Chemistry:

The Study of Change

Chapter 1
Chemistry is the study of matter and the
changes it undergoes

Matter is anything that occupies space and

has mass.
A substance is a form of matter that has a
definite composition and distinct properties.

liquid nitrogen gold ingots silicon crystals

A mixture is a combination of two or more substances
in which the substances retain their distinct identities.

1. Homogenous mixture – composition of the

mixture is the same throughout.

soft drink, milk, solder

2. Heterogeneous mixture – composition is not

uniform throughout.

cement,
iron filings in sand
3
Physical means can be used to separate a mixture
into its pure components.

magnet

distillation

4
An element is a substance that cannot be
separated into simpler substances by chemical
means.
• 118 elements have been identified
• 94 elements occur naturally on Earth
gold, aluminum, lead, oxygen, carbon, sulfur

• 24 elements have been created by scientists

technetium, americium, seaborgium
5
6
A compound is a substance composed of atoms
of two or more elements chemically united in fixed
proportions.

Compounds can only be separated into their

pure components (elements) by chemical
means.

lithium fluoride quartz dry ice – carbon dioxide

7
Classifications of Matter

8
A Comparison: The Three States of Matter

9
 The Three States of Matter: Effect of a Hot
Poker on a Block of Ice

GAS
Vaporization Condensation
(heat or reduce pressure) (cool or increase pressure)

Liberates Energy
Requires Energy

LIQUID

Melting Freezing
(heat) (cool)

SOLID
 Types of Changes

A physical change does not alter the composition

or identity of a substance.
sugar dissolving
ice melting
in water
A chemical change alters the composition or
identity of the substance(s) involved.

hydrogen burns in
air to form water

11
PROBLEM: Decide whether each of the following
process is primarily a physical or a chemical change,
and explain briefly.
(a) Frost forms as the temperature drops on a humid winter
night.
(b) Dynamite explodes to form a mixture of gases.
(c) Dissolving sugar and water.
(d) A silver fork tarnishes in air.
Criteria: “Does the substance change composition or
just change form?”
SOLUTION:
(a) physical change
(b) chemical change
(c) physical change
(d) chemical change
 Extensive and Intensive Properties
An extensive property of a material depends upon
how much matter is is being considered.
• mass
• length
• volume
An intensive property of a material does not
depend upon how much matter is is being
considered.
• density
• temperature
• color 14
International System of Units (SI)

15
16
Volume – SI derived unit for volume is cubic meter (m3)
1 cm3 = (1 x 10-2 m)3 = 1 x 10-6 m3
1 dm3 = (1 x 10-1 m)3 = 1 x 10-3 m3
1 L = 1000 mL = 1000 cm3 = 1 dm3
1 mL = 1 cm3

17
 Density
The density a substance is its mass per unit
volume (the volumetric mass).

SI derived unit for density is kg/m3

1 g/cm3 = 1 g/mL = 1000 kg/m3

mass m
density =
volume d= V

18
19
A piece of platinum metal with a density of 21.5
g/cm3 has a volume of 4.49 cm3. What is its mass?
m
d= V
m = d x V = 21.5 g/cm3 x 4.49 cm3 = 96.5 g

20
21
22
A Comparison of Temperature Scales

K = 0C + 273.15
273 K = 0 0C
373 K = 100 0C

0F = 9 x 0C + 32
5
32 0F = 0 0C
212 0F = 100 0C

23
Convert 172.9 0F to degrees Celsius.

0F = 9 x 0C + 32
5
0F – 32 = 9 x 0C
5
5 x (0F – 32) = 0C
9
0C = 5 x (0F – 32)
9
0C = 5 x (172.9 – 32) = 78.3
9

24
25
Atoms, Molecules and Ions

2
 Atomic structure

Atom is the basic unit of an element that enter into

chemical combination .
mass p ≈ mass n ≈ 1840 x mass e-

28
 Atomic number, Mass number and Isotopes
Atomic number (Z) = number of protons in nucleus
Mass number (A) = number of protons + number of neutrons
= atomic number (Z) + number of neutrons
Isotopes are atoms of the same element (X) with different
numbers of neutrons in their nuclei

Mass Number A
ZX
Element Symbol
Atomic Number

1 2 3
1H 1H (D) 1H (T)
H isotopes names: hydrogen deuterium tritium

235 238
92 U 92 U 29
Atomic number, Mass number and Isotopes

The Isotopes of Hydrogen

hydrogen deuterium tritium

30
 Atomic number, Mass number and Isotopes

14
How many protons, neutrons, and electrons are in 6 C ?

6 protons, 8 (14 - 6) neutrons, 6 electrons

11
How many protons, neutrons, and electrons are in 6 C ?

6 protons, 5 (11 - 6) neutrons, 6 electrons

31
 Atomic number, Mass number and Isotopes

Find number of electrons, protons, and neutrons?

63 239 26 17 202 48
29
Cu 94
Pu 13
Al O 80
Hg 22
Ti
8

e 29 94 13 8 80 22
p 29 94 13 8 80 22
n 34 145 13 9 122 26
Atomic number, Mass number and Isotopes

33
 The Modern Periodic Table
Alkali Earth Metal
Alkali Metal

Noble Gas
Group

Halogen
Period

½ of elements discovered between (1800-1900)

Only noble gases exists as single atoms called monoatomic
34
 Period : increasing Z
Group : similar chemical metals metalloids
nonmetals
properties

Metals -good conductors of heat and electricity

-occupy most of the table

Nonmetals poor conductors of heat and electricity

-only 17 elements
METALLOIDS - INTERMEDIATE BETWEEN
METALS AND NON METALS
-ONLY 8 ELEMENTS
 Molecules and Ions
A molecule is an aggregate of two or more atoms in a
definite arrangement held together by chemical forces

H2 H2O NH3 CH4

A diatomic molecule contains only two atoms
H2
same
element
is not a
H2, N2, O2, Br2, HCl, CO compou
nd but
pure
element diatomic elements

A polyatomic molecule contains more than two atoms

36
O3, H2O, NH3, CH4
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 11 electrons Na+ 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 17 electrons Cl- 18 electrons
37
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-

38
 27 3+
How many protons and electrons are in 13 Al ?

13 protons, 10 (13 – 3) electrons

78 2-
How many protons and electrons are in 34 Se ?

34 protons, 36 (34 + 2) electrons

39
 Chemical Formulas
A molecular formula shows the exact number of
atoms of each element in the smallest unit of a
substance

An empirical formula shows the simplest

whole-number ratio of the atoms in a substance

molecular empirical
H2O H2O
C6H12O6 CH2O

O3 O
40
N2H4 NH2
ionic compounds consist of a combination of cations
and an anions
• The formula is usually the same as the empirical formula
• The sum of the charges on the cation(s) and anion(s) in
each formula unit must equal zero
The ionic compound NaCl

41
The most reactive metals (green) and the most reactive
nonmetals (blue) combine to form ionic compounds.

42
o If the charges on the cation and anion are numerically
different, we apply the following rule to make the formula
electrically neutral:
The subscript of the cation is numerically equal to the charge on the
anion, and the subscript of the anion is numerically equal to the charge
on the cation.

Aluminum Oxide. The cation is Al3+ and the oxygen anion is O2-.

The sum of the charges is 2(+3) + 3(-2) = 0.

Thus, the formula for aluminum oxide is Al2O3.
Formula of Ionic Compounds
2 x +3 = +6 3 x -2 = -6

3+
Al2O3 2-
Al O

1 x +2 = +2 2 x -1 = -2

2+
CaBr2 -
Ca Br

2 x +1= +2 1 x -2 = -2

+
Na2CO3 2-
Na CO3
Common Ions Shown on the Periodic Table

45
 Naming Compound
Ionic Compounds
– Often a metal + nonmetal
– Anion (nonmetal), add “ide” to element name
BaCl2 barium chloride

K2O potassium oxide

Mg(OH)2 magnesium hydroxide

KNO3 potassium nitrate

46
47
• Transition metal ionic compounds
– indicate charge on metal with Roman numerals, it is
called Stock system

FeCl2 2 Cl- -2 so Fe is +2 iron(II) chloride

FeCl3 3 Cl- -3 so Fe is +3 iron(III) chloride

48
Cr2S3 3 S-2 -6 so Cr is +3 (6/2) chromium(III) sulfide
Old System
If transition metals can form more than one type of
cations we use (–ic ) for higher charge and (-ous )
for lower charge .

FeCl2 iron(II) chloride becomes ferrous chloride

FeCl3 iron(III) chloride becomes ferric chloride

CuCl cupper(I) chloride becomes cupperous chloride

CuCl2 cupper(II) chloride becomes cupperic chloride

50
51
52
Molecular compounds

− They are usually composed of nonmetallic elements.

− Many molecular compounds are binary compounds.
− Naming binary molecular compounds is similar to
naming binary ionic compounds.
− We place the name of the first element in the
formula first, and the second element is named by
adding -ide to the root of the element name.

HCl hydrogen chloride

HBr hydrogen bromide
SiC silicon carbide
− If a pair of elements form more
than one compound, use prefixes
to indicate number of each kind of
atom
Notes in naming compounds with
prefixes:
 The prefix “mono-” may be
omitted for the first element.
For example, PCl3 is named
phosphorus trichloride, not
monophosphorus trichloride.
 For oxides, the ending “a” in the
prefix is sometimes omitted.
For example, N2O4 may be
called dinitrogen tetroxide rather
than dinitrogen tetraoxide.
Name the following compounds?
HI hydrogen iodide

NF3 nitrogen trifluoride

SO2 sulfur dioxide

N2Cl4 dinitrogen tetrachloride

NO2 nitrogen dioxide

N2O dinitrogen monoxide

55
56
57
 Acids
 An acid can be defined as a substance that yields
hydrogen ions (H+) when dissolved in water.

For example: HCl gas and HCl in water

 Pure substance, hydrogen chloride

 Dissolved in water (H3O+ and Cl−),

hydrochloric acid

 Anions whose names end in “-ide” form acids with a “hydro-

” prefix and an “-ic” ending.

HCl hydrogen chloride

HCl hydrochloric acid
Some Examples of acids
 Naming Oxoacids and Oxoanions
An oxoacid is an acid that contains hydrogen, oxygen, and
another element.
nitric acid carbonic acid phosphoric acid

The formulas of oxoacids are usually written with the H first,

followed by the central element and then O.

H2CO3 (carbonic acid), HClO3 (chloric acid),

HNO3 (nitric acid), H3PO4 (phosphoric acid),
H2SO4 (sulfuric acid) 60
Two or more oxoacids have the same central atom but a
different number of O atoms; the following rules to name
these compounds.
1. Addition of one O atom to the “-ic” acid: The acid is
called “per . . -ic” acid. ( --ate)
HClO3 chloric acid
HClO4 perchloric acid
2. Removal of one O atom from the “-ic” acid: The acid is
called “-ous” acid. ( --ite)

HNO3 nitric acid

HNO2 nitrous acid
3. Removal of two O atoms from the “-ic” acid: The acid is
called “hypo . . . -ous” acid.
HBrO3 Bromic acid
HBrO hypobromous acid.
o The rules for naming oxoanions, anions of oxoacids,
are as follows:
1. When all the H ions are removed from the “-ic” acid,
the anion’s name ends with “-ate.”
2. When all the H ions are removed from the “-ous” acid,
the anion’s name ends with “-ite.”
3. The names of anions in which one or more but not all the
hydrogen ions have been removed must indicate the
number of H ions present.
For example:
– H3PO4 phosphoric acid
– H2PO4- dihydrogen phosphate
– HPO4 2- hydrogen phosphate
– PO43- phosphate
parent acid for all halogenic acids is
HXO3 Halogenic acid
64
65
Bases
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

66
 Hydrated compounds
Hydrates are compounds that have a specific number
of water molecules attached to them.

BaCl2•2H2O barium chloride dihydrate

LiCl•H2O lithium chloride monohydrate
MgSO4•7H2O magnesium sulfate heptahydrate
Sr(NO3)2 •4H2O strontium nitrate tetrahydrate

CuSO4•5H2O cupper sulfate

CuSO4
pper sulfate pentahydrate

67
68
 Quantum Theory and the
Electronic Structure of Atoms

69
 Quantum numbers

Quantum numbers are used to differentiate

between electrons
i. In quantum theory, each electron in an
atom is assigned a set of four quantum
numbers.
ii. Three of these give the location of the
electron, and the fourth gives the orientation
of the electron within the orbital
iii. Definitions of numbers

70
quantum numbers (n, l, ml, ms)

principal quantum number n

n = 1, 2, 3, 4, ….

distance of e- from the nucleus

n=1 n=2 n=3

71
 quantum numbers: (n, l , ml , ms)
angular momentum quantum number l
for a given value of n, l = 0, 1, 2, 3, … n -1

l=0 s orbital
n = 1, l = 0 l=1 p orbital
n = 2, l = 0 or 1 l=2 d orbital
n = 3, l = 0, 1, or 2 l=3 f orbital
Shape of the “volume” of space that the e - occupies
 quantum numbers: (n, l , ml, ms)

magnetic quantum number ml

for a given value of l

ml = -l ,…., 0, …. + l
if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2
orientation of the orbital in space
 Schrodinger Wave Equation

(n, l, ml, ms)

spin quantum number ms

ms = +½ or -½

ms = +½ ms = -½
l = 0 (s orbitals)

l = 1 (p orbitals)

75
Periodic Relationships Among
the Elements
When the Elements Were Discovered

77
 ns2np6
ns1 Ground State Electron Configurations of the Elements

ns2np3

ns2np4
ns2np1

ns2np2

ns2np5
ns2

d10
d1

d5

4f
5f
78
Classification of the Elements

79
 Electron Configurations of Cations and Anions
Of Representative Elements

Na [Ne]3s1 Na+ [Ne]

Atoms lose electrons so that
Ca [Ar]4s2 Ca2+ [Ar] cation has a noble-gas outer
electron configuration.
Al [Ne]3s23p1 Al3+ [Ne]

H 1s1 H- 1s2 or [He]

Atoms gain electrons
so that anion has a F 1s22s22p5 F- 1s22s22p6 or [Ne]
noble-gas outer
O 1s22s22p4 O2- 1s22s22p6 or [Ne]
electron configuration.
N 1s22s22p3 N3- 1s22s22p6 or [Ne]
80
 Cations and Anions Of Representative Elements
+1
+2

+3

-3
-2
-1
 Isoelectronic: have the same number of electrons, and
hence the same ground-state electron configuration

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 electron
configuration

What neutral atom is isoelectronic with H- ?

H-: 1s2 same electron configuration as He

Electron Configurations of Cations of Transition Metals

When a cation is formed from an atom of a transition metal,

electrons are always removed first from the highest ns orbital
and then from the (n – 1)d orbitals.

Fe: [Ar]4s23d6 Mn: [Ar]4s23d5

Fe2+: [Ar]4s03d6 or [Ar]3d6 Mn2+: [Ar]4s03d5 or [Ar]3d5
Fe3+: [Ar]4s03d5 or [Ar]3d5

83
 Atomic Radii

Diatomic molecules
I2

metallic radius covalent radius

Trends in Atomic Radii

86
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) + e- I1 first ionization energy

I2 + X+(g) X2+(g) + e- I2 second ionization energy

I3 + X2+(g) X3+(g) + e- I3 third ionization energy

I 1 < I2 < I3

87
88
Variation of the First Ionization Energy with Atomic Number

Filled n=1 shell

Filled n=2 shell

Filled n=3 shell

Filled n=4 shell
Filled n=5 shell

89
 General Trends in First Ionization Energies

Increasing First Ionization Energy

Increasing First Ionization Energy

90
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- X-(g) DH = -328 kJ/mol EA = +328 kJ/mol

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

91
92
Variation of Electron Affinity With Atomic Number (H – Ba)

93
ml = -1, 0, or 1 3 orientations is space

94
l = 2 (d orbitals)

95
ml = -2, -1, 0, 1, or 2 5 orientations is space

96
 quantum numbers: (n, l, ml , ms)

Existence (and energy) of electron in atom is described

by its unique wave function y.

Pauli exclusion principle - no two electrons in an atom

can have the same four quantum numbers.

Each seat is uniquely identified (E, R12, S8)

Each seat can hold only one individual at a
time
97
98
 Schrodinger Wave Equation
quantum numbers: (n, l , ml , ms)
Shell – electrons with the same value of n
Subshell – electrons with the same values of n and l
Orbital – electrons with the same values of n, l , and ml
If n, l, and ml are fixed, then ms = ½ or - ½
y = (n, l, ml, ½) or y = (n, l, ml -½)
An orbital can hold 2 electrons
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 2l +1
5 orbitals which can hold a total of 10 e-
l=2 100
 The Energies of Orbitals
Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n

n=3

n=2

n=1 101
 Shielding Effect in Many-Electron
atoms
-1s shields 2s and 2p
-2s can penetrates more than 2p or less
shielded
-For same n the penetration power decrease
when l increases
-stability of e- determined by the strength of it’s
attraction to the nucleus thus the energy of
2s<2p

102
Energy of orbitals in a multi-electron atom
Energy depends on n and l

n=3 l = 2

n=3 l = 1
n=3 l = 0

n=2 l = 1
n=2 l = 0

n=1 l = 0
103
“Fill up” electrons in lowest energy orbitals (Aufbau principle)
The most stable arrangement of electrons in subshells is the
one with the greatest number of parallel spins (Hund’s
rule).

Ne 10 Ne 1s22s22p6
electrons
F 9 electrons F 1s22s22p5
O 8 electrons O 1s22s22p4
104
N 7 electrons N 1s22s22p3
 Order of orbitals (filling) in multi-electron atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 105
6s
Electron configuration is how the electrons are
distributed among the various atomic orbitals in an
atom.
number of electrons
in the orbital or subshell
1s1
principal quantum angular momentum
number n quantum number l

Orbital diagram

H
1s1
106
What is the electron configuration of Mg?
Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s
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 1s < 2s < 2p < 3s < 3p < 4s
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 -½107

Paramagnetic substances are those that contain net
unpaired
spins and are attracted by a magnet. On the other hand, if the
electron spins are paired, or antiparallel to each other ( or ),
the magnetic effects cancel out. Diamagnetic substances do
not contain net unpaired spins and are slightly repelled by a
magnet.

Paramagnetic Diamagnetic
all electrons paired
unpaired electrons

2p 2p
112
113
114
115
116
Mass Relationships in
Chemical Reactions
 Micro World Macro World
atoms & molecules grams

Atomic mass is the mass of an atom in

atomic mass units (amu)
amu definition: the mass exactly equal to 1/12 the
mass of one 12C atom
12C = 6e ,6p,6n =12.00 amu me-=0

Experiment show one atom 1H = 8.400% of 12C

atom thus mass of one atom1H =1.008
amu(12.00x.08400)
16O = 16.00 amu , 26Fe = 55.85 amu 118
The average atomic mass is the weighted average of
all of the naturally occurring isotopes of the element.

13C=13.00335 amu
average atomic mass of C=(0.9890x 12.00000
amu)+(0.0110x13.00335) =12.01 amu
119
 Naturally occurring lithium is:
7.42% 6Li (6.015 amu)
92.58% 7Li (7.016 amu)

Average atomic mass of lithium:

7.42 x 6.015 + 92.58 x 7.016

= 6.941 amu
100

120
121
Average atomic mass (6.941)

122
The Mole (mol): A unit to count numbers of particles

Dozen = 12

Pair = 2

The mole (mol) is the amount of a substance that

contains as many elementary entities as there
are atoms in exactly 12.00 grams of 12C
1 mol = NA = 6.0221367 x 1023
Avogadro’s number (NA) 123
 eggs
shoes in grams
Molar mass is the mass of 1 mole of students
atoms
1 mole of 12C atoms = 6.022 x 1023 atoms = 12.00 g
1 12C atom = 12.00 amu

1 mole 12C atoms = 12.00 g 12C

1 mole lithium atoms = 6.941 g of Li

For any element

atomic mass (amu) = molar mass (grams)
124
 One Mole of:

C S

Hg

Cu Fe
125
1 12C atom 12.00 g 1.66 x 10-24 g
x 23 12
=
12.00 amu 6.022 x 10 C atoms 1 amu

1 amu = 1.66 x 10-24 g or 1 g = 6.022 x 1023 amu

M = molar mass in g/mol

NA = Avogadro’s number
126
How many atoms are in 0.551 g of potassium (K) ?

1 mol K = 39.10 g K
1 mol K = 6.022 x 1023 atoms K

1 mol K 6.022 x 1023 atoms K

0.551 g K x x =
39.10 g K 1 mol K

8.49 x 1021 atoms K

127
128
129
130
Molecular mass (or molecular weight) is the sum of
the atomic masses (in amu) in a molecule.

1S 32.07 amu
2O + 2 x 16.00 amu
SO2 SO2 64.07 amu

For any molecule

molecular mass (amu) = molar mass (grams)

1 molecule SO2 = 64.07 amu

1 mole SO2 = 64.07 g SO2
131
132
How many H atoms are in 72.5 g of C3H8O ?

1 mol C3H8O = (3 x 12.01) + (8 x 1.008) + 16.00 = 60.0

1 mol C3H8O molecules = 8 mol H atoms
1 mol H = 6.022 x 1023 atoms H

1 mol C3H8O 8 mol H atoms 6.022 x 1023 H atoms

72.5 g C3H8O x x x =
60.09 g C3H8O 1 mol C3H8O 1 mol H atoms

5.81 x 1024 atoms H

133
134
Formula mass is the sum of the atomic masses
(in amu) in a formula unit of an ionic compound.

1Na 22.99 amu

NaCl 1Cl + 35.45 amu
NaCl 58.44 amu

For any ionic compound

formula mass (amu) = molar mass (grams)

1 formula unit NaCl = 58.44 amu

1 mole NaCl = 58.44 g NaCl
135
What is the formula mass of Ca3(PO4)2 ?

1 formula unit of Ca3(PO4)2

3 Ca 3 x 40.08
2P 2 x 30.97
8O + 8 x 16.00
310.18 amu

136
 Heavy
Mass Spectrometer

Light
Light

Heavy
Mass Spectrum of Ne

137
Percent composition of an element in a compound =
n x molar mass of element
x 100%
molar mass of comnpoud
n is the number of moles of the element in 1 mole
of the compound(can be number of atomes of the
element in the formula)
2 x (12.01 g)
%C = x 100% = 52.14%
46.07 g
6 x (1.008 g)
%H = x 100% = 13.13%
46.07 g
1 x (16.00 g)
%O = x 100% = 34.73%
46.07 g
C2H6O 52.14% + 13.13% + 34.73% = 100.0%
138
139
Examples
What is the mass of H and Cl in 10 g HCl?

What is % composition of the elements C in CH3COOH?

What is % composition of the elements in 25.00 g H2SO4 if mH

= 0.5142 g and mO = 16.3239 g and mS= 8.1619 g ?

140
Percent Composition and Empirical Formulas
Determine the empirical formula of a
compound that has the following
percent composition by mass:
K 24.75, Mn 34.77, O 40.51 percent.

1 mol K
nK = 24.75 g K x = 0.6330 mol K
39.10 g K
1 mol Mn
nMn = 34.77 g Mn x = 0.6329 mol Mn
54.94 g Mn
1 mol O
nO = 40.51 g O x = 2.532 mol O
16.00 g O

141
Percent Composition and Empirical Formulas

nK = 0.6330, nMn = 0.6329, nO = 2.532

0.6330 ~
K: ~ 1.0
0.6329
0.6329
Mn : = 1.0
0.6329
2.532 ~
O: ~ 4.0
0.6329

KMnO4

142
143
Combust 11.5 g ethanol
Collect 22.0 g CO2 and 13.5 g H2O

g CO2 mol CO2 mol C gC 0.5 mol C = 6.0 g C

g H2O mol H2O mol H gH 1.5 mol H =1.5 g H

g of O = g of sample – (g of C + g of H) 4.0 g O = 0.25 mol O

Empirical formula C0.5H1.5O0.25

Divide by smallest subscript (0.25)
Empirical formula C2H6O 144
Molecular Formulas

Molecular weight of the compound should be known

M actual
Multiply the empirical formula by the
X= integer x
M empirical

a compound has empirical formula C6H10S2O but its

molecular weight is 324 g/mol
C12H20S4O2

Calculate the number of grams of Al in 371 g of Al2O3 ?

196.5 g
145
146
A process in which one or more substances is changed into one
or more new substances is a chemical reaction
A chemical equation uses chemical symbols to show what
happens during a chemical reaction
reactants products
3 ways of representing the reaction of H2 with O2 to form H2O

147
 How to “Read” Chemical Equations

2 Mg + O2 2 MgO

2 atoms Mg + 1 molecule O2 makes 2 formula units MgO

2 moles Mg + 1 mole O2 makes 2 moles MgO
48.6 grams Mg + 32.0 grams O2 makes 80.6 g MgO

NOT
2 grams Mg + 1 gram O2 makes 2 g MgO

148
 Balancing Chemical Equations

1. Write the correct formula(s) for the reactants on

the left side and the correct formula(s) for the
product(s) on the right side of the equation.
Ethane reacts with oxygen to form carbon dioxide and water
C2H6 + O2 CO2 + H2O

2. Change the numbers in front of the formulas

(coefficients) to make the number of atoms of
each element the same on both sides of the
equation. Do not change the subscripts.
2C2H6 NOT C4H12
149
 Balancing Chemical Equations

3. Start by balancing those elements that appear in

only one reactant and one product.
C2H6 + O2 CO2 + H2O start with C or H but not O

2 carbon 1 carbon
multiply CO2 by 2
on left on right
C2H6 + O2 2CO2 + H2O

6 hydrogen 2 hydrogen
multiply H2O by 3
on left on right
C2H6 + O2 2CO2 + 3H2O 150
 Balancing Chemical Equations

4. Balance those elements that appear in two or

more reactants or products.
C2H6 + O2 2CO2 + 3H2O multiply O2 by 7
2

2 oxygen 4 oxygen + 3 oxygen = 7 oxygen

on left (2x2) (3x1) on right

C2H6 + 7 O2 remove fraction

2CO2 + 3H2O
2 multiply both sides by 2
2C2H6 + 7O2 4CO2 + 6H2O

151
 Balancing Chemical Equations

5. Check to make sure that you have the same

number of each type of atom on both sides of the
equation.
2C2H6 + 7O2 4CO2 + 6H2O
4 C (2 x 2) 4C
12 H (2 x 6) 12 H (6 x 2)
14 O (7 x 2) 14 O (4 x 2 + 6)
Reactants Products
4C 4C
12 H 12 H
14 O 14 O
152
 Amounts of Reactants and Products

1. Write balanced chemical equation

2. Convert quantities of known substances into moles
3. Use coefficients in balanced equation to calculate the
number of moles of the sought quantity
153
4. Convert moles of sought quantity into desired units
 Methanol burns in air according to the equation
2CH3OH + 3O2 2CO2 + 4H2O
If 209 g of methanol are used up in the combustion, what
mass of water is produced?
grams CH3OH moles CH3OH moles H2O grams H2O

molar mass coefficients molar mass

CH3OH chemical equation H2O

1 mol CH3OH 4 mol H2O 18.0 g H2O

209 g CH3OH x x x =
32.0 g CH3OH 2 mol CH3OH 1 mol H2O

235 g H2O

154
Limiting Reagent:
Reactant used up first in
the reaction.

2NO + O2 2NO2

NO is the limiting reagent

O2 is the excess reagent

155
 In one process, 124 g of Al are reacted with 601 g of Fe2O3
2Al + Fe2O3 Al2O3 + 2Fe

Calculate the mass of Al2O3 formed.

g Al mol Al mol Fe2O3 needed g Fe2O3 needed

OR
g Fe2O3 mol Fe2O3 mol Al needed g Al needed

1 mol Al 1 mol Fe2O3 160. g Fe2O3

124 g Al x x x = 367 g Fe2O3
27.0 g Al 2 mol Al 1 mol Fe2O3

Start with 124 g Al need 367 g Fe2O3

Have more Fe2O3 (601 g) so Al is limiting reagent 156

 Use limiting reagent (Al) to calculate amount of product that
can be formed.

g Al mol Al mol Al2O3 g Al2O3

2Al + Fe2O3 Al2O3 + 2Fe

1 mol Al 1 mol Al2O3 102. g Al2O3

124 g Al x x x = 234 g Al2O3
27.0 g Al 2 mol Al 1 mol Al2O3

At this point, all the Al is consumed

and Fe2O3 remains in excess.

157
 Another method
2Al + Fe2O3 Al2O3 + 2Fe

124 g 601 g
4.596mol 3.7633mol

4.599 mol Al 3.763 mol Al

2 mol Al 1 mol Al

2.300 3.763

Al is the least thus it is the limiting reagent

158
 Use limiting reagent (Al) to calculate amount of product that
can be formed.

g Al mol Al mol Al2O3 g Al2O3

2Al + Fe2O3 Al2O3 + 2Fe

1 mol Al 1 mol Al2O3 102.0 g Al2O3

124 g Al x x x = 234.4 g Al2O3
26.98.0 g Al 2 mol Al 1 mol Al2O3

At this point, all the Al is consumed

and Fe2O3 remains in excess.

159
 Reaction Yield

Theoretical Yield is the amount of product that would

result if all the limiting reagent reacted.

Actual Yield is the amount of product actually obtained

from a reaction.

Actual Yield
% Yield = x 100%
Theoretical Yield

160
 5Ca + V2 O 5 5 CaO + 2V

1.96 x 103 g 1.54 x 103 g ?g

Calculate % yield if 803g of CaO is produced?

48.90 mol 8.467 mol 42.34 mol

48.90 mol Ca 8.467 mol V2O5

5 mol Ca 1 mol V2O5 2374.2 g CaO

9.78 8.467
803 g
% Yield = x 100 = 33.8%
161
2374.2g
162
Gases

Chapter 5
Elements that exist as gases at 250C and 1 atmosphere

Ionic compounds can not be gases at 25 0C and 1 atm because

of its strong ionic forces
Molecular compounds at 25 0C and 1 atm varies some are gases
CO, HCl and others are liquid or solid CH3OH (l)
No simple rule to help determine if substance is g or l or s
It depends on magnitude of the intermolecular forces among molecules
165
 Physical Characteristics of Gases
• Gases assume the volume and shape of their containers.
• Gases are the most compressible state of matter.
• Gases will mix evenly and completely when confined to
the same container.
• Gases have much lower densities than liquids and solids.

NO2 gas 166

 Chang of velocity
Distance (m s-1) acceleration = (m s-2)
velocity = time
time
(force = mass x acceleration) (kg m s-2) or N

Force
Pressure = Area N m-2
Units of Pressure
1 pascal (Pa) = 1 N/m2
1 atm = 760 mmHg = 760 torr
1 atm = 101,325 Pa

Blood pressure is 120 mm Hg.Expresse

it in torr ,atm, Pa, kPa?
120 torr,1.58x10-1 atm , 1.59987x104Pa 167
• The result of weight of the column of air above it.
• Act on all directions (not down wordonly)

• Depends on location,T,
32 km 0.001 atm Weather conditions

16 km 0.2 atm

6.4 km 0.5 atm

Sea level 1 atm

168
169
Gas Laws Boyle’s (1627-1691)Law

P a 1/V
P x V = constant Constant T
Constant n
P1 x V1 = P2 x V2
170
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?

P x V = constant
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
171
 Charles’ & Gay-Lussac’s Law

Variation in Gas Volume with Temperature at Constant Pressure

As T increases V increases 172

 Variation of Gas Volume with Temperature
at Constant Pressure

Charles’ &
Gay-Lussac’s
Law

VaT Temperature must be

V = constant x T in Kelvin
V1/T1 = V2 /T2 T (K) = t (0C) + 273.15 173
A sample of carbon monoxide gas occupies 3.20 L at 125 0C.
At what temperature will the gas occupy a volume of 1.54 L if
the pressure remains constant?

V1 /T1 = V2 /T2

V1 = 3.20 L V2 = 1.54 L
T1 = 398.15 K T2 = ?
T1 = 125 (0C) + 273.15 (K) = 398.15 K

V2 x T1 1.54 L x 398.15 K
T2 = = = 192 K
V1 3.20 L
174
 Avogadro’s Law
V a number of moles (n) Constant temperature
Constant pressure
V = constant x n

V1 / n1 = V2 / n2

175
Ammonia burns in oxygen to form nitric oxide(nitrogen monoxide)
(NO) and water vapor. How many volumes of NO, H2O are
obtained from 1.5 volume of ammonia at the same temperature
and pressure?

4NH3 + 5O2 4NO + 6H2O

1 mole NH3 1 mole NO

At constant T and P

1.5 volume NH3 1.5 volume NO

4 mole NH3 6 mole H2O
1.5 volume NH3 2.25 volume H2O
176
 Ideal Gas Equation
Boyle’s law: P a 1 (at constant n and T)
V
Charles’ law: V a T (at constant n and P)
Avogadro’s law: V a n (at constant P and T)

nT
Va
P
nT nT
V = constant x =R R is the gas constant
P P

PV = nRT
177
The conditions 0 0C and 1 atm are called standard
temperature and pressure (STP).

Experiments show that at STP, 1 mole of an ideal

gas occupies 22.414 L.

PV = nRT
PV (1 atm)(22.414L)
R= =
nT (1 mol)(273.15 K)

R = 0.082057 L • atm / (mol • K)

178
 Summary of Gas Laws

Boyle’s Law

179
Charles Law

180
Avogadro’s Law

181
Ideal gas:

It is a hypothetical gas which follows ideal gas equation

1) don’t attract or repel one another

2) It’s volume is negligible compare to the volume of the
container

If all variables changes we use:

P1V1
= R = P2V2 In general n1 = n2 P1V1 = P2V2
n1T1 n2T2 thus T1 T2
182
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
n = 49.8 g x = 1.37 mol
V = nRT 36.45 g HCl
P
L•atm
1.37 mol x 0.0821 mol•K
x 273.15 K
V=
1 atm

V = 30.7 L

183
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
184
185
186
Examples

1) 20.8 g of CH4 gas was confined in 5.200 L vessel at 50

0C.Calculate the pressure exerted by the gas?

M CH =16.04 g mol-1 6.529 atm

4

2 ) 1.05 L balloon at 250C , Calculate it’s volume in a summer

day at 50 0C?
1.138 L

3 ) Gas volume is 2.31L at 1 atm, Calculate it’s pressure in

mmHg when it’s volume becomes 7.32 L?
239.8mmHg
Density (d) Calculations

m PM m is the mass of the gas in g

d= =
V RT M is the molar mass of the gas

Molar Mass (M ) of a Gaseous Substance

dRT
M= d is the density of the gas in g/L
P

188
A 2.10-L vessel contains 4.65 g of a gas at 1.00 atm and 27.0
0C. What is the molar mass of the gas?

dRT m 4.65 g g
M= d= = = 2.21
P V 2.10 L L

g L•atm
2.21 x 0.0821 mol•K
x 300.15 K
L
M=
1 atm

M = 54.5 g/mol

189
190
191
 Gas Stoichiometry

What is the volume of CO2 produced at 37 0C 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 192
 Dalton’s Law of Partial Pressures
V and T are constant

P1 P2 Ptotal = P1 + P2
193
Consider a case in which two gases, A and B, are in a
container of volume V.

nART
PA = nA is the number of moles of A
V
nBRT nB is the number of moles of B
PB =
V
nA nB
PT = PA + PB XA = XB =
nA + nB nA + nB

PA = XA PT PB = XB PT
ni
Pi = Xi PT mole fraction (Xi ) =
nT
194
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

195
Collecting a Gas over Water

PT = PO2 + PH2 O

2KClO3 (s) 2KCl (s) + 3O2 (g)

196
PT = PO2 + PH2 O
Vapor of Water and Temperature

197
198
Calculate the mass of Zn(s) used to produce H2(g) over water at
25.00C in a 7.80L vessel and pressure 0.980 atm knowing that
pH2O = 23.8 mmHg according to the following equation:
Zn(s) + 2HCl (g) ZnCl2 (aq) + H2 (g)

m = 19.8 g
Zn

199
 Kinetic Molecular Theory of Gases
1. A gas is composed of molecules that are separated from
each other by distances far greater than their own
dimensions. The molecules can be considered to be points;
that is, they possess mass but have negligible volume.
2. Gas molecules are in constant motion in random directions,
and they frequently collide with one another. Collisions
among molecules are perfectly elastic.
3. Gas molecules exert neither attractive nor repulsive forces
on one another.
4. The average kinetic energy of the molecules is proportional
to the temperature of the gas in kelvins. Any two gases at
the same temperature will have the same average kinetic
energy
KE = ½ mu2
200
 The distribution of speeds
of three different gases
at the same temperature

The distribution of speeds

for nitrogen gas molecules
at three different temperatures

urms = M3RT
201
 Kinetic theory of gases and …
• Compressibility of Gases
• Boyle’s Law
P a collision rate with wall
Collision rate a number density
Number density a 1/V
P a 1/V
• Charles’ Law
P a collision rate with wall
Collision rate a average kinetic energy of gas molecules
Average kinetic energy a T
PaT
202
 Kinetic theory of gases and …
• Avogadro’s Law
P a collision rate with wall
Collision rate a number of piraticals ( density)
number of piraticals ( density) a n
P a n T/V
V a n T/P
Van
• Dalton’s Law of Partial Pressures
Molecules do not attract or repel one another
P exerted by one type of molecule is unaffected by the
presence of another gas
Ptotal = SPi
203
Gas diffusion is the gradual mixing of molecules of one gas
with molecules of another by virtue of their kinetic properties.


r1 M2
=
r2 M1

molecular path
NH4Cl

NH3 HCl
17 g/mol 36 g/mol
204
Apparatus for Studying Molecular Speed Distributiona

205
Gas effusion is the is the process by which gas under
pressure escapes from one compartment of a container to
another by passing through a small opening.


r1 t2 M2
= =
r2 t1 M1

Nickel forms a gaseous compound of the formula Ni(CO)x What

is the value of x given that under the same conditions methane
(CH4) effuses 3.3 times faster than the compound?
r1 2
r1 = 3.3 x r2 M2 = ( ) r2
x M1 = (3.3)2 x 16 = 174.2

M1 = 16 g/mol 58.7 + x • 28 = 174.2 x = 4.1 ~ 4 206

 Deviations from Ideal Behavior

Repulsive Forces
1 mole of ideal gas
PV = nRT
n= PV = 1.0
RT
Attractive Forces

207
Effect of intermolecular forces on the pressure exerted by a gas.

208
 The van der Waals Equation
an 2
(P + V 2 ) (V − nb) = nRT

}
corrected corrected
pressure volume
 The van der Waals Equation
If 1.000 mol of an ideal gas were confined to 22.41 L at 0.0 °C, it
would exert a pressure of 1.000 atm. Use the van der Waals
equation and the constants in Table 5.4 to estimate the pressure
exerted by 1.000 mol of Cl2(g) in 22.41 L at 0.0 °C.

PRACTICE EXERCISE
A sample of 1.000 mol of CO2 (g) is confined to a 3.000-L container
at 0.000 °C. Calculate the pressure of the gas using (a) the ideal-gas
equation and (b) the van der Waals equation.
Answers: (a) 7.47 atm, (b) 7.18 atm
Thermochemistry
Chapter 6
 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

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.
The surroundings are the rest of the universe outside the
system.
matter

energy
energy

open closed isolated

Exchange: matter & 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 that absorbs heat –

transfers thermal energy to the system from the surroundings

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

energy + H2O (s) H2O (l)

 Schematic of Exothermic and Endothermic Processes

2H2 (g) + O2 (g) 2H2O (l) + energy energy + 2HgO (s) 2Hg (l) + O2 (g)
Thermodynamics is the scientific study of the interconversion of
heat and other kinds of energy.

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 = Efinal - Einitial
DP = Pfinal - Pinitial

DV = Vfinal - Vinitial
DT = Tfinal - Tinitial

Potential energy of hiker 1 and hiker 2

is the same even though they took
different paths.
First law of thermodynamics – energy can be
converted from one form to another, but cannot be
created or destroyed.
DEsystem + DEsurroundings = 0
or
DEsystem = -DEsurroundings

C3H8 + 5O2 3CO2 + 4H2O

Exothermic chemical reaction!

Chemical energy lost by combustion = Energy gained by the surroundings

217
system surroundings
 Another form of the first law for DEsystem
DE = q + w
DE is the change in internal energy of a system
q is 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

218
 Work Done On the System
w=Fxd
DV > 0
w = -P DV
-PDV < 0
F
PxV= 2 xd3=Fxd=w wsys < 0
d

Work is not a
state function.

Dw = wfinal - winitial initial final

The units for work done by or on a gas are liters atmospheres.
219
1 L . atm = 101.3 J
A sample of nitrogen gas expands in volume from 1.6 L to 5.4 L
at constant temperature. What is the work done in joules if the
gas expands (a) against a vacuum and (b) against a constant
pressure of 3.7 atm?

w = -P DV
(a) DV = 5.4 L – 1.6 L = 3.8 L P = 0 atm
W = -0 atm x 3.8 L = 0 L•atm = 0 J

(b) DV = 5.4 L – 1.6 L = 3.8 L P = 3.7 atm

w = -3.7 atm x 3.8 L = -14.1 L•atm

w = -14.1 L•atm x 101.3 J = -1430 J

1L•atm
220
Enthalpy and the First Law of Thermodynamics
DE = q + w
At constant pressure:
q = DH and w = -PDV
DE = DH - PDV
DH = DE + PDV

221
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

222
DH < 0 DH > 0
 Thermochemical Equations

Is DH negative or positive?

System absorbs heat

Endothermic

DH > 0 thus DH is +ev

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/mol

223
 Thermochemical Equations

Is DH negative or positive?

System gives off heat

Exothermic

DH < 0 thus DH is -ev

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/mol
224
 Thermochemical Equations

(1) The stoichiometric coefficients always refer to the number

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

(2) If you reverse a reaction, the sign of DH changes

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

(2) 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

225
 Thermochemical Equations

(4) The physical states of all reactants and products must be

specified in thermochemical equations.
H2O (s) H2O (l) DH = 6.01 kJ/mol
H2O (l) H2O (g) DH = 44.0 kJ/mol

How much heat is evolved when 266 g of white phosphorus (P4)

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

1 mol P4 3013 kJ
266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4

226
 A Comparison of DH and DE

DE = DH - PDV At 25 oC, 1 mol H2 = 24.5 L at 1 atm

PDV = 1 atm x 24.5 L = 2.5 kJ
DE = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol
The reason DH is smaller than DE in magnitude is that some of the internal
energy released is used to do gas expansion work, so less heat is evolved.

227
 A Comparison of DH and DE

To calculate the internal energy change of a gaseous reaction

is to assume ideal gas behavior and constant temperature
229
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=mxs

Heat (q) absorbed or released:

q = C x Dt
q = m x s x Dt

Dt = tfinal - tinitial

230
How much heat is given off when an 869 g iron bar cools
from 94oC to 5oC?

s (Fe) = 0.444 J/g • oC

Dt = tfinal – tinitial = 5oC – 94oC = -89oC

q = msDt = 869 g x 0.444 J/g • oC x –89oC = -34,000 J

231
232
 Standard Enthalpy of Formation and Reaction

Because there is no way to measure the absolute value of

the enthalpy of a substance, must I measure the enthalpy
change for every reaction of interest?
Establish an arbitrary scale with the standard enthalpy of
formation (DH0)f as a reference point for all enthalpy
expressions.
Standard enthalpy of formation (DH0) isf the heat change
that results when one mole of a compound is formed from
its elements in its most stable form at a pressure of 1 atm.
The standard enthalpy of formation of any element in its
most stable form is zero.
DH 0
(C, graphite) = 0
DH f (O2) = 0
0 f

DH (O ) = 142 kJ/mol
0 DH 0
f (C, diamond) = 1.90 kJ/mol
f 3 233
The standard enthalpy of reaction (DH0 rxn
) is the enthalpy of a
reaction carried out at 1 atm.

aA+bB cC+dD

DHrxn
0
= c
[ DH0
f (C) + dDH0
f (D) ] - [a DH0
(A) + bDH0
f (B) ]
f

DH0 = S nDH0f (products) - S mDHf0 (reactants)

rxn

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.)
235
The direct Method
o Suppose we want to know the enthalpy of formation of carbon dioxide.
o We must measure the enthalpy of the reaction when carbon (graphite)
and molecular oxygen in their standard states are converted to carbon
dioxide in its standard state:

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

Benzene (C6H6) burns in air to produce carbon dioxide and
liquid water.? What is the enthalpy of the fowiowing reaction:
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l) DH0rxn = ?
The standard enthalpy of formation of C6H6, CO2, H2O (l) are 49
and -393.5 and- 285.8 kJ/mol.? How much heat is released per
mole of C6H6 combusted?

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

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

DH0rxn = [ 12x–393.5 + 6x–285.8 ] – [ 2x49 ] = -6534.8 kJ

-6534.8 kJ
= - 3267.4 kJ/mol C6H6
2 mol 237
The Indirect Method (Hess’s Law)

o Many compounds cannot be directly synthesized from their

elements.
o The reaction proceeds too slowly, or side reactions produce
substances other than the desired compound.

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.)
Let’s say we are interested in the standard enthalpy of formation of
carbon monoxide (CO).

However, burning graphite also produces some carbon dioxide (CO2), so

we cannot measure the enthalpy change for CO directly.
We must employ an indirect route, based on Hess’s law.
It is possible to carry out the following two separate reactions:

First, we reverse Equation (b) to get

we carry out the operation (a) + (c) and obtain

C (graphite) + 1/2O2 (g) CO (g)
CO (g) + 1/2O2 (g) CO2 (g)
C (graphite) + O2 (g) CO2 (g)

240
Calculate the standard enthalpy of formation of CS2 (l) given
that:
C(graphite) + O2 (g) CO2 (g) DH0rxn = -393.5 kJ/mol
S(rhombic) + O2 (g) SO2 (g) DH0rxn = -296.1 kJ/mol
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) DHrxn
0 = -1072 kJ/mol

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) DH0rxn = -393.5 kJ/mol
2S(rhombic) + 2O2 (g) 2SO2 (g) DH0rxn = -296.1 kJ/mol x 2
+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) DHrxn
0 = +1072 kJ/mol

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

DH0rxn= -393.5 + (2x-296.1) + 1072 = 86.3 kJ/mol
241
 Chapter 12

Physical Properties of Solutions

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.

12.1
A saturated solution contains the maximum amount of a
solute that will dissolve in a given solvent at a specific
temperature.
An unsaturated solution contains less solute than the
solvent has the capacity to dissolve at a specific
temperature.

Sodium acetate crystals rapidly form when a seed crystal is

added to a supersaturated solution of sodium acetate.

12.1
 “like dissolves like”

Two substances with similar intermolecular forces are likely

to be soluble in each other.

• non-polar molecules are soluble in non-polar solvents

CCl4 in C6H6
• polar molecules are soluble in polar solvents
C2H5OH in H2O
• ionic compounds are more soluble in polar solvents
NaCl in H2O or NH3 (l)

12.2
 Temperature and Solubility
Solid solubility and temperature

solubility increases with

increasing temperature
solubility decreases with
increasing temperature

12.4
 Temperature and Solubility
O2 gas solubility and temperature

solubility usually
decreases with
increasing temperature

12.4
 Concentration Units
The concentration of a solution is the amount of solute
present in a given quantity of solvent or solution.

Molarity (M) or molar concentration, which is the number of

moles of solute per liter of solution.
moles of solute
M =
liters of solution

Molality (m) is the number of moles of solute dissolved in 1 kg

(1000 g) of solvent
moles of solute
m =
mass of solvent (kg) 12.3
Comparison of Concentration Units
o The advantage of molarity is that it is generally easier to
measure the volume of a solution.
For this reason, molarity is often preferred over molality.
o Molality is independent of temperature, because the
concentration is expressed in number of moles of solute and
mass of solvent.
The volume of a solution typically increases with increasing
temperature, so that a solution that is 1.0 M at 25°C may
become 0.97 M at 45°C because of the increase in volume
on warming.
o This concentration dependence on temperature can
significantly affect the accuracy of an experiment.
Therefore, it is sometimes preferable to use molality instead
of molarity.
What mass of KI is required to make 500. mL of
a 2.80 M KI solution?
M KI M KI
volume of KI solution moles KI grams KI

1L 2.80 mol KI 166 g KI

500. mL x x x = 232 g KI
1000 mL 1 L soln 1 mol KI
Percent by Mass The percent by mass (also called percent by
weight or weight percent) is the ratio of the mass of a solute to
the mass of the solution, multiplied by 100 percent:
mass of solute
% by mass = x 100%
mass of solute + mass of solvent
mass of solute
= x 100%
mass of solution

Mole Fraction (X) The mole fraction of a component of a

solution, say, component A, is written XA and is defined as
moles of A
XA =
sum of moles of all components

12.3
To convert one concentration unit of a
solution to another
Example;
Express the concentration of a 0.396 m glucose (C6H12O6)
solution in molarity? (density of solution=1.16 g/mL)
0.396 m glucose (C6H12O6) i.e. there is 0.396 mole of
glucose in 1000 g of the solvent.
To calculate molarity; we need to determine the volume
of this solution.
First, we calculate the mass of the solution from the
molar mass of glucose:
The density of the solution is1.16 g/mL.
We can now calculate the volume of the solution in liters

The molarity of the solution is given by

What is the molality of a 5.86 M ethanol (C2H5OH) solution whose
density is 0.927 g/mL?
moles of solute moles of solute
m = M =
mass of solvent (kg) liters of solution

Assume 1 L of solution:
5.86 moles ethanol = 270 g ethanol
927 g of solution (1000 mL x 0.927 g/mL)
mass of solvent = mass of solution – mass of solute
= 927 g – 270 g = 657 g = 0.657 kg

moles of solute 5.86 moles C2H5OH

m = = = 8.92 m
mass of solvent (kg) 0.657 kg solvent

12.3
 Pressure and Solubility of Gases
The solubility of a gas in a liquid is proportional to the
pressure of the gas over the solution (Henry’s law).
c is the concentration (M) of the dissolved gas
c = kH P P is the pressure of the gas over the solution
kH is a constant for each gas (mol/L•atm) that
depends only on temperature

low P high P

low c high c
12.5
o Most gases obey Henry’s law, but there are some important
exceptions.
o For example, if the dissolved gas reacts with water, higher
solubilities can result.
The solubility of ammonia is much higher than
expected because of the reaction

Carbon dioxide also reacts with water, as follows:

Another interesting example is the dissolution of

molecular oxygen in blood.
Colligative Properties of Nonelectrolyte Solutions

Colligative properties are properties that depend only on the

number of solute particles in solution and not on the nature of
the solute particles.

o The colligative properties are

 vapor-pressure lowering,
 boiling-point elevation,
 freezing-point depression,
 osmotic pressure.

12.6
Vapor-Pressure Lowering
0 0
P1 = X1 P 1 P 1 = vapor pressure of pure solvent

Raoult’s law X1 = mole fraction of the solvent

If the solution contains only one solute:
X1 = 1 – X2
- P1 = DP = X2 P 1
0 0
P1 X2 = mole fraction of the solute

We see that the decrease in vapor pressure, DP, is directly

proportional to the solute concentration (measured in mole
fraction).

12.6
Boiling-Point Elevation
DTb = Tb – T b0
T b0 is the boiling point of
the pure solvent
T b is the boiling point of
the solution

Tb > T b0 DTb > 0

DTb = Kb m
m is the molality of the solution
Kb is the molal boiling-point
elevation constant (0C/m)
for a given solvent
12.6
Freezing-Point Depression
DTf = T 0f – Tf
0
T fis the freezing point of
the pure solvent
T f is the freezing point of
the solution

T 0f > Tf DTf > 0

DTf = Kf m
m is the molality of the solution
Kf is the molal freezing-point
depression constant (0C/m)
for a given solvent
12.6
12.6
What is the freezing point and the boiling point of a solution
containing 478 g of ethylene glycol (antifreeze) in 3202 g of
water? The molar mass of ethylene glycol is 62.01 g/mol.
Kb water = 0.52 0C/m Kf water = 1.86 0C/m

DTf = Kf m
1 mol
478 g x
moles of solute 62.01 g
m = = = 2.41 m
mass of solvent (kg) 3.202 kg solvent

DTf = Kf m = 1.86 0C/m x 2.41 m = 4.48 0C

Tf = T 0f – DTf = 0.00 0C – 4.48 0C = -4.48 0C
DTb = Kb m =0.520C/m x 2.41 m = 1.25 0C

Tb = DTb + T 0b = 1.25 0C + 100 0C = 101.250C

12.6
Osmotic Pressure (p)
Osmosis is the selective passage of solvent molecules through a porous
membrane from a dilute solution to a more concentrated one.
A semipermeable membrane allows the passage of solvent molecules but
blocks the passage of solute molecules.
Osmotic pressure (p) is the pressure required to stop osmosis.

more
dilute
concentrated

12.6
Osmotic Pressure (p)

High Low
P P

p = MRT
M is the molarity of the solution
R is the gas constant
T is the temperature (in K) 12.6
 Summary - Colligative Properties of
Nonelectrolyte Solutions
Colligative properties are properties that depend only on the
number of solute particles in solution and not on the nature of
the solute particles.
Vapor-Pressure Lowering P1 = X1 P 10
Boiling-Point Elevation DTb = Kb m
Freezing-Point Depression DTf = Kf m
Osmotic Pressure (p) p = MRT
Using Colligative Properties to Determine Molar Mass
From the experimentally determined freezing-point depression
or osmotic pressure, We can calculate the molality or molarity
of the solution. Knowing the mass of the solute, we can readily
determine its molar mass, 12.6