiny
particles that are in constant, random
motion.
2) The gas particles themselves occupy a
net volume so small in relation to the
volume of their container that their
contribution to the total volume can be
ignored.
3) The collisions between particle and with
the walls of the container are perfectly
elastic.
Calculations show that PV is
proportional to the average kinetic
energy and the Kelvin temperature,
thusPV  average molecular KE
PV  T
 T  average molecular KE

The kinetic theory also explains the gas


laws
Graham’s law requires that the rate of
effusion for the different gases be
compared at the same temperature and
pressure
When different gases have the same
temperature, they have the same
average kinetic energy
The average kinetic energy can be
expressed in terms of the average of
the velocities squared or root mean
square
For the two gases labeled 1 and 2
KE1  KE 2
1 1
m1 v1  m2 v22 rearrangin g
2

2 2


2
v m2
1
 or with vi rms
 v
2
i
v2 m1
2

v  
m2

M2
v 
1 rms

2 rms
m1 M1
Note that heavier gases move slower
than lighter gases
The rate of effusion is proportional to
the average molecular speed, thus
effusion rate (gas 1)

v1 rms

M2
 
effusion rate (gas 2) v2 rms M1
The kinetic theory predicts that
absolute zero is the temperature at
which the average kinetic energy of an
ideal gas is zero
Real gases exhibit non-ideal behavior
Gas Stoichiometry

What is the volume of CO2 produced at 370 C and 1.00


atm when 5.60 g of glucose are used up in the reaction:
C6H12O6 (s) + 6O2 (g) 6CO2 (g) + 6H2O (l)

g C6H12O6 mol C6H12O6 mol CO2 V CO2

1 mol C6H12O6 6 mol CO2


5.60 g C6H12O6 x x = 0.187 mol CO2
180 g C6H12O6 1 mol C6H12O6

L•atm
0.187 mol x 0.0821 x 310.15 K
nRT mol•K
V= = = 4.76 L
P 1.00 atm
Ideal Gas Law and Reaction
Stoichiometry

Sodium azide (NaN3) is used in some air bags in


automobiles. Calculate the volume of nitrogen gas
generated at 21 oC and 823 mm Hg by the
decomposition of 60.0 g of NaN3 .

2 NaN3 (s) 2 Na (s) + 3 N2 (g)


A sample of natural gas contains 8.24 moles of CH4,
0.421 moles of C2H6, and 0.116 moles of C3H8. If the
total pressure of the gases is 1.37 atm, what is the
partial pressure of propane (C3H8)?

Pi = Xi PT PT = 1.37 atm

0.116
Xpropane = = 0.0132
8.24 + 0.421 + 0.116

Ppropane = 0.0132 x 1.37 atm = 0.0181 atm


Thermochemistry
Chapter 6
Thermochemical Definitions
System : That part of the Universe whose change we are
going to measure.
Surroundings : Every thing else that is relevant to the change
is defined as the “surroundings”.
Internal Energy : The sum of the kinetic and potential energy
of all the particles in a system.
Heat (q) : Is the energy transferred between a system
and it’s surroundings as result in the differences in
their temperatures only!
Work (w) : The energy transferred when an object is moved by
a force.

Therefore: E=q+w
Thermodynamics
State functions are properties that are determined by the state
of the system, regardless of how that condition was achieved.
energy, pressure, volume, temperature
DE = q + w

DE is the change in internal energy of a system

q = the heat exchange between


the system and the surroundings

w is the work done on (or by) the system

w = -PDV when a gas expands against


a constant external pressure
Thermodynamics
Determining Energy Change in a System
Problem: In the internal combustion engine, the heat produced by the
combustion of the fuel causes the carbon dioxide and water that is
produced during the combustion to expand, pushing the pistons. Excess
heat is removed by the cooling system. Determine the change in energy
( E) in J, kJ, and kcal if the expanding gases do 515 J of work on the
pistons, and and the system loses 407 J of heat to the cooling system.

q = - 407 J w = -515
J
E = q + w = - 407 J + ( - 515 J) = - 922 J

E = - 922 J x 1 kJ = -0.922 kJ
1000 J
E = - 922 J x 1 cal = - 220 cal
4.184 J
E is a state function, q and w are not.
First Law of Thermodynamics

( Law of Conservation of Energy )

“The Total Energy of the Universe is Constant”

E of Universe = ESystem + ESurroundings = 0


Energy Changes in Chemical Reactions
Heat is the transfer of thermal energy between two bodies that
are at different temperatures.

Temperature is a measure of the thermal energy.

Temperature = Thermal Energy

900C
400C
greater thermal energy
Thermochemistry is the study of heat change in chemical
reactions.
The system is the specific part of the universe that is of
interest in the study. SURROUNDINGS
SYSTEM

open closed isolated


Exchange: mass & energy energy nothing
Exothermic process is any process that gives off heat –
transfers thermal energy from the system to the surroundings.

2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

Endothermic process is any process in which heat has to be


supplied to the system from the surroundings.

energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)


Change in Enthalpy = H
Enthalpy is defined as the system’s internal energy
plus the product of its pressure and volume.
H = E + PV
For a change in enthalpy:
H = E+ PV
Exothermic and Endothermic Reactions:
H = H final - H initial = H products - H reactants

Exothermic : H final H initial H 0


Endothermic : H final H initial H 0
For processes occurring at
constant pressure the
enthalpy change equals the
heat gained or lost.

DH = qp

enthalpy of reaction or heat of


reaction. (Energy change +
small correction factor.)
Enthalpy (H) is used to quantify the heat flow into or out of a
system in a process that occurs at constant pressure.
DH = H (products) – H (reactants)
DH = heat given off or absorbed during a reaction at constant pressure

Hproducts < Hreactants Hproducts > Hreactants


DH < 0 DH > 0
Thermochemical Equations

Is DH negative or positive?

System absorbs heat

Endothermic

DH > 0

6.01 kJ are absorbed for every 1 mole of ice that


melts at 00C and 1 atm.

H2O (s) H2O (l) DH = 6.01 kJ


Thermochemical Equations

Is DH negative or positive?

System gives off heat

Exothermic

DH < 0

890.4 kJ are released for every 1 mole of methane


that is combusted at 250C and 1 atm.

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH = -890.4 kJ


Thermochemical Equations

• The stoichiometric coefficients always refer to the number


of moles of a substance
H2O (s) H2O (l) DH = 6.01 kJ

• If you reverse a reaction, the sign of DH changes


H2O (l) H2O (s) DH = -6.01 kJ

• If you multiply both sides of the equation by a factor n,


then DH must change by the same factor n.

2H2O (s) 2H2O (l) DH = 2 x 6.01 = 12.0 kJ


Thermochemical Equations

• The physical states of all reactants and products must be


specified in thermochemical equations.
H2O (s) H2O (l) DH = 6.01 kJ

H2O (l) H2O (g) DH = 44.0 kJ

How much heat is evolved when 266 g of white


phosphorus (P4) burn in air?
P4 (s) + 5O2 (g) P4O10 (s) DH = -3013 kJ

1 mol P4 3013 kJ
266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4
The specific heat (s) of a substance is the amount of heat (q)
required to raise the temperature of one gram of the
substance by one degree Celsius.
The heat capacity (C) of a substance is the amount of heat (q)
required to raise the temperature of a given quantity (m) of
the substance by one degree Celsius.
C = ms
Heat (q) absorbed or
released:
q = msDt
q = CDt
Dt = tfinal -
tinitial
How much heat is given off when an 869 g iron bar cools
from 940C to 50C?

s of Fe = 0.444 J/g • 0C

Dt = tfinal – tinitial = 50C – 940C = -890C

q = msDt = 869 g x 0.444 J/g • 0C x –890C = -34,000 J


Constant-Volume Calorimetry

qsys = qwater + qbomb + qrxn


qsys = 0
qrxn = - (qwater + qbomb)
qwater = msDt
qbomb = CbombDt

Reaction at Constant V
DH = qrxn
DH ~ qrxn
No heat enters or leaves!
Constant-Pressure Calorimetry

qsys = qwater + qcal + qrxn


qsys = 0
qrxn = - (qwater + qcal)
qwater = msDt
qcal = CcalDt

Reaction at Constant P
DH = qrxn

No heat enters or leaves!


Standard enthalpy of formation (DH0) is
f the heat change
that results when one mole of a compound is formed from
its elements (in most stable form) at a pressure of 1 atm.

The standard enthalpy of formation of any element in its


most stable form is zero.

DHof (O2) = 0 DHof (C, graphite) = 0

DHof (O3) = 142 kJ/mol DHof (C, diamond) = 1.90 kJ/mol


The standard enthalpy of reaction (DH0 rxn
) is the enthalpy of a
reaction carried out at 1 atm.

aA + bB cC + dD

DHorxn = [ cDHof (C) + dDHof (D) ] - [aDHof (A) + bDHof (B) ]

DHorxn = S nDHof (products) - S mDHfo (reactants)

Hess’s Law: When reactants are converted to products, the


change in enthalpy is the same whether the reaction takes
place in one step or in a series of steps.

(Enthalpy is a state function. It doesn’t matter how you


get there, only where you start and end.)
Hess’s Law of Heat Summation
The enthalpy change of an overall process is the sum of
the enthalpy changes of its individual steps.

Example:
Problem: Calculate the energy involved in the oxidation of elemental
sulfur to sulfur trioxide from reactions:
1) S (s) + O2 (g) SO2 (g) H1 = -296.0 kJ

2) 2 SO2 (g) + O2 (g) 2 SO3 (g) H2 = -198.2 kJ

3) S (s) + 3/2 O2 (g) SO3 (g) H3 = ?


If you add two or more
equations to get a new
equation, you must add the
H’s to get the H for
the new equation.
Calculate the standard enthalpy of formation of CS2 (l)
given that:
C(graphite) + O2 (g) CO2 (g) DH
rxn = -393.5 kJ
0

S(rhombic) + O2 (g) SO2 (g) DH


rxn = -296.1 kJ
0

CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) DH


rxn = -1072 kJ
0

1. Write the enthalpy of formation reaction for CS2

C(graphite) + 2S(rhombic) CS2 (l)


2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g) CO2 (g) DH
rxn = -393.5 kJ
0

2S(rhombic) + 2O2 (g) 2SO2 (g) DH


rxn = -296.1x2 kJ
0

+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) DH


rxn = +1072 kJ
0

C(graphite) + 2S(rhombic) CS2 (l)


DH0rxn= -393.5 + (2x-296.1) + 1072 = 86.3 kJ
Benzene (C6H6) burns in air to produce carbon dioxide and
liquid water. How much heat is released per mole of
benzene combusted? The standard enthalpy of formation
of benzene is 49.04 kJ/mol.

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

DH0rxn = S nDH0f (products) - S mDHf0 (reactants)

DH0rxn = [ 12DHf0 (CO2) + 6DH0f (H2O)] - [ 2DHf0 (C6H6)]

DH0rxn = [ 12(–393.5) + 6(–285.8) ] – [ 2(49.04) ] = -6534.88

-6535kJ
= - 3267 kJ/mol C6H6
2 mol
The
Quantum Mechanical Atom
Chapter 7
Properties of Waves

Waves are an oscillation that moves outward from a


disturbance.
Wavelength (l) is the distance between identical points
on successive waves.
Properties of Waves

Frequency (n) is the number of waves that pass through a


particular point in 1 second (Hz = 1 cycle/s).

Amplitude is the vertical distance from the midline of a


wave to the peak or trough.

The speed (u) of the wave = l x n


Maxwell (1873), proposed that visible light consists of
electromagnetic waves.

Electromagnetic
radiation is the emission
and transmission of energy
in the form of
electromagnetic waves.

Speed of light (c) in vacuum = 3.00 x 108 m/s

All electromagnetic radiation


lxnc
In 1900 Max Planck proposed that atoms and
molecules can emit (or absorb) energy only in
discrete quantities. The smallest quantity of
energy that can be emitted is called a quantum
(photon) whose energy is given by

E = hn

*Einstein proposed that light itself is quantized


* Photons are the quanta of electromagnetic
energy
*Photons have an energy equal to: E = hv
*h = Plank’s Constant, and is equal to:
6.6260755 x 10 - 3 4J · sec
When copper is bombarded with high-energy electrons,
X rays are emitted. Calculate the energy (in joules)
associated with the photons if the wavelength of the X
rays is 0.154 nm.

E = hn
E = hc
l
E = 6.63 x 10-34 (J•s) x 3.00 x 10 8 (m/s)
0.154 x 10-9 (m)

E = 1.29 x 10 -15 J
Bohr’s Model of
the Atom (1913)
1. e- can only have specific
(quantized) energy
values
2. light is emitted as e-
moves from one energy
level to a lower energy
level
1
En = -RH( )
n2

n (principal quantum number) = 1,2,3,…


RH (Rydberg constant) = 2.18 x 10-18J
Calculate the wavelength (in nm) of a photon
emitted by a hydrogen atom when its electron
drops from the n = 5 state to the n = 3 state.

1 1
Ephoton = DE = RH( )
n2i n2f
Ephoton = 2.18 x 10-18 J x (1/25 - 1/9)=1.55 x 10-19 J
Ephoton = h x c / l
l = h x c / Ephoton
= 6.63 x 10-34 (J•s) x 3.00 x 108 (m/s)/1.55 x 10-19J
= 1.28 x 10-6 m
= 1.28 x 10-6 m x 1nm = 1280 nm
10-9m
Problems with the Bohr model.
Bohr’s approach only works for the hydrogen atom. It can not explain the
spectra of atoms with more than one electron.

According to de Broglie an electron bound to a nucleus behaves like


a standing wave.

An allowed energy state is one in which an integral number of


waves will fit around the circumference of the orbit.
Thus de Broglie suggested that the wave length of a matter wave
is given by
l= h
mv
Where:
h = planck’s constant = 6.63 x 10-34
λ = wavelength
m = mass of particle
v = velocity of particle
Bohr’s and de Broglie’s approach did not
work for atoms other than hydrogen.

In the 1920’s Heisenberg, Schrödinger,


and Dirac developed the modern theory of
the atom which we call QUANTUM
MECHANICS.

The Heisenberg Uncertainty Principle: It is


impossible to know simultaneously both
the momentum and position of a particle
with certainty.
When the Schrödinger equation is
solved for the H atom we get the
exact energy states that the electron
can occupy. Associated with each
energy state is a wave function ,
psi.
The square of  gives the probability
that the electron will be found in a
particular region. This region is called an
orbital.
Orbital: the region in space where
the electron is most likely to be
found.

Note: QM tells us nothing about the


path of the electron. Only
probability information is given.
When the Schrödinger equation is
solved, the energies and orbitals are
found to depend on several quantum
numbers.

THE PRINCIPAL QUANTUM NUMBER


n = 1, 2, 3, 4, 5, ….
It tells the principle energy level of the
electron and its average distance from
the nucleus.
THE ANGULAR MOMENTUM Q.N.
l = 0,1, 2, 3, …(n-1)
s, p, d, f
It tells the sub-level of the electron
and the shape of the orbital.

THE MAGNETIC Q.N.


ml = - l …. + l
It tells the number of orbitals and their
orientation in space.
l = 0 (s orbitals)

l = 1 (p orbitals)

l = 2 (d orbitals)
Electron Spin

Experiments indicate that the electron possesses an


intrinsic angular momentum which is constant and a
basic property of the electron. A spinning charge
generates a magnetic field - thus the electron
produces a tiny magnetic field.

When an electron is placed in an external magnetic


field
its own magnetic field is quantized. It can line up with
the external field or oppose the external field.

We say the spin quantum number ms= +½ or -½


The Pauli Exclusion Principle

No two electrons in an atom can have the same


four quantum numbers.

This means that no more than two electrons can exist in


the same orbital and these electrons must have opposite
spins.

Note: the first three quantum numbers designate a


particular orbital in the atom.
How many 2p orbitals are there in an atom?
n=2
If l = 1, then ml = -1, 0, or +1
2p
3 orbitals
l=1

How many electrons can be placed in the 3d


subshell?
n=3 If l = 2, then ml = -2, -1, 0, +1, or +2

3d 5 orbitals which can hold a total of 10 e-

l=2
Atoms With More Than One Electron

In the hydrogen atom the electron energies depend only


on the principle quantum number, n.

If an atom has more than one electron the different


sublevels have different energies. The reasons for this are
complicated.
“Fill up” electrons in lowest energy orbitals (Aufbau principle)

? ?

Li
Be
B5
C 634electrons
electrons
BBe
Li1s1s
1s
2 2s
222s
2s
2 2p
12 1

H
He12electron
electrons
He
H 1s
1s12
Paramagnetic Diamagnetic
unpaired electrons all electrons paired

2p 2p
The most stable arrangement of electrons
in subshells is the one with the greatest
number of parallel spins (Hund’s rule).

C 967
N
O
F
Ne 810
electrons
electrons
electrons
Ne
N
O
C
F 1s
1s222s
22s222p
22p5
2346
Orbital Diagrams H Be
Element Symbol Electron Orbital Diagrams
Configuration

Hydrogen H 1s1
1s 2s

Helium He 1s2
1s 2s

Lithium Li 1s22s1
1s 2s

Beryllium Be 1s22s2
1s 2s
Orbital Diagrams - II : B Ne

B (5 e-) 1s2 2s2 2p1


1s 2s 2px 2py 2pz
C (6 e-) 1s2 2s2 2p2
1s 2s 2px 2py 2pz
N (7 e-) 1s2 2s2 2p3
1s 2s 2px 2py 2pz
O (8 e-) 1s2 2s2 2p4
1s 2s 2px 2py 2pz

F (9 e-) 1s2 2s2 2p5


1s 2s 2px 2py 2pz

Ne (10 e-) 1s2 2s2 2p6


1s 2s 2px 2py 2pz
Condensed Ground-State Electron
Configurations in the First Three
Periods
Electron Configuration - III
K [Ar] 4s 1
Ca [Ar] 4s 2 Or this order is OK !
Sc [Ar] 4s 2 3d 1 [Ar] 3d 1 4s
2

Ti [Ar] 4s 2 3d 2 [Ar] 3d 2 4s
2

V [Ar] 4s 2 3d 3 [Ar]Anomalies
3d 3 4s
2 to Filling
Cr [Ar] 4s 1 3d 5
Mn [Ar] 4s 2 3d 5
Fe [Ar] 4s 2 3d 6 Either order will be OK !
Co [Ar] 4s 2 3d 7 But it’s normally best to
Anomalies
Ni [Ar] 4s 2 3d 8 put the one filling last!!!
to Filling
Cu [Ar] 4s 1 3d 10
2 10
The Periodic Table of the Elements
H Electronic Structure He
Li Be B C N O F Ne
N Mg Al Si P S Cl Ar
aK Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr NbM Tc R Rh Pd A Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta oW Re uOs Ir Pt gAu Hg Tl Pb Bi Po At Rn
Fr Ra Ac Rf Ha Sg

Ce Pr Nd PmSm EuGd T DyHo Er Tm Yb Lu


Th Pa U Np PuAmC b Bk Cf Es FmMd N Lr
m o
“ s” Orbitals “ p” Orbitals
“ d” Orbitals “ f ” Orbitals
What is the electron configuration of Mg?
Mg 12 electrons

1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons
Abbreviated as [Ne]3s2 [Ne] 1s22s22p6

What are the possible quantum numbers for the


last (outermost) electron in Cl?
Cl 17 electrons
1s22s22p63s23p5 2 + 2 + 6 + 2 + 5 = 17 electrons
Last electron added to 3p orbital

n=3 l=1 ml = -1, 0, or +1 ms = ½ or -½


ns2np6
ns1 Ground State Electron Configurations of the Elements

ns2np1

ns2np2
ns2np3

ns2np4
ns2np5
ns2

d10
d1

d5

4f
5f
Electron Configurations of
Metal Ions

All metals lose electrons to form cations. Many of the


metals which are representative elements lose all their
valence electrons to have noble gas configurations.

Transition metal ions rarely attain a noble gas configuration.


They always lose the outer s electrons first. Usually they
lose one or more d electrons as well.

Example: Fe (how many unpaired electrons?)


Na+: [Ne] Al3+: [Ne] F-: 1s22s22p6 or [Ne]

O2-: 1s22s22p6 or [Ne] N3-: 1s22s22p6 or [Ne]

Na+, Al3+, F-, O2-, and N3- are all isoelectronic with Ne

What neutral atom is isoelectronic with H- ?


Trends in Key Periodic Atomic
Properties

Atomic Size: There is no real limit to how far an electron


can be away from the nucleus. But, atomic size is a
measurable quantity. In practice we measure the distance
between two identical, adjacent atomic nuclei and divide
distance in half.

Many of the properties of elements are related to the size


of their atoms.
Cation is always smaller than atom from
which it is formed.
Anion is always larger than atom from
which it is formed.
Ionization energy is the minimum energy (kJ/mol)
required to remove an electron from a gaseous atom in its
ground state.

I1 + X (g) X+(g) + I1 first ionization energy


e-
I2 + X+(g) X2+(g) + I2 second ionization energy
e-
I3 + X2+(g) X3+(g) + I3 third ionization energy
e-
I1 < I2 <
I3
There is a rough inverse
correlation between I1 and
atomic radius.
General Trend in First Ionization Energies
Increasing First Ionization Energy
Increasing First Ionization Energy
Electron affinity is the negative of the energy change that
occurs when an electron is accepted by an atom in the
gaseous state to form an anion.

X (g) + e- X-(g)

F (g) + e- F-(g) DH = -328 kJ/mol EA = +328 kJ/mol

O (g) + e- O-(g) DH = -141 kJ/mol EA = +141 kJ/mol


Chemical Bonding:
General Concepts
Chapter 8
Valence electrons are the outer shell electrons of an
atom. The valence electrons are the electrons that
participate in chemical bonding.
Group e- configuration # of valence e-
1A ns1 1
2A ns2 2
3A ns2np1 3
4A ns2np2 4
5A ns2np3 5
6A ns2np4 6
7A ns2np5 7
Ionic Bonding
Electron Configurations of Ions of the
Representative Elements
• These are derived from the electron configuration of
elements with the required number of electrons added or
removed from the most accessible orbital.
• Electron configurations can predict stable ion formation:
• Mg: [Ne]3s2
• Mg+: [Ne]3s1 not stable
• Mg2+: [Ne] stable
• Cl: [Ne]3s23p5
• Cl: [Ne]3s23p6 = [Ar] stable
The Ionic Bond

Li + F Li+ F -
1s22s1 1s22s22p5 [He]
1s2[2Ne]
1s 2s22p6

Li Li+ + e-
e- + F F -

Li+ + F - Li+ F -

In all ionic compounds there is electro


Covalent Bonding II

In the Lewis structure model valence electrons are


presented as dots. The covalent bond is represented by a
shared pair (bonding pair) of electrons. An electron pair
that is not involved in bonding is called a lone pair or
unshared pair or nonbonding pair.
A covalent bond is a chemical bond in which two or more
electrons are shared by two atoms.

Why should two atoms share electrons?

F + F F F
7e- 7e- 8e- 8e-

Lewis structure of F2

single covalent bond lone pairs F F lone pairs

single covalent bond


lone pairs F F lone pairs
Lewis structure of water single covalent bonds

H + O + H H O H or H O H
2e-8e-2e-

Double bond – two atoms share two pairs of electrons

O C O or O C O
8e- 8ebonds
double - 8e- double bonds

Triple bond – two atoms share three pairs of electrons

N N or N N
8e-8e
triple -
bond
triple bond
Lengths of Covalent Bonds
Bond
Bond Length
Type (pm)

C-C 154

CC 133

CC 120

C-N 143

CN 138

Bond Lengths CN 116


Triple bond < Double Bond < Single Bond
Electronegativity and Bond Polarity

Some bonds are purely ionic - a complete transfer of


electrons has occurred. EX: NaCl

Some bonds are pure covalent - the bonding electrons are


shared equally. EX: H2 or Cl2

In many cases the electrons are shared, but not equally.


These bonds are called polar-covalent and are considered to
be partially positively charged and partially negatively
charged. EX: HCl

Electronegativity: the relative ability of a bonded atom to


attract the shared electrons.
Polar covalent bond or polar bond is a covalent
bond with greater electron density around one of the
two atoms

electron rich
electron poor
region
region e- poor e- rich

H F H F
d+ d-
Electronegativity is the ability of an atom to attract
toward itself the electrons in a chemical bond.

Electron Affinity - measurable, Cl is highest

X (g) + e- X-(g)

Electronegativity - relative, F is highest


Classification of bonds by difference in electronegativity

Difference Bond Type


0 Non-Polar Covalent
2 Ionic
0 < and <2 Polar Covalent

Increasing difference in electronegativity

Non-Polar Covalent Polar Covalent Ionic


share e- partial transfer of e- transfer e-
Classify the following bonds as ionic, polar covalent, or
non-polar covalent: The bond in CsCl; the bond in H2S; and
the NN bond in H2NNH2.

Cs – 0.7 Cl – 3.0 3.0 – 0.7 = 2.3 Ionic

H – 2.1 S – 2.5 2.5 – 2.1 = 0.4 Polar Covalent

N – 3.0 N – 3.0 3.0 – 3.0 = 0 Non-Polar Covalent


Writing Lewis Structures
1. Draw skeletal structure of compound showing
what atoms are bonded to each other. Put least
electronegative element in the center.
2. Count total number of valence e-.
Add 1 for each negative charge.
Subtract 1 for each positive charge.

3. Complete an octet for all atoms except H


until all are complete or you run out of electrons.

4. Form double and triple bonds on central atom


if needed to complete octet
Writing Lewis Structures
1. S = N-A
Where:
S = # of shared electrons
N = # of needed electrons
A = # of available electrons
1. To calculate N: Multiple the number of atoms
that are not H in the structure by 8; If H is
present, multiple the number of H’s by 2
2. To calculate A: Add the total number of valence
electrons for each atom
Writing Lewis Structures
Example:
What is the Lewis Structure for water?
H2O
N = (1x8)+(2x2) = 12
A = 6 e- + 2 e- = 8
S=N-A = 4

H O H or H O H
Two possible skeletal structures of formaldehyde (CH2O)

H
H C O H C O
H

An atom’s formal charge is the difference between the


number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis
structure.
formal charge total number

( )
total number 1 total number
on an atom in of valence
a Lewis
= electrons in - of nonbonding - of bonding
electrons 2 electrons
structure the free atom

The sum of the formal charges of the atoms in a molecule


or ion must equal the charge on the molecule or ion.
Formal Charge

Formal charge: the charge an atom would have if the bonding


electrons were shared equally.

The formal charges must add up to equal the actual charge on


the species.
Formal Charge and Lewis Structures
1. For neutral molecules, a Lewis structure in which there
are no formal charges is preferable to one in which
formal charges are present.
2. Lewis structures with large formal charges are less
plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of
formal charges, the most plausible structure is the one in
which negative formal charges are placed on the more
electronegative atoms.
Formal Charge and Lewis Structures
Which is the most likely Lewis structure for CH2O?

-1 +1 H 0 0
H C O H C O
H

FC C1 = 4 – 2 - ½(6) = -1 FC C2 = 4 – 0- ½(8) = 0
FC O1 = 6 – 2- ½(6) = +1 FC O2= 6-4-½(4) =
0
Resonance

For some molecules and ions no single Lewis


Structure can be drawn that agrees with experimental
data.
In cases like this we can:

1. Go on to a more sophisticated model of


the covalent bond
or
2. We can try to patch up the simple Lewis
structure model to make it work.
Resonance

Resonance: the use of two or more Lewis


structures to represent a particular molecule
or ion.

Resonance structures are connected by a


double-headed arrow. The true structure is a
blend of the resonance structures.

Resonance indicates that electron delocalization


occurs in the molecule.
A resonance structure is one of two or more Lewis
structures for a single molecule that cannot be represented
accurately by only one Lewis structure.

+ - - +
O O O O O O

What are the resonance structures of the


carbonate (CO32-) ion?

- - - -
O C O O C O O C O

O O O
- -
Exceptions to the Octet Rule

The Incomplete Octet

Be – 2e-
BeH2 2H – 2x1e- H Be H
4e-

B – 3e- 3 single bonds (3x2) =


3F – 3x7e- F B F 6 9 lone pairs (9x2) = 18
BF3
24e- Total = 24
F
Exceptions to the Octet Rule

Odd-Electron Molecules

N – 5e-
NO O – 6e- N O
11e-

The Expanded Octet (central atom with principal quantum number n > 2)

F
F F
S – 6e- 6 single bonds (6x2) = 12
SF6 6F – 42e- S 18 lone pairs (18x2) = 36
48e- Total = 48
F F
F
How the Model Explains the Properties
of Covalent Compounds

The covalent bonding model proposes that electron sharing


leads to strong, localized bonds. But most compounds with
covalent bonds are gases, liquids, or low-melting solids.
Ionic compound are high-melting solids.

Why is this? Are covalent bonds weaker than ionic bonds?

Within a molecule there are strong intramolecular bonds.


Between molecules there are weak intermolecular forces.
The latter are what determine melting and boiling points.
Comparison of Ionic and Covalent Compounds
The enthalpy change required to break a particular bond in
one mole of gaseous molecules is the bond energy.

Bond Energy
H2 (g) H (g ) + H (g ) DH0 = 436.4 kJ
Cl2 (g) Cl (g)+ Cl (g ) DH0 = 242.7 kJ
HCl (g) H (g ) + Cl (g ) DH0 = 431.9 kJ
O 2 (g ) O (g ) + O (g ) DH0 = 498.7 kJ O O
N2 (g) N (g ) + N (g ) DH0 = 941.4 kJ N N

Bond Energies
Single bond < Double bond < Triple bond
Thus the relationship between bond length, bond strength, and bond energy is :

The shorter the bond length,


the greater the bond strength,
the greater the bond energy!

VS

The longer the bond length,


the lower the bond strength,
the lower the bond energy!
Molecular Geometry and
Hybridization of Atomic Orbitals
Chapter 10
Molecular Shapes

Valence Shell Electron-Pair Repulsion


(VSEPR) Theory

Each group of valence electrons around a


central atom is located as far away from the
others as possible in order to minimize
repulsion.

An electron group may be a single, double,


or triple bond or a lone pair.
Balloon Analogy for the Mutual
Repulsion of Electron Groups

Two Three Four Five Six

Number of Electron Groups


Valence shell electron pair repulsion (VSEPR) model:

Predict the geometry of the molecule from the electrostatic


repulsions between the electron (bonding and nonbonding) pairs.

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

B B

10.1
BeCl2

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear


trigonal trigonal
AB3 3 0
planar planar

10.1
BF3

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear


trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral

10.1
CH4

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear


trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal

10.1
PCl5

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear


trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
AB6 6 0 octahedral octahedral

10.1
SF6

10.1
Molecular Shapes

You must distinguish between the electron-group


arrangement and the molecular shape. The
molecular shape is defined by the relative positions
of the atomic nuclei. If there are no lone pairs of
electrons the molecular shape is the same as the
electron-group arrangement.
Bonding-pair vs. lone-pair vs. bonding lone-pair vs. lone
bonding pair
< pair repulsion
< pair repulsion
repulsion
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

trigonal trigonal
AB3 3 0
planar planar
trigonal
AB2E 2 1 bent
planar

SO2

10.1
SO2

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral


trigonal
AB3E 3 1 tetrahedral
pyramidal

10.1
NH3

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral


trigonal
AB3E 3 1 tetrahedral
pyramidal

AB2E2 2 2 tetrahedral bent


O
H H

10.1
H2O

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal seesaw
AB4E 4 1
bipyramidal

SF4

10.1
SF4

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedro
trigonal n
AB3E2 3 2 T-shaped
bipyramidal
F

F Cl

10.1
BrF3

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedro
trigonal n
AB3E2 3 2 T-shaped
bipyramidal
trigonal
AB2E3 2 3 linear
bipyramidal
I

I 10.1
ICl2 -

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral


square
AB5E 5 1 octahedral
pyramidal
F
F F
Br
F F

10.1
BrF5

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral


square
AB5E 5 1 octahedral
pyramidal
square
AB4E2 4 2 octahedral
planar
F F
Xe
F F

10.1
ICl4 -

10.1
Predicting Molecular Geometry
What are the molecular geometries of AsH3,
OF2, AlCl4-, H3O+, SnCl5-?

AsH3 Trigonal pyramid

bent
OF2

Trigonal pyramid
H3O+

SnCl5- Trigonal bipyramid


10.1
Polar Molecules - Dipole
moments

A polar molecule is one the has a positive end and a


negative end. (The center of positive charge and
the center of negative charge do not coincide.) A
polar molecule is said to have a dipole moment.

A molecule with two or more polar bonds can be


nonpolar if it is symmetrical.
Dipole Moments and Polar Molecules

electron rich
electron poor
region
region

H F

d d

10.2
Polarity of CO2 and H2O

Water - H2O Carbon Dioxide - CO2


- - - + -
O O C O
H H A non- polar molecule
+ +
A Polar molecule The bonds are polar,
The bonds are polar, and but the molecule is
the molecule is symmetrical, so that the
non-symmetrical. molecule overall is
non-polar.
Predicting The Polarity of Molecules
Problem: From electronegativity, and their periodic trends, predict
whether each of the following molecules is polar and show the direction
of bond dipoles and the overall molecular dipole.
(a) Phosphine, PH3
(b) Carbon disulfide, CS2 (also OCS)

(a) .. .. ..
P P P
H H H H
H H
H H Bond dipoles H Molecular Dipole
Molecular shape
10.2
Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CH4

O S

dipole moment dipole moment


polar molecule polar molecule

H C H
O C O

no dipole moment H
nonpolar molecule no dipole moment
nonpolar molecule
10.2
Valence Bond Theory
Basic Principle of Valence Bond Theory:
a covalent bond forms when the orbitals from
two atoms overlap and a pair of electrons
occupies the region between the nuclei.
Usually this means that each bonding orbital
should contain one electron. The electrons
must have opposite spins.

The bond strength depends on the attraction of nuclei for


the shared electrons, so the greater the orbital overlap,
the stronger the bond.
The sp Hybrid Orbitals in Gaseous BeCl2
Hybridization is the mixing of atomic
orbitals in an atom to generate a set of
new orbitals called hybrid orbitals.

The total number of orbitals doesn’t


change.
Covalent bonds are formed by:
a. Overlap of hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid
orbitals
10.4
10.4
How do I predict the hybridization of the central atom?

Count the groups of electrons


and determine the electron geometry.
# electron groups
+
Electron geometry
Hybridization Examples

2 (linear) sp BeCl2

3 (trigonal planar) sp2 BF3

4 (tetrahedral) sp3 CH4, NH3, H2O

5 (trig. bipyramid) sp3d PCl5

6 (octahedral) sp3d2 SF6


10.4
The sp3d Hybrid Orbitals in PCl5
The sp3d2 Hybrid Orbitals in
SF6

Sulfur Hexafluoride -- SF6


Predict correct
bond angle
All the bonds we have seen so far are called
sigma bonds: the highest electron density is along
the bond axis. All single bonds are sigma bonds
and the first bond in double or triple bonds is a
sigma bond.

A pi bond is formed by a side-to-side overlap of


p orbitals. There are regions of high electron
density above and below the bond axis. The second
bond of a double bond is a pi bond, as are two of the
bonds in a triple bond.
10.5
Pi bond (p) – electron density above and below plane of nuclei
Sigma bond (s) – electron density between the 2 atoms
of the bonding atoms 10.5
10.5
Sigma (s) and Pi Bonds (p)

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

How many s and p bonds are in the acetic acid


(vinegar) molecule CH3COOH?

H
O

s bonds = 6 + 1 = 7
H C C O H
p bonds = 1
H
10.5
Skip pages 318-326 molecular orbitals
Resonance implies electron delocalization. This
can be explained by valence bond and molecular
orbital theory.
This occurs when a p orbital overlaps with more
than one other p orbital. The p electrons are free
to move around three or more atoms.
Examples: ozone, benzene, sulfur trioxide.
Structures with delocalized electrons always
have greater stability than similar structures
without delocalized electrons.
Delocalized electrons are not confined between two
adjacent bonding atoms, but actually extend over three or
more atoms.

10.8
Experiments show O2 is paramagnetic

O
O

No unpaired e-
Should be diamagnetic

Molecular orbital theory – bonds are formed from


interaction of atomic orbitals to form molecular
orbitals.

10.6
Energy levels of bonding and antibonding molecular
orbitals in hydrogen (H2).

A bonding molecular orbital has lower energy and greater


stability than the atomic orbitals from which it was formed.

An antibonding molecular orbital has higher energy and


lower stability than the atomic orbitals from which it was
formed. 10.6
10.6
10.6
Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

10.7
Number of Number of
bond order =
1
2 ( electrons in
bonding
MOs
-
electrons in
antibonding
MOs
)

bond
½ 1 ½ 0
order
10.7