Chem 101 New Syllabus Alowais 461 07 Aug 2024 Students
Chem 101 New Syllabus Alowais 461 07 Aug 2024 Students
Chem 101 New Syllabus Alowais 461 07 Aug 2024 Students
CHEMISTRY DEPARTMENT
CHEM 101
LECTURES IN
GENERAL CHEMISTRY (1)
CONTENT PAGE
TABLE OF CONTENTS II
PERSONAL INFORMATION IX
SYLLABUS X
INTRODUCTION XII
II
2.3 Atomic number, mass number and isotopes 18
2.3.1 The atomic number (Z) 18
2.3.2 The mass number (A) 18
2.4 The periodic table of elements 20
2.5 Molecules 21
2.6 Ions 21
2.6.1 Definition of ions 21
2.6.2 Definition of ionic compounds 21
2.7 Naming inorganic compounds 23
2.7.1 Naming ionic compounds 23
2.7.2 Naming molecular compounds 24
2.7.3 Naming acids 25
2.7.4 Naming bases 27
2.5 Naming hydrates 27
2.8 Common and systematic names of some
28
compounds
3 MASS RELATIONSHIPS IN CHEMICAL
29
REACTIONS
3.1 Atomic mass and average atomic mas 29
3.2 Avogadro’s number and the molar mass of an
29
element
3.3 Molecular mass 30
3.4 The mass spectrometer 32
3.5 Percent composition of elements in compounds 33
3.6 Experimental determination of empirical formula 34
3.7 Chemical reactions and chemical equations 35
III
3.8 Amounts of reactants and products in chemical
36
reactions
3.9 Limiting reactants (reagents) 38
3.10 Reaction yield (Yield percentage) 40
4 REACTIONS IN AQUEOUS SOLUTIONS 42
4.1 General properties of aqueous solutions 42
4.2 Electrolytic properties 42
4.3 Precipitation reactions 42
4.3.1 Solubility 42
4.3.2 Molecular equations, ionic Equations, and net
43
ionic equations
4.3 Acid-base reactions 44
4.3.1 General properties of acids and bases 44
4.3.2 Acid-Base Neutralization 47
4.3.3 Acid-base reactions leading to gas formation 47
4.4 Oxidation-reduction reactions 48
4.4.1 The concept 48
4.4.2 Terminology 48
4.4.3 Oxidation number 48
4.4.4 Rules to assign oxidation numbers 49
4.4.5 Types of redox reactions 50
4.5 Concentration of solutions 53
4.6 Gravimetric analysis 54
4..7 Acid-base titration 55
4.8 Redox titration 57
IV
5 Gases 77
5.1 Substances that exist as gases 58
5.1.1 Elements that exist as gases 58
5.1.2 Compounds that exist as gases 58
5.2 Pressure of the gas 58
5.2.1 The four important properties in studying gases 59
5.2.1 Atmospheric pressure and standard
59
atmospheric pressure and temperature (STP)
5.3 The gas laws 59
5.3.1 The ideal gas law (The relation between n, P, V
59
and T of an ideal gas) and the gas constant “R”
5.3.2 Boyle’s law 60
5.3.3 Charles’s and Gay-Lussac’s law 60
5.3.4 Avogadro’s law 61
5.3.5 The combined gas law 61
5.3.6 Other gas laws 61
5.4 The relation between the gas density and molar
63
mass
5.5 Gas stoichiometry 64
5.6 Dalton’s law of partial pressures 65
5.7 The kinetic molecular theory of gases 67
5.7.1 The five hypotheses of the theory 68
5.7.2 Application of kinetic theory to the gas laws 69
5.7.3 Distribution of molecular speeds 69
5.7.4 Gas diffusion and effusion 70
5.8 Deviation from ideal behavior 71
V
6 THEMOCHEMISTRY 74
6.1 The nature of energy and types of energy 74
6.1.1 Types of energy 74
6.1.2 The law of conservation of energy 74
6.2 Energy change in chemical reactions 74
6.3 The system the surroundings and the universe 75
6.4 Introduction to thermodynamics 75
6.4.1 Work and heat 75
6.4.2 The first law of thermodynamics 77
6.5 Enthalpy of chemical reactions 78
6.5.1 Thermochemical equations 78
6.5.2 Relationship between ΔH and ΔE 79
6.6 Calorimetry 79
6.7 Standard enthalpy of formation and reaction 82
6.8 Heat or enthalpy of solution and dilution 85
7 QUANTUM THEORY AND THE
86
ELECTRONIC STRUCTURE OF ATOMS
7.1 From classical physics to quantum theory 86
7.2 The electromagnetic radiation 86
7.3 Bohr’s Theory of the Hydrogen Atom 87
7.4 Emission Spectrum of the Hydrogen Atom 88
7.5 The dual nature of the electron 91
7.6 Quantum mechanics 92
7.7 Quantum Numbers 94
VI
7.7.1 The principal quantum number (n) 94
7.7.2 The angular momentum quantum number (l) 94
7.7. The magnetic quantum number (𝒎𝒍 ) 94
7.7.4 The spin quantum number, 𝐦𝐬 94
7.8 Atomic orbitals 95
7.9 The rules of electronic distribution 97
7.10 Electron configurations of anions and cations 101
7.11 The electron configurations and the location of
102
elements in the periodic table
8 SOLUTIONS 104
8.1 Types of solutions 104
8.2 A Molecular view of the solution process 104
8.2.1 How solution is formed? 104
8.2.2 The “like dissolve like” proverb 105
8.3 Concentration units 106
8.3.1 Mass percent of solute (Solute%) 106
8.3.2 Mole fraction (X) 106
8.3.3 Molality (m) 107
8.3.5 Interconversion between concentration’s units 107
8.4 The effect of temperature on solubility 108
8.4.1 Solid solubility and temperature 108
8.4.2 Gas solubility and temperature 109
8.5 The effect of pressure on the solubility of gases 110
8.6 Colligative Properties of Nonelectrolyte Solutions 112
VII
8.6.1 Vapor pressures lowering 112
8.6.2 Boiling point elevation 114
8.6.3 Freezing point depression 114
8.6.4 Osmotic pressure 115
ANSWERS OF PRAXTICE EXERCISES 118
VIII
PERSONAL INFORMATION
STUDENT UNIVERCIY
NUMBER →
MOBILE NUMBER →
FIRST MIDTERM
EXAM →
(15 grades)
SECONDMIDTERM
EXAM →
(15 grades)
FINAL EXAM →
(40 grades)
أحمد العويس.د
CHEMISTRY DEPARTMENT
المقرر
ّ مدرس
ّ → OFFICE: 2A15
COLLEDGE OF SCIENCE
BUILDING: 5
IX
SYLLABUS
Text book: Raymond Chang, Chemistry, 14th edition, 2022
Page Lecture
Topics
number hours
1 Chemistry: The Study of Change
1.1 Chemistry: A Science for the Twenty-First Century 2
1.2 The scientific method 4
1.3 Measurements 6
1.4 Classification of matter 3
1.5 Handling numbers 13
20
1.6 Dimensional analysis in solving problems
Review and Exercises
2 Atoms, Molecules and Ions
2.1 The Atomic Theory 41
2.2 The Structure of the Atom 43
2.3 Atomic Number, Mass Number, and Isotopes 49
2.4 The Periodic Table 51
2.5 Molecules and Ions 54 5
2.6 Chemical Formulas 55
2.7 Naming Compounds 60
Review and Exercises
3 Mass Relationships in Chemical Reactions
3.1 Atomic Mass 80
3.2 Avogadro’s Number and Molar Mass of an Element 82
3.3 Molecular Mass 85
3.4 The Mass Spectrometer 88
3.5 Percent Composition of Compounds 90
3.6 Experimental Determination of Empirical Formulas 93 6
3.7 Chemical Reactions and Chemical Equations 95
3.8 Amounts of Reactants and Products 100
3.9 Limiting Reagents 104
3.10 Reaction Yield and Atom Economy 108
Review and Exercises
4 Reactions in aqeueos solutions
4.1 General Properties of Aqueous Solutions 125
4.2 Precipitation Reactions 127
4.3 Acid-Base Reactions 132
4.4 Oxidation-Reduction Reactions 138
4.5 Concentration of Solutions 150 6
4.6 Gravimetric Analysis 155
4.7 Titrations 157
Review and Exercises
5 Gases
X
5.1 Substances that Exist as gases 176
5.2 Pressure of a gas 178
5.3 The gas laws 181
5.4 The ideal gas law 188
5.5 Gas stoichiometry 196 7
5.6 Dalton's law of partial pressures 199
5.7 The kinetic molecular theory of gases 206
5.8 Deviation from ideal behavior 214
Review and Exercises
6 Thermochemistry
6.1 The Nature of Energy and Types of Energy 231
6.2 Energy Changes in Chemical Reactions 232
6.3 Introduction to Thermodynamics 234
6.4 Enthalpy of Chemical Reactions 241
6.5 Calorimetry 247 5
6.6 Standard Enthalpy of Formation and Reaction 253
6.7 Heat of Solution and Dilution 259
Review and Exercises
7 Quantum theory and the electronic structure of atoms
7.1 From Classical Physics to Quantum Theory 274
7.2 The Photoelectric Effect 281
7.3 Bohr’s Theory of the Hydrogen Atom 283
7.4 The Dual Nature of the Electron 290
7.5 Quantum Mechanics 294 5
7.6 Quantum Numbers 297
7.7 Atomic Orbitals 300
7.8 Electron Configuration 305
7.9 The Building-Up Principle 312
Review and Exercises
12 Solutions
12.1 Types of Solutions 528
12.2 A Molecular View of the Solution Process 529
12.3 Concentration Units 532
12.4 The Effect of Temperature on Solubility 536
12.5 The Effect of Pressure on the Solubility of Gases 538 7
12.6 Colligative Properties of Nonelectrolyte Solutions 541
12.7 Colligative Properties of Electrolyte Solutions 552
Review and Exercises
TOTAL HOURS 42
DISTRIBUTION OF GRADES
First theoretical midterm exam 15 grades
Second theoretical midterm exam 15 grades
Laboratory experiments 30 grades
Final theoretical midterm exam 40 grades
Total 100 grades
XI
INTRODUCTION
This course helps to understand the so many applications of chemistry findings in our life.
I, greatly, thank the Chemistry Department at King Saud University, I have a great appreciation
to my students and colleagues previous and now a day.
AHMAD ALOWAIS
1446 H
2024 G
XII
1. CHEMISTRY: THE STUDY OF CHANGE
1.1 Chemistry: A Science for the Twenty-First Century
CHEMISTRY is the study of matter and the changes it undergoes
It is THE CENTRAL SCIENCE, because it is essential for biology, physics, geology,
ecology, and many other subjects
Although it is an ancient science, its modern foundation was laid in the nineteenth
century, when intellectual and technological advances enabled scientists to break down
substances into ever smaller components and consequently to explain many of their
physical and chemical characteristics
The rapid development of technology throughout the twentieth century has given us
even greater means to study things that cannot be seen with the naked eye
Using computers and special microscopes, for example, chemists can analyze the
structure of atoms and molecule and design new substances with specific properties,
such as drugs and environmentally friendly consumer products.
As we enter the twenty-first century, it is fitting to ask what part the central science
will have in this century. Almost certainly, chemistry will continue to play a pivotal
role in all areas of science and technology
Whatever your reasons for taking general chemistry, a good knowledge of the subject
will better enable you to appreciate its impact on society and on you as an individual
1.2 The Scientific Method
The scientific method, a systematic approach to research
All sciences employ various scientific methods
For example, a chemist who is interested in measuring the heat given off when
hydrogen gas burns in air would follows a scientific method in carrying out his
investigations
The first step is to carefully define the problem
The next step includes performing experiments, making careful observations, and
recording information, or data, about the system (IN THE EXAMPLES JUST
DISCUSSED, THE SYSTEMS IS A MIXTURE OF HYDROGEN AND AIR)
The data obtained in a research study may be both qualitative, consisting of general
observations about the system, and quantitative, comprising numbers obtained by
various measurements of the system
Chemists generally use standardized symbols and equations in recording their
measurements and observations. This form of representation not only simplifies the
process of keeping records, but also provides a common basis for communication with
other chemists
When the experiments have been completed and the data have been recorded, the next
step in the scientific method is interpretation (THE SCIENTIST ATTEMPTS TO
EXPLAIN THE OBSERVED PHENOMENON)
Based on the data that were gathered, the researcher formulates a hypothesis (A
TENTATIVE EXPLANATION FOR A SET OF OBSERVATIONS)
Further experiments are devised to test the validity of the hypothesis in as many ways
as possible, and the process begins anew
Figure 1.3 summarizes the main steps of the research process
1
After a large amount of data has been collected, it is often desirable to summarize the
information in a concise way, as a law (A LAW IS A CONCISE VERBAL OR
MATHEMATICAL STATEMENT OF A RELATIONSHIP BETWEEN PHENOMENA
THAT IS ALWAYS THE SAME UNDER THE SAME CONDITIONS)
Hypotheses that survive many experimental tests of their validity may evolve into
theories (A THEORY IS A UNIFYING PRINCIPLE THAT EXPLAINS A BODY OF
FACTS AND/OR THOSE LAWS THAT ARE BASED ON THEM)
Theories, too, are constantly being tested. If a theory is disproved by experiment, then
it must be discarded or modified so that it becomes consistent with experimental
observations
Proving or disproving a theory can take years, even centuries, in part because the
necessary technology may not be available (IT TOOK ATOMIC THEORY MORE
THAN 2000 YEARS TO WORK OUT THIS FUNDAMENTAL PRINCIPLE OF
CHEMISTRY PROPOSED BY AN ANCIENT GREEK PHILOSOPHER
“DEMOCRITUS”)
Scientific progress is seldom made in a rigid, step-by-step fashion. Sometimes a law
precedes a theory; sometimes it is the other way around
Two scientists may start working on a project with exactly the same objective but will
end up taking drastically different approaches
Scientists are human beings, and their modes of thinking and working are very much
influenced by their background, training, and personalities
The development of science has been irregular and sometimes even illogical
Great discoveries are usually the result of the cumulative contributions and experience
of many workers, even though the credit for formulating a theory or a law is usually
given to only one individual
There is, of course, an element of luck involved in scientific discoveries, but it has been
said that “chance favors the prepared mind”
It takes an alert and well-trained person to recognize the significance of an accidental
discovery and to take full advantage of it
More often the public learns only of spectacular scientific breakthroughs
2
For every success story, there are hundreds of cases in which scientists have spent years
working on projects that ultimately led to a dead end, and in which positive
achievements came only after many wrong turns and at such a slow pace that they went
unheralded. Yet even the dead ends contribute something to the continually growing
body of knowledge about the physical universe
It is the love of the search that keeps many scientists in the laboratory
1.3 Classifications of matter
3
Second: Mixtures: A mixture is a combination of two or more substances in which
the substances retain their distinct identities. Mixtures do not have constant
composition. They are two types:
Homogeneous mixture: A Homogeneous mixture is a mixture in which the
composition of the mixture is the same throughout (the composition is uniform).
Examples: air, soft drinks, milk, and cement
Heterogeneous mixture: A Heterogeneous mixture is a mixture in which the
composition of the mixture is not the same throughout (the composition is not
uniform). Examples: the mixture of sand and iron filing
Any mixture can be separated to its components by physical means without
changing the identities of the components
1.4 Measurement
The measurements chemists make are often used in calculations to obtain other related
quantities
Different instruments enable us to measure a substance’s properties:
The meterstick measures length or scale
The burette, the pipet, the graduated cylinder, and the volumetric flask measure volume
The balance measures mass
The thermometer measures temperature.
These instruments provide measurements of macroscopic properties, which can be
determined directly; Microscopic properties, on the atomic or molecular scale, must be
determined by an indirect method
A measured quantity is usually written as a number with an appropriate unit
To say that the distance between Dammam and Jeddah is 1355 is meaningless, we must
specify that the distance is 1355 kilometers. The same is true in chemistry; units are
essential to stating measurements correctly
1.4.1 SI Units
In 1960, the General Conference of Weights and Measures, the international authority
on units, proposed a revised metric system called the International System of Units
(abbreviated SI UNITS)
Physical quantities are two types: the base physical quantities that are given seven base
SI units, and the derived physical quantities that are given derived SI units.
First: Base units
The following table shows the seven base physical quantities and their SI base units:
4
SI base unit
Base quantity
Name Symbol
length meter m
mass kilogram kg
time second s
electric current ampere A
Thermodynamic temperature kelvin K
amount of substance mole mol
luminous intensity candela cd
The SI units of length and mass are in decimal fashion. The table below shows the
prefixes used for their large and small quantities:
Prefixes used with SI Units
Prefix (Symbol) Power Example
tera (T) 1012 1 Tm = 1 × 1012 m
giga (G) 109 1 Gm = 1 × 109 m
mega (M) 106 1 Mm = 1 × 10 m
kilo (k) 103 1 km = 1 × 106 m
deci (d) 10-1 1 dm = 1 × 103 m
centi (c) 10 -2
1 cm = 1 × 10−1 m
milli (m) 10-3 1 mm = 1 × 10−3 m
micro (µ) 10-6 1 µm = 1 × 10−6 m
nano (n) 10 -9
1 nm = 1 × 10−9 m
pico (p) 10-12 1 pm = 1 × 10−12 m
Second: Derived units
All the rest of physical quantities are derived from these seven quantities and their units
are “derived units”.
1.4.2 Some important units
First: Mass and weight
The SI unit of mass is the kilogram (kg). Smaller gram (g) is convenient
sometimes:
1 kg = 1000 g
Pound (lb), is a non- SI Unit of mass
1 lb = 0.4536 kg
1 kg = 2.2046 lb
Second: Volume
The SI unit of volume is the cubic meter (m3)
1 m3 = 1 × 103 dm3 = 1 × 106 cm3
Liter (L), is a non- SI Unit of volume occupied by one cubic decimeter
1 L = 1 dm3= 1000 cm3 = 1000 mL
Third: Density
The equation for density is
mass m
density = volume OR d = V
5
kg
The SI-derived unit for density is the kilogram per cubic meter (m3)
g g
Gram per cubic centimeter (cm3) and its equivalent, grams per milliliter (mL) are
commonly used for solid and liquid densities
g g
Gram per liter (L) and its equivalent, grams per milliliter (dm3 ) are commonly
used for gas densities
kg g
1 m3 = 1 × 10−3 cm3
The following table lists the densities of several substances
g
Material Density ( )
cm3
Gold 19.3
Mercury 13.6
Lead 11.3
Silver 10.5
Iron 7.86
Aluminum 2.7
Rubber 1.1
Water 1.0
Air 0.0013
EXAMPLE 1.1
A piece of gold with a mass of 301 g has a volume of 15.6 cm3. Calculate the density of gold.
Solution
m 301 g g
d = V = 15.6 cm3 = 19.3 cm3
Practice Exercise 1.1
A piece of platinum with a density of 21.5 g/cm3 has a volume of 4.49 cm3. What is its mass?
EXAMPLE 1.2
g
The density of mercury is 13.6 cm3. Calculate the mass of 5.50 mL of the liquid.
Solution
5.50 mL = 5.50 cm3
g
m = d × V = 13.6 cm3 × 5.5 cm3 = 74.8 g
Practice Exercise 1.2
The density of sulfuric acid solution in a certain car battery is 1.41 g/mL. Calculate the mass of
242 mL of this solution.
Fourth: Temperature
Temperature is an arbitrary measure of the degree of hotness or coldness of matter.
There are three temperature scales, their units are degrees Fahrenheit (°F), degrees
Celsius (°C), and Kelvin (K):
The Celsius scale, commonly used scale worldwide, divides the range between the
normal freezing point (0°C) and boiling point (100°C) of water into 100 degrees,
therefore it is sometimes called “the centigrade scale”
6
The Fahrenheit scale, least used scale worldwide, defines the normal freezing and
boiling points of water to be exactly 32 °F and 212 °F, respectively. The following
equations are used to convert between degrees Celsius and degrees Fahrenheit:
5 °C
Temperature in °C = (Temperature in °F − 32 °F) × (9 °F)
9 °F
Temperature in °F = (Temperature in °C × 5 °C) + (32 °F)
The Kelvin scale (also called the absolute temperature scale) is the SI base unit of
temperature. By “absolute” we mean that the zero on the Kelvin scale, denoted by
0 K, is the lowest temperature that can be attained theoretically. The Kelvin scale
defines the normal freezing and boiling points of water to be exactly 273.15 K and
373 K, respectively. The Celsius and the Kelvin scales have units of equal
magnitude; that is, one degree Celsius is equivalent to one Kelvin:
0 K= – 273.15°C = – 459.67 °F
The following equations are used to convert between degrees Celsius and Kelvin:
Temperature in K = (Temperature in °C + 273.15 °C)
Temperature in °C = (Temperature in K − 273.15 K)
The following equations are used to convert between degrees Fahrenheit and
Kelvin:
5K
Temperature in K = (Temperature in °F + 459.67 °F) × 9 °F
9 °F
Temperature in °F = (Temperature in K × ) – (459.67 °F)
5K
EXAMPLE 1.3
A) Mercury melting point is − 38.9 °C. How much is it in Kelvin and °F?
B) Normal human temperature is 98.6 °F. How much is it in Kelvin and °C?
C) Iron boiling point is 3135.35 K. How much is it in °C and °F?
Solution
A) Temperature in K = (Temperature in °C + 273.15 °C)
Temperature in K = (– 38.9 °C + 273.15 °C) = 234.3 K
9 °F
Temperature in °F = (5 °C × Temperature in °C) + 32 °F
9 °F
Temperature in °F = (5 °C × – 38.9 °C) + 32 °F = − 38.02 °F
5
B) Temperature in K = (Temperature in °F + 459.67 °F) × 9
7
5K
Temperature in K = (98.6 °F + 459.67 °F) × 9 °F = 310.15 K
5 °C
Temperature in °C = (Temperature in °F − 32 °F) × (9 °F)
5 °C
Temperature in °C = (98.6 °F − 32 °F) × (9 °F) = 37 °C
1 °C
C) Temperature in °C = (Temperature in K − 273.15 K) × ( 1 K )
1 °C
Temperature in °C = (3135.35 K − 273.15 K) × ( 1 K ) = 2862.20 °C
9 °F
Temperature in °F = (Temperature in K × ) – (459.67 °F)
5K
9 °F
Temperature in °F = (3135.35 K × ) – (459.67 °F) = 5183.96 °F
5K
Practice Exercise 1.3
A) Convert – 38.83 °C, (the freezing point of mercury) to °F and to K.
B) Convert 346 °F, (the freezing point of nitrogen) to °C and to K.
C) Convert 77 K, (the boiling point of nitrogen) to °C and to °F.
Fifth: Pressure
Pressure is the force applied on unit area:
kg m
Force SI Unit ( 2 ) kg
Pressure SI Unit = = ( (ms 2 ) ) = m s2
Area SI Unit
kg
This unit “m s2”, is called “Pascal” and abbreviated “Pa”:
kg
1 m s2 = 1 Pa
Pressure is measured by other units:
The atmosphere unit, abbreviated “atm”:
1 atm = 101325 Pa
The centimeter mercury unit, abbreviated “cmHg”:
1 cmHg = 1333.22 Pa
The millimeter mercury unit, abbreviated “mmHg”:
1 mmHg = 0.1 cmHg = 133.322 Pa
This unit “mmHg” is called “Torricelli” and abbreviated “Torr”:
1 Torr = 1 mmHg
The pound per inch square unit, abbreviated “psi”:
1 psi = 6894.76 Pa
The bar unit, abbreviated “bar”:
1 bar = 100,000 Pa
EXAMPLE 1.4
A) It is found, in a cold day, that the atmospheric pressure in Riyadh is 743 mmHg. How much
this pressure in “atm” unit and in the SI Units?
B) If the pressure inside your car tire is 35 psi, how much is this pressure in bar unit and in the
SI Units?
C) A balloon full of air at a pressure equals to 0.35 atm. What would its pressure be in “mmHg”
unit and in the SI Units?
Solution
1 atm 1 atm
A) Pressure in atm = Pressure in mmHg × 760 mmHg = 743 mmHg × 760 mmHg = 0.978 atm
133.322 Pa 133.322 Pa
Pressure in Pa = Pressure in mmHg × = 743 mmHg × = 99058.2 Pa
1 mmHg 1 mmHg
8
1 bar 1 bar
B) Pressure in bar = Pressure in psi × 14.504 psi = Pressure in Pa = 35 psi × 14.504 psi = 2.41 bar
6894.76 Pa 6894.76 Pa
Pressure in Pa = Pressure in psi × = 35 psi × = 241316.6 Pa
1 psi 1 psi
760 mmHg 760 mmHg
C) Pressure in mmHg = Pressure in atm × = 0.35 atm × = 266 mmHg
1 atm 1 atm
101325 Pa 101325 Pa
Pressure in Pa = Pressure in atm × 1 atm = 0.35 atm × 1 atm = 35463.75 Pa
Practice Exercise 1.4
A) It is found, in a hot day, that the atmospheric pressure in Riyadh is 737 mmHg. How much
is this pressure in “Pa” and in “bar” units?
B) If the pressure inside a gaseous cylinder is 4.6 atm, how much is it in “Pa” and in “Torr”.
C) If the pressure outside an airplane at 40000 ft-altitude reads 0.18 bar. What would this
pressure be in “mmHg” unit and in the SI Unit of pressure
Sixth: Energy
Energy is usually defined as the ability to do work:
Work = force × distance
The SI Units of work is the SI Units of force times the the SI Unit of distance:
kg m kg m2
The SI Units of work = ×m= =J
s2 s2
kg m2
This unit of work itself is the unit of energy. This SI Unit, s2 , is named “Joule”
and abbreviated as “J”
The unit “calorie” abbreviated as “cal” is another unit for energy:
kg m2
1 cal = 4.184 s2 = 4.184 J
It might be useful to mention that when the word “calorie” is written with capital
“C” as “Calorie” its value changes:
1 Cal = 1 kcal = 1000 cal = 4184 J
“Calorie” is used in the fields of food, nutrients and physical exercises. If there are
78 Calories in an average-mass apple (150 g), this equals 78000 calorie or 18642 J.
And a moderate-speed waking for one kilometer burns 55 Calories which equals
55000 calorie or 230120 J. Therefore, we should not confuse calorie with Calorie.
1.5 Handling Numbers: Scientific notation and Significant figures
1.5.1 Scientific notation
Chemists often deal with numbers that are either extremely large or extremely small.
For example:
In 1 g of hydrogen there are 602,200,000,000,000,000,000,000 hydrogen atoms
The mass of a hydrogen atom is 0.00000000000000000000000166 g
Consider the following multiplication:
0.0000000056 × 0.00000000048 = 0.000000000000000002688
It is easy to miss one zero or add one more zero after the decimal point
When working with very large and very small numbers, we use a system called
scientific notation
Regardless of their magnitude, all numbers can be expressed in the form
N × 10𝑛
N is a number between 1 and 10
n, the exponent, is a positive or negative integer (whole number)
Any number expressed in this way is said to be written in scientific notation
9
To express a number in scientific notation:
We must find n
We count the number of places that the decimal point must be moved to give the
number N (which is between 1 and 10)
If the decimal point has to be moved to the left, then n is a positive integer; if it has
to be moved to the right, n is a negative integer
The following examples illustrate the use of scientific notation:
568.762 = 5.68762 × 102
n = 2 because the decimal point is moved 2 places to the left
0.00000772 = 7.72 × 10–6
n = – 6 because the decimal point is moved 6 places to the right
Keep in mind the following two points:
n = 0 is used for numbers that are not expressed in scientific notation. For example,
74.6 × 100 (n = 0) is equivalent to 74.6
The superscript is omitted when n = 1. Thus, the scientific notation for 74.6 is 7.46
× 10 and not 7.46 × 101
Addition and subtraction: To add or subtract using scientific notation:
Write each quantity, say N1 and N2, with the same exponent n
Combine N1 and N2; the exponents remain the same.
(7.4 × 103) + (2.1 × 103) = 9.5 × 103
(4.31 × 104) + (3.9 × 103) = (4.31 × 104) + (0.39 × 104) = 4.70 × 104
(2.22 × 10–2) – (4.10 × 10–3) = (2.22 × 10–2) – (0.41 × 10–2) = 1.81 × 10–2
Multiplication and division: To multiply numbers expressed in scientific notation:
Multiply N1 and N2 in the usual way
Add the exponents together
(8.0 × 104) × (5.0 × 102) = (8.0 × 5.0) (104+2) = 40 × 106 = 4.0 × 107
(4.0 × 10–5) × (7.0 × 103) = (4.0 × 7.0) (10–5+3) = 28 × 10–2 = 2.8 × 10–1
To divide using scientific notation:
Divide N1 and N2 as usual
Subtract the exponents
6.9 × 107 6.9
= 3.0 × 107 – (–5) = 2.3 × 1012
3.0 × 10–5
8.5 × 104 8.5
5.0 × 109 = 5.0 × 104 – 9 = 1.7 × 10–5
1.5.2 Significant figures
Except when all the numbers involved are integers (for example, in counting the
number of students in a class), it is often impossible to obtain the exact value of the
quantity under investigation
For this reason, it is important to indicate the margin of error in a measurement by
clearly indicating the number of significant figures
Significant figures are the meaningful digits in a measured or calculated quantity
When significant figures are used, the last digit is understood to be uncertain
we might measure the volume of a given amount of liquid using a graduated
cylinder with a scale that gives an uncertainty of 1 mL in the measurement
If the volume is 6 mL, then the actual volume is in the range of 5 mL to 7 mL
We represent the volume of the liquid as (6 ± 1) mL
10
In this case, there is only one significant figure (the digit 6) that is uncertain by
either plus or minus 1 mL
If we used a graduated cylinder that has finer divisions, so that the volume we
measure is uncertain by only 0.1 mL
If the volume of the liquid is found to be 6.0 mL, we may express the quantity
as (6.0 ± 0.1) mL
The actual value is somewhere between 5.9 mL and 6.1 mL
We can further improve the measuring device and obtain more significant figures,
but in every case, the last digit is always uncertain; the amount of this uncertainty
depends on the measuring device we use.
Modern balances that measure the mass of objects to four or more decimal places are
being used in many chemistry laboratories
Tracking the number of significant figures in a measurement such as mass ensures that
calculations involving the data will reflect the precision of the measurement.
Guidelines for Using Significant Figures:
1. Any digit that is not zero is significant
845 cm has three significant figures
1.234 kg has four significant figures
and so on
2. Zeros between nonzero digits are significant
606 m contains three significant figures
40501 kg contains five significant figures
and so on
3. Zeros to the left of the first nonzero digit are not significant
Their purpose is to indicate the placement of the decimal point
0.08 L contains one significant figure.
0.0000349 g contains three significant figures
and so on
4. If a number is greater than 1, then all the zeros written to the right of the decimal
point count as significant figures
2.0 mg has two significant figures
40.062 mL has five significant figures
3.040 dm has four significant figures
and so on
5. If a number is less than 1, then only the zeros that are at the end of the number
and the zeros that are between nonzero digits are significant.
0.090 kg has two significant figures.
0.3005 L has four significant figures.
0.00420 min has three significant figures.
and so on
6. Numbers that do not contain decimal points, the trailing zeros (zeros after the
last nonzero digit) may or may not be significant
400 cm may have one significant figure (the digit 4), two significant figures (40),
or three significant figures (400). We cannot know which is correct without more
information. However, by using scientific notation we avoid this ambiguity:
We can express the number 400 in three different ways:
11
4 × 102 for one significant figure
4.0 × 102 for two significant figures
4.00 × 102 for three significant figures
EXAMPLE 1.5
Determine the number of significant figures in the following measurements:
a) 478 cm b) 6.01 g c) 0.825 m
d) 0.043 kg e) 1.310 × 1022 atoms f) 7000 mL
Solution
a) Three, because each digit is a nonzero digit
b) Three, because zeros between nonzero digits are significant
c) Three, because zeros to the left of the first nonzero digit do not count as significant figures
d) Two. Same reason as in (c)
e) Four, because the number is greater than one, so all the zeros written to the right of the
decimal point count as significant figures
f) This is an ambiguous case. The number of significant figures may be four (7.000 × 103),
three (7.00 × 103), two (7.0 × 103) or one (7 × 103). This example illustrates why scientific
notation must be used to show the proper number of significant figures.
Practice Exercise 1.5
Determine the number of significant figures in each of the following measurements:
A) 24 mL B) 3001 g C) 0.0320 m3
4
D) 6.4 × 10 molecules E) 560 kg
A second set of rules specifies how to handle significant figures in calculations:
1. In addition, and subtraction
The answer cannot have more digits to the right of the decimal point than either of
the original numbers:
89.332
+ 1.1 one digit after the decimal point
90.432 round off to 90.4
12
6.85
= 0.0611388789 round off to 0.0611
112.04
3. Keep in mind
Keep in mind that exact numbers obtained from definitions or by counting numbers
of objects can be considered to have an infinite number of significant figures. For
example:
The inch is defined to be exactly 2.54 centimeters:
1 in = 2.54 cm
Thus, the “2.54” in the equation should not be interpreted as a measured number
with three significant figures. In calculations involving conversion between
“in” and “cm,” we treat both “1” and “2.54” as having an infinite number of
significant figures.
if an object has a mass of 5.0 g, then the mass of nine such objects is:
5.0 g × 9 = 45 g
The answer has two significant figures because 5.0 g has two significant figures.
The number 9 is exact and does not determine the number of significant figures.
EXAMPLE 1.6
Carry out the following arithmetic operations to the correct number of significant figures:
a) 11,254.1 g + 0.1983 g b) 66.59 L – 3.113 L c) 8.16 m × 5.1355
d) 0.0154 kg ÷ 88.3 mL e) 2.64 × 103 cm + 3.27 × 102 cm.
Solution
a) 11,254.1 g
+ 0.1983 g
11,254.2983 g round off to 11,254.3 g
b) 66.59 L
– 3.113 L
63.477 L round off to 63.48 L
0.0154 kg
d) = 0.000174405436 kg/mLround off to 0.000174 kg/mL
88.3 mL
or 1.74 × 10–4 kg/mL
e) First we change 3.27 × 102 cm to 0.327 × 103 cm and then carry out the addition (2.64 cm +
0.327 cm) × 103. Following the procedure in (a), we find the answer is 2.97 × 103 cm.
Practice Exercise 1.6
Carry out the following arithmetic operations and round off the answers to the appropriate
number of significant figures:
A) 26.5862 L + 0.17 L B) 9.1 g – 4.682 g C) 7.1 × 104 dm × 2.2654 × 102 dm
D) 6.54 g ÷ 86.5542 mL E) 7.55 × 10 m – 8.62 × 103 m
4
13
Let’s suppose that A = 3.66, B = 8.45, and D = 2.11.
Depending on whether we round off C to three or four significant figures,
we obtain a different number for E:
Method 1 Method 2
3.66 × 8.45 = 30.9 3.66 × 8.45 = 30.93
30.9 × 2.11 = 65.2 30.93 × 2.11 = 65.3
However, if we had carried out the calculation as:
3.66 × 8.45 × 2.11 = 65.3
on a calculator without rounding off the intermediate answer, we would
have obtained 65.3 as the answer for E
Although retaining an additional digit past the number of significant figures
for intermediate steps helps to eliminate errors from rounding, this
procedure is not necessary for most calculations because the difference
between the answers is usually quite small
1.6 Accuracy and precision
Carefully, look at the following figure:
14
Because the average value of Student C is closest to the true value, we say:
Results of Student C are the most precise and the most accurate
Highly accurate measurements are usually precise too. On the other hand, highly
precise measurements do not necessarily guarantee accurate results. For example,
an improperly calibrated meterstick or a faulty balance may give precise readings
that are in error
1.7 Dimensional analysis in solving problems (Conversion factors)
Procedure we use to convert between units in solving chemistry problems is called
dimensional analysis (also called the factor-label method). It is based on the
relationship between different units that express the same physical quantity. For
example:
Because 1 cal = 4.184 J we can covert one to the other by the conversion factors:
1 cal 4.184 J
= 1 or 1 cal = 1
4.184 J
Because 1 atm = 101325 Pa we can covert one to the other by the conversion
factors:
1 atm 101325 Pa
= 1 or =1
101325 Pa 1 atm
Because 1 in = 2.54 cm we can covert one to the other by the conversion factors:
1 in 2.54 cm
= 1 or 1 in = 1
2.54 cm
To apply dimensional analysis, we use the following relationship to cancel the given
unit and to end up with the desired unit:
𝐝𝐞𝐬𝐢𝐫𝐞𝐝 𝐮𝐧𝐢𝐭
given unit × = desired unit
𝐠𝐢𝐯𝐞𝐧 𝐮𝐧𝐢𝐭
EXAMPLE 1.8
An average adult has 5.2 L of blood. What is the volume of blood in m3?
Solution
1 m3
=1
1000 L
1 m3
5.2 L = 5.2 L × 1000 L = 5.2 × 10–3 m3
15
Practice Exercise 1.8
The volume of a room is 1.08 × 108 dm3. What is the volume in m3?
EXAMPLE 1.9
Liquid nitrogen is obtained from liquefied air and is used to prepare frozen goods and in low-
temperature research. The density of liquid nitrogen at its boiling point (– 196 °C or 77 K) is 0.808
g/cm3. Convert the density to units of kg/m3.
Solution
1000000 cm3 1 kg
=1 =1
1 m3 1000 g
1 kg
g 1000 g 1 kg
0.808 × 1 m3
= 808 1
1 cm3 m3
1000000 cm3
Practice Exercise 1.9
The density of the lightest metal, lithium (Li), is 5.34 × 102 kg/m3. Convert the density to g/cm3.
16
2. ATOMS, MOLECULES AND IONS
2.1 The atomic theory
The word “atom” came from the Greek word “atomos” which means “indivisible”. It
was chosen by Democritus about 2400 years ago. The theory of Democritus is that
atoms are indivisible, infinite in number, uncreated, and eternal. Democritus attributed
the properties of matter to the kind of its atoms
The brilliant vision of Democritus was overlooked because the theory of the four
elements (soil, water, air and fire) created by Empedocles was adopted by the greatest
Greek philosopher Aristotle
Our present understanding of the structure of matter began to take shape with the
following Dalton’s atomic theory in 1808:
1) Elements are composed of extremely small particles called atoms
2) All atoms of a given element are identical, having the same size, mass, and chemical
properties. The atoms of one element are different from the atoms of all other
elements
3) Compounds are composed of atoms of more than one element. In any compound,
the ratio of the numbers of atoms of any two of the elements present is either an
integer or a simple fraction.
4) A chemical reaction involves only the separation, combination, or rearrangement
of atoms; it does not result in their creation or destruction
2.2 The structure of the atom
After Dalton’s theory, a series of investigations that began in the 1850s and extended
into the twentieth century clearly demonstrated that atoms possess internal structure
made up of even smaller particles, which are called subatomic particles. This led to
the discovery of the following well-known three subatomic particles:
The Electron
Electron was discovered by an English physicist, J. J. Thomson in 1897
Electrons are negatively charged atomic particles
The electron mass and electric charge are 9.10 × 10–28 g and 1.6022 × 10–19 C
The Proton and the nucleus
Because atoms are neutral, an atom must contain equal number of positive and
negative charges
In 1904 Thomson proposed that an atom could be thought of as a uniform, positive
sphere of matter in which electrons are embedded like raisins in a cake. This why
Thomson model is called the “plum-pudding model” for “plum-pudding” is a kind
of sweets originally offered in England at Christmas dinner. The following figures
display Thompson’s model of the atom (left) and a typical “plum-pudding” (right):
17
In 1909, Ernest Rutherford discovered that the positive particles of the atom
constitute the center of the atom. These positive particles are called the “protons”
The number of protons of any atom equals the number of its electrons and its
electric charge equals that of the electron while its mass equals about 1840 times
the mass of the electron
The mass of the proton is 1.67262 × 10–24 g. Thus, the mass of a nucleus constitutes
most of the mass of the entire atom
Regarding the volume of the space that an atom occupies it is found that the nucleus
𝟏
occupies only about 𝟏𝟎𝟏𝟑 of the entire volume of the atom
A typical atomic radius is about 100 pm, whereas the radius of an atomic nucleus
is about 5 × 10–3 pm. If we imagine that the size of the nucleus is the same as that
of a ping pong ball, then the first electron orbiting around it would be 666 m away
The neutron
In 1932, James Chadwick showed that atoms consist of a third type of subatomic
particles, which he named neutrons, because they are electrically neutrals.
The mass of the neutron almost equals that of the proton.
The following figure shows the location of the elementary particles (protons,
neutrons, and electrons) in an atom.
The following figure shows that electrons are as “clouds” around the nucleus.
mass number A
atomic numberZ X
Hydrogen which has 1 proton and no neutrons is written as:
1
1 H
Uranium which has 92 protons and 143 neutrons is written as:
235
92 U
Isotopes
Isotopes are atoms that have the same atomic number but different mass numbers
Therefore, toms of a given element do not all have the same mass
Most elements have two or more isotopes. For example:
Hydrogen: There are three isotopes of hydrogen
Hydrogen, “ 11𝐻 ”, each atom has one proton and no neutrons
Deuterium, “21𝐻 ”, each atom has one proton and one neutron
Tritium, “31𝐻 ”, each atom has one proton and two neutrons
Uranium: There are two isotopes of uranium
Uranium-235, “ 235 92𝑈”, each atom has 92 protons and 143 neutrons
Uranium-238, “ 235 92𝑈”, each atom has 92 protons and 146 neutrons
EXAMPLE 2.1
Give the number of protons, electrons, and neutrons in each of the following:
A) 20
11Na B) 22
11Na C) 178O D) 146C
Solution
A) number of protons = atomic number = number of electrons = 11
number of neutrons = mass number – number of protons = 20 – 11 = 9
B) number of protons = atomic number = number of electrons = 11
number of neutrons = mass number – number of protons = 22 – 11 = 11
C) number of protons = atomic number = number of electrons = 8
number of neutrons = mass number – number of protons = 17 – 8 = 9
D) number of protons = atomic number = number of electrons = 6
number of neutrons = mass number – number of protons = 14 – 6 = 8
Practice Exercise 2.1
How many protons, neutrons, and electrons are in the isotope of copper: 63
29Cu?
19
2.4 The periodic table of elements
More than half of the elements known today were discovered between 1800 and 1900
During this period, chemists noted that many elements show strong similarities to one
another and there are periodic regularities in physical and chemical behavior and the
need to organize the large volume of available information about the structure and
properties of elemental substances
This led to the development of the periodic table, a chart in which elements having
similar chemical and physical properties are grouped together
The figure below shows the modern IUPAC periodic table
In the periodic table, the elements are arranged by atomic number (shown above the
element symbol)
Horizontal rows called periods and in vertical columns known as groups or families
according to similarities in their chemical properties
The elements can be divided into three categories:
Metals: A metal is a good conductor of heat and electricity
Nonmetal: A nonmetal is usually a poor conductor of heat and electricity
Metalloid: A metalloid has properties that are intermediate between those of
metals and nonmetals
The periodic table shows that the majority of its elements are metals; only 17
elements are nonmetals, and 8 elements are metalloids.
From left to right across any period, the physical and chemical properties of the
elements change gradually from metallic to nonmetallic
There are 18 groups in the periodic table groups is 18 and they are numbered group
1, group 2, group 3 and so on to group 18
Some element groups are given special names.
The Group 1 elements (Li, Na, K, Rb, Cs, and Fr) are called alkali metals
The Group 2 elements (Be, Mg, Ca, Sr, Ba, and Ra) are called alkaline earth
metals
The Group 17 elements (F, Cl, Br, I, and At) are called halogens
The Group 18 elements (He, Ne, Ar, Kr, Xe, Rn and Og) are called noble gases
20
2.5 Molecules
A molecule is an aggregate of at least two atoms in a definite arrangement held
together by chemical forces (also called chemical bonds)
A molecule is the smallest particle of a substance that reflects the substance properties.
A molecule may contain atoms of the same element or atoms of two or more elements
joined in a fixed ratio
A molecule is not necessarily a compound, which, by definition, is made up of two or
more elements
Hydrogen gas, for example, is a pure element, but it consists of molecules made up of
two H atoms each. Water, on the other hand, is a molecular compound that contains
two hydrogen atoms and on oxygen in a ratio of two H atoms and one O atom
Molecules are electrically neutral
monatomic gases
Only the noble gases (group 18) in the periodic table (He, Ne, Ar, Kr, Xe, Rn, and Og)
exist as single atoms. Therefore, they are called monatomic gases
diatomic molecules
Some elements normally exist as diatomic molecules, examples are: hydrogen (𝐻2 )
are nitrogen (𝑁2 ) oxygen (𝑂2), fluorine (𝐹2 ), chlorine (𝐶𝑙2), bromine (𝐵𝑟2), and
iodine (𝐼2 )
Of course, a diatomic molecule can contain atoms of different elements. Examples
are hydrogen chloride (HCl) and carbon monoxide (CO)
polyatomic molecules
Most molecules contain more than two atoms
They can be atoms of the same element, as in ozone (𝑂3) and sulfur (𝑆8 )
They can be combinations of two or more different elements like water (𝐻2 𝑂) and
ammonia (𝑁𝐻3 ) are polyatomic
2.6 Ions
2.6.1 Definition of ions
Ions: An ion is an atom or a group of atoms that has an electric charge
Positive ions (Cations): Loss of electrons by an atom is the reason behind the
positive charges of cations. Also, two or more atoms can combine to form cations
and are classified as polyatomic cations such as H3 O+ , NH4+ and PH4+
Negative ions (Anions): Gain of electrons by an atom is the reason behind the
negative charges of anions
Na atom 𝑁𝑎 + Cl 𝐶𝑙 −
11 protons 11 protons 17 protons 17 protons
11 electrons 10 electrons 17 electrons 18 electrons
2.6.2 Definition of ionic compounds
The “ionic compounds” are the substances that are formed from positive and negative
ions. Example: sodium chloride (NaCl) because it is formed from Na+, and chloride Cl–
The cations in ionic compounds is mostly metals such as sodium, calcium, iron…etc
Most positive ions are metals’ ions but there are some positive ions that are not metals
such as H3 O+ (hydronium), NH4+ (ammonium) and PH4+ (phosphonium)
The anions are nonmetals such as nitride, oxide, fluoride…etc
The following table shows the most common positive ions (CATIONS)
21
Hydrogen H+ Tin Sn2+
Lithium Li+ Chromium Cr 3+
Sodium Na+ Manganese(II) Mn2+
+
Potassium K Iron(II) Fe2+
Cesium Cs + Iron(III) Fe3+
Rubidium Rb+ Cobalt(II) Co2+
Magnesium Mg 2+ Copper(I) Cu+
Manganese(II) Mn2+ Copper(II) Cu2+
Manganese(IV) Mn4+ Zinc Zn2+
3+
Cobalt(III) Co Silver Ag +
Calcium Ca2+ Cadmium Cd2+
Strontium Sr 2+ Mercury(I) Hg 2+
2
Barium Ba2+ Mercury(II) Hg 2+
Aluminum Al3+ Hydronium H3 O+
Lead(II) Pb2+ Ammonium NH4+
Lead(IV) Pb4+ Phosphonium PH4+
There are many nonmetals anions. Examples: CO2– 2–
3 (carbonate), SO4 (sulfate) and
PO3–
4 (phosphate).
The following table shows many anions ending with “-ide”, “-ate” and “-ite”
Hydride H−
Carbide C4−
Nitride N3−
Oxide O2−
Peroxide O2−
2
Sulfide S 2−
Selenide Se2−
Telluride Te2−
Fluoride F−
Chloride Cl−
Bromide Br −
Iodide I−
Hydroxide OH −
Cyanide CN−
Hydrogen carbonate
Carbonate CO2−
3 HCO− 3
(bicarbonate)
Hydrogen phosphate HPO2− 4
Phosphate PO3−
4 Diydrogen phosphate H2 PO− 4
Nitrate NO− 3 Nitrite NO −
2
Sulfite SO2− 3
Sulfate SO2−
4 Hydrogen sulfate
HSO− 4
(bisulfate)
− −
Chlorate ClO3 Chlorite ClO2
2−
Chromate CrO4 dichromate Cr2 O2− 7
22
2.7 Naming inorganic compounds
Organic compounds have their special way to name them. Here we discuss naming
inorganic compounds of only inorganic compounds
These compounds are four types:
1) Ionic compounds
2) Molecular compounds
3) Acids
4) Bases
5) Hydrates
2.7.1 Naming ionic compounds
The tables given in section 2.6 provide the names of many cations and anions
For ionic compounds formed from just two elements (binary compounds) the first
word of its name is the metal name and the second word is the nonmetallic anion by
taking the first part of its name with “ide” attached to it as a suffix. Examples are:
KBr is potassium bromide
ZnF2 is zinc fluoride
Al2O3 is aluminum oxide
Na3N is sodium nitride
KCN is potassium cyanide
Na3N is sodium nitride
Note that although OH − and CN− are not single-atomic anions their names end with
the suffix “ide”. Therefore, their ionic compounds with metal cations follows the
previous rule
LiOH is lithium hydroxide
Ca(CN)2 is calcium cyanide
Cations of many transition metals can form more than one type of cation. Iron can form
two cations: Fe3+ and Fe2+.
The old nomenclature system assigns “-ic” the ending to the cation with more
positive charges: Fe3+ is ferric ion as in ferric chloride, FeCl3; and the ending “ous”
to the cation with fewer positive charges: Fe2+ is ferrous ion as in ferrous chloride,
FeCl2.
The new nomenclature system, done by the German chemist Stock, assigns the
Roman numeral:
“I” means one positive charge
“II” means two positive charges
“III” means three positive charges
“IV” means four positive charges
Therfore FeCl2 is iron(II) chloride and FeCl3 is iron(III) chloride. Other examples
are:
CuCl is copper(I)chloride
CuCl2 is copper(II)chloride
MnCl2 is manganese(II) chloride
MnCl3 is manganese(III) chloride
MnCl4 is manganese(IV) chloride
EXAMPLE 2.2
Name the following compounds:
23
A) Cu(NO3)2 B) KH2PO4 C) NH4ClO3
Solution
A) The nitrate anion (NO–3 ) has only one negative charge, so the copper cation must have two
positive charges: the compound copper(II) nitrate.
B) The cation is potassium ion and the anion is dihydrogen phosphate: the compound is
potassium dihydrogen phosphate.
C) The cation is ammonium ion and the anion is chlorate: the compound is ammonium
chlorate.
Practice Exercise 2.2
Name the following compounds:
A) PbO B) Li2SO3 C) Mn(SO4)2
EXAMPLE 2.3
Write chemical formulas for the following compounds:
A) mercury(I) nitrite B) cesium sulfide C) calcium phosphate
Solution
A) The mercury ion has one positive charge, but it exists as diatomic (Hg 2+ 2 ) and the anion is
–
the nitrite ion (NO2 ): the formula is Hg2(NO2)2.
B) Sulfide ion has 2 negative charges, and cesium ion has 1 positive charge: the formula is Cs2S.
C) The calcium ion has two positive charges (Ca2+), and phosphate ion is PO3– 4 : the formula is
Ca3(PO4)2.
Practice Exercise 2.3
Write formulas for the following ionic compounds:
A) rubidium sulfate B)) barium hydride C) aluminum carbonate
2.7.2 Naming molecular compounds
Molecular compounds consist of two or more different elements
Binary compounds consist of two different elements
Tertiary compounds consist of three different elements.
Binary molecular compounds are named similarly as binary ionic compounds by
placing 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
There are some cases where two elements form several different compounds (C and O
form CO and CO2); in such cases Greek prefixes are used to denote the number of
atoms of each element presents. The table below shows these Greek prefixes.
Mono- Di- Tri- Tetra- Penta- Hexa- Hepta- Octa- Nona- Deca-
1 2 3 4 5 6 7 8 9 10
The following are some examples:
“CO” is carbon monoxide and “CO2” is carbon dioxide
“SO2” is sulfur dioxide and “SO3” is sulfur trioxide
“NO2” is nitrogen dioxide and “N2O4” is dinitrogen tetroxide
The following guidelines are helpful in naming molecular compounds with prefixes:
The prefix “mono-” may be omitted for the first element, this means that there is
only one atom of that element in the molecule. For example, PCl3 is phosphorus
trichloride not monophosphorus trichloride
For oxides, the ending “a” in the prefix is usually omitted. For example, N2O4 is
dinitrogen tetroxide rather than dinitrogen tetraoxide.
24
Writing formulas for molecular compounds is usually straightforward. Thus, the
name “arsenic trifluoride” means that there are three nonmetallic “F” atoms and
one nonmetallic “As” atom in each molecule, and the molecular formula is “AsF3”.
Note that the order of elements in the formula is the same as in its name.
Compounds containing hydrogen are named exceptionally. Many of them are
called by their common and nonsystematic names or by names that do not indicate
the number of hydrogen atoms. Also, in some formulas, hydrogen is written first
not like other were it is written last. The following are some examples:
B2H6 is diborane not diboron hexahydride
CH4 is methane not carbon tetrahydride
SiH4 is silane not silicon tetrahydride
NH3 is ammonia not nitrogen triahydride
PH3 is phosphine not phosphorus triahydride
H2O is water not dihydrogen oxide
H2S is hydrogen sulfide not dihydrogen sulfide
EXAMPLE 2.4
Name the following molecular compounds:
A) SiCl4 B) P4O10.
Solution
A) There are one silicon atom and four chlorine atoms: the compound is silicon tetrachloride.
B) There are four phosphorus atoms and ten oxygen atoms: the compound is tetraphosphorus
decoxide.
Practice Exercise 2.4
Name the following molecular compounds:
A) SiF4 b) Cl2O7
EXAMPLE 2.5
Write chemical formulas for the following molecular compounds:
A) carbon disulfide B) disilicon hexabromide
Solution
A) There are one carbon atom and two sulfur atoms: the formula is CS2.
B) There are two silicon atoms and six bromine atoms: the formula is Si2Br6.
Practice Exercise 2.5
Write chemical formulas for the following molecular compounds:
A) sulfur tetrafluoride B) dinitrogen pentoxide
2.7.3 Naming acids
An acid is a substance that has hydrogen atoms in its composition and give them as
ions, H+, when dissolved in water. Also, it is defined as substances that increases
hydrogen ions concentration of water after it dissolves in it
Naming binary acids:
The following table gives the names anions which ends with the suffix “-ide”:
Sulfide Fluoride Chloride Bromide Iodide Cyanide
S 2− F− Cl− Br − I− CN −
When one hydrogen ion (or more) is attached to any anion in the above table, the
molecular compound formed is named as in the table below: (note: HCN is not a
binary acid. However its name ends with the suffix “ide”)
25
Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen
sulfide fluoride chloride bromide iodide cynide
H2 S HF HCl HBr HI HCN
The aqueous solution of any one of the above compounds is a binary acid and it is
named as in the following table:
Hydrosulfuric Hydrofluoric Hydrochloric Hydrobromic Hydroiodic Hydrocyanic
acid acid acid acid acid acid
H2 S HF HCl HBr HI HCN
Naming oxoacids:
The reference oxacids and the derived oxacids
The reference oxacids: When one or more hydrogen ion is attached to an anion
ending with the suffix “ate”, the product is an oxoacid named as follows:
Nitrate Carbonate Sulfate Phosphate Fluorate Chlorate Bromate Iodate
− − −
NO3 CO32−
SO42−
PO4 3−
FO3 ClO3 BrO− 3 IO3−
Nitric Carbonic Sulfuric Phosphoric Fluoric Chloric Bromic Iodic
acid acid acid acid acid acid acid acid
HNO3 H2 CO3 H2 SO4 H3 PO4 𝐇𝐅𝐎𝟑 𝐇𝐂𝐥𝐎𝟑 𝐇𝐁𝐫𝐎𝟑 𝐇𝐈𝐎𝟑
These above acids are called “the reference oxoacids” because some other
oxoacids are derived from them. The last four acids are called “halic acids
The derived oxacids
Addition of one “O” atom to a halic acid
The addition of one “O” atom to a “halic acid” gives a “perhalic acid”:
Perfluorate Perchlorate Perbromate Periodate
− − −
FO4 ClO4 BrO4 IO4−
Perfluoric acid Perchloric acid Perbromic acid Periodic acid
𝐇𝐅𝐎𝟒 𝐇𝐂𝐥𝐎𝟒 𝐇𝐁𝐫𝐎𝟒 𝐇𝐈𝐎𝟒
Removal of one “O” atoms from the reference acids except 𝐇𝟐 𝐂𝐎𝟑
Removal of one “O” atom from any reference acid except H2 CO3 changes
the suffix “ic” to “ous” and the oxoions suffixes changes from “ate” to “ite”:
Nitrite Sulfite Phosphite Fluorite Chlorite Bromite Iodite
NO2 −
SO3 2−
PO33−
𝐅𝐎−𝟐 𝐂𝐥𝐎−𝟐 𝐁𝐫𝐎− 𝟐 𝐈𝐎−𝟐
Nitrous Sulfurous Phosphorous Fluorous Chlorous Bromous Iodous
acid acid acid acid acid acid acid
HNO2 H2 SO3 H3 PO3 𝐇𝐅𝐎𝟐 𝐇𝐂𝐥𝐎𝟐 𝐇𝐁𝐫𝐎𝟐 𝐇𝐈𝐎𝟐
Removal of two “O” atoms from the reference acids except 𝐇𝟐 𝐂𝐎𝟑,
Removal of two “O” atoms from any reference acid except H2 CO3 and
HNO3 adds a “hypo” prefix and changes the suffix “ic” to “ous”:
Hyposulfite Hypophosphite Hypofluorite Hypochlorite Hypobromite Hypoiodite
ion ion ion ion ion ion
2− 3− − − −
SO2 PO2 𝐅𝐎 𝐂𝐥𝐎 𝐁𝐫𝐎 𝐈𝐎−
Hyposulfurous hypophosphorous hypofluorous hypochlorous Hypobromous hypoiodous
acid acid acid acid acid acid
H2 SO3 H3 PO3 𝐇𝐅𝐎 𝐇𝐂𝐥𝐎 𝐇𝐁𝐫𝐎 𝐇𝐈𝐎
26
Removal of hydrogen ions from some oxoacids
The names of anions in which one or more but not all the hydrogen ions
have been removed must indicate the number of remaining hydrogen ions.
For example:
H3PO4: The removal of one hydrogen ion produces dihydrogen
phosphate ion, H2PO4– , and the removal of two hydrogen ions produces
hydrogen phosphate ion HPO2– 4
H2SO4: the removal of one hydrogen ion produces hydrogen sulfate ion,
HSO–4
EXAMPLE 2.6
Name the following oxoacid and oxoanion:
A) H3PO3 B) IO4–
Solution
A) The reference acid is phosphoric acid (H3PO4). Because H3PO3 has one fewer O atom,
it is phosphorous acid.
B) The reference acid is chloric acid (HIO3). Because the acid HIO4 has one more O atom
than our reference acid, it is called periodic acid and its oxanion, IO–4 , is periodate ion.
Practice Exercise 2.6
Name the following oxoacid and oxoanion:
A) HBrO B) HSO–4 .
2.7.4 Naming bases
A base is a substance that yields hydroxide ions (OH–) when dissolved in water. Some
examples are NaOH, KOH and Ba(OH)2. These compounds are named as ionic
compounds are named. The name starts with metal name and ends with the anion name
which is hydroxide. Therefore, the names of the previous three bases are sodium
hydroxide, potassium hydroxide and barium hydroxide respectively.
Ammonia (NH3) is a very famous base but it does not have OH– in its formula. It is a
molecular compound in its gaseous state or when it is a pure. When NH3 is dissolved
in water, it reacts partially with water to yield NH4+ and OH– ions:
NH3 + H2O ⇌ NH4+ + OH–
Thus, its aqueous solution is properly classified as a base.
2.7.5 Naming hydrates
Hydrates are compounds that have a specific number of water molecules attached to
them. For example, in its normal state, each unit of copper(II) sulfate has five water
molecules associated with it
The systematic name for this compound is copper(II) sulfate pentahydrate and its
formula is written as:
CuSO4·5H2O
The water molecules can be driven off by heating. When this occurs, the resulting
compound is CuSO4, which is named copper sulfate and sometimes called anhydrous
copper(II) sulfate. The word “anhydrous” means that the compound no longer has water
molecules associated with it
Other examples are:
Barium chloride dihydrate, BaCl2·2H2O
Lithium chloride monohydrate, LiCl·H2O
Magnesium sulfate heptahydrate, MgSO4·7H2O
27
Strontium nitrate tetrahydrate, Sr(NO3)2·4H2O
2.8 Common and systematic names of some compounds
There are several compounds acquired their names since remote human history or have
names that are so common among people worldwide and among chemists. These
compounds kept their common names. The following table gives the formula and their
common and systematic names.
28
3. MASS RELATIONSHIPS IN CHEMICAL REACTIONS
3.1 Atomic mass and average atomic mass
The mass of an atom depends on the number of protons and neutrons it contains
Atoms are extremely small particles. The smallest speck of dust that our eyes can detect
contains as many as 1 × 1016 atoms
It is possible to determine the mass of one atom relative to another experimentally
Atomic mass is the mass of the atom in atomic mass units (amu)
1 amu is the mass which equals one-twelfth the mass of one carbon-12 atom which
equals 1.993 × 10–23 g
The mass of one carbon-12 atom is exactly 12 amu
Hydrogen atom is 8.4% as massive as the carbon-12 atom. Thus, the atomic mass of
hydrogen is 0.084 × 12.00 amu = 1.008 amu
Similar calculations show that the atomic mass of oxygen is 15.999 amu and that of
iron is 55.845 amu
The atomic mass of carbon in the periodic table of elements, is not 12.00 amu but
12.0111 amu
The reason for the difference is that most naturally occurring elements (including
carbon) have more than one isotope
This means that when we measure the atomic mass of an element, we must generally
settle for the average atomic mass of the naturally occurring mixture of isotopes using
the following equation:
Average atomic mass = ∑percent of isotope × atomic mass of isotope
For example, 98.90% is carbon-12 (The atomic mass of carbon-12 = 12.0000 amu) and
1.10% is carbon-13 (The atomic mass of carbon-13 = 13.0033 amu):
average atomic mass = aam
aam an element = ∑percent of isotope × atomic mass of isotope
aam of carbon = {(0.9890) × (12.0000 amu)} + {(0.0110) × (13.0033 amu)}
aam of carbon = 12.011 amu
It is important to understand that when we say that the atomic mass of carbon is 12.011
amu, we are referring to the average value. But for simplicity, the word “average” is
usually omitted when discussing the atomic masses
EXAMPLE 3.1
The abundance of the copper isotope 63 65
29Cu is 69.09% and of the copper isotope 29Cu is 30.91%.
Calculate the average atomic mass of copper.
Solution
Average atomic mass = ∑percent of isotope × atomic mass of isotope
Average atomic mass = (0.6909) × (63 amu) + (0.3091) × (65 amu) = 63.62 amu
Practice Exercise 3.1
The abundance of the boron isotope, 105B is 19.78% and of the boron isotope 115B is 80.22%.
Calculate the average atomic mass of boron.
3.2 Avogadro’s number and the molar mass of an element
The idea of a unit to denote a certain number of objects is not new. For examples of
familiar units are: the pair = 2 items, the dozen = 12 items
29
In 1811, the Italian scientist, Avogadro introduced the idea that if we express the
atomic mass of an element in the unit of “gram” rather than in the unit of “amu” we
will have the same number of atoms regardless of the type of the element we chose
Avogadro died before achieving his goal to determine this number
The value was first determined in 1865 by the Austrian scientist Josef Loschmidt. This
number was named “Avogadro’s number” by the French scientist Jean Perrin
Now, Avogadro’s number, NA, is the number of carbon-12 atoms in 0.012 kg of
carbon-12 isotope. Its currently accepted value is:
NA = 6.0221415 × 1023 = 6.022 × 1023
Avogadro’s number is enormous: For example, spreading 6.022 × 1023 oranges over
the entire surface of Earth would produce a layer of no less than 14 km into space!
The symbol “N” is given for the number of particles we have
The value of “N” may equal Avogadro’s number, more than Avogadro’s number or
less than Avogadro’s number
The mole is the SI unit for the “amount of substance”
The IUPAC definition of the mole is that the mole is the amount of substance of a
system which contains as many elementary entities as there are atoms in 0.012
kilogram of carbon-12
The molar mass is discussed below
3.3 Molecular mass
“Atomic mass, molecular mass, formula mass and the molar mass”
“Molar mass” of the substance is the mass of one mole of it
Substances are either atoms, molecules of the same element, molecular compound or
ionic compounds
When the compound is molecular compound the mass of one mole of it is called
“molecular mass” and when the compound is ionic compound the mass of one mole of
it is called “formula mass”
1) “Atomic mass” and “Molar mass”:
The periodic table shows that the atomic masses H is 1.008 amu, therefore the mass
g
of one mole of atomic hydrogen (H) using SI UNITS is 1.008 mol. This mass is
called the atomic mass of H; it is also called the molar mass of H
2) “Molecular mass” and “Molar mass”:
The periodic table shows that the atomic masses oxygen, O, is 16 amu, therefore
g
the mass of one mole of molecular oxygen, (O2 ), using SI UNITS is 32 mol. This
mass is called the molecular mass of O2 ; it is also called the molar mass of O2 .
Another example: the periodic table shows that the atomic masses carbon, C, is
12.01 amu and the atomic masses oxygen, O, is 16 amu. Therefore, the mass of one
g
mole of CO2 , using SI UNITS is 44.01 mol. This mass is called the molecular mass
of CO2 ; it is also called the molar mass of CO2
3) “Formula mass” and “Molar mass”:
The periodic table shows that the atomic masses sodium, Na, is 22.99 amu and of
chlorine, Cl, is 35.45 amu. Therefore, the mass of one mole of NaCl, using SI
g
UNITS is 58.44 mol. This mass is the formula mass of NaCl; it is also called the
molar mass of carbon NaCl
30
The above examples show that the mass of one mole of any substance is called its
“molar mass” regardless whether it consists of atoms, molecules or ions
Relations between M”, “m”, “n”, and “N”
It is important to know the relations between “M”, “m”, “n”, “N” and “NA”
M = Molar mass of a substance in g/mole units (or kg/mole units)
m =Mass of a substance in g units (or kg units)
n = Number of moles of a substance
N = Number of particles (atoms, molecules or ions) of a substance
NA = Avogadro’s number
The relations between M”, “m”, “n”, and “N” are:
𝐦 𝐍 𝐦 𝐍
n=𝐌 n=𝐍 =𝐍
𝐀 𝐌 𝐀
EXAMPLE 3.2
How many moles of He atoms are in 6.46 g of He?
Solution
m 6.46 g
n=M= g = 1.61 mol
4.003
mol
Practice Exercise 3.2
How many moles of magnesium (Mg) are there in 87.3 g of Mg?
EXAMPLE 3.3
How many grams of Zn are in 0.356 mole of Zn?
Solution
m = n × M = 0.356 mole × 65.39 g/mol = 23.3 g
Practice Exercise 3.3
Calculate the number of grams of lead (Pb) in 12.4 moles of lead.
EXAMPLE 3.4
How many atoms are in 16.3 g of S?
Solution
m N
=N
M A
16.3 g N
g = atoms
32.07
mol
6.022 × 1023
mol
atoms
16.3 g × 6.022 × 1023
N= g
mol
= 3.06 × 1023 atoms
32.07
mol
Practice Exercise 3.4
Calculate the number of atoms in 0.551 g of potassium (K).
EXAMPLE 3.5
How many hydrogen atoms are present in 25.6 g of urea [(NH2)2CO], which is used as a
fertilizer, in animal feed, and in the manufacture of polymers? The molar mass of urea is 60.06
g/mol.
Solution
31
m N
=N
M A
m × NA
N= M
Nhydrogen atoms = 4 × Nurea molecules
atoms
m × NA 25.6 g × 6.022 × 1023
Nhydrogen atoms = 4 × =4× g
mol
= 1.03 × 1024 H atoms
M 60.06
mol
Practice Exercise 3.5
How many H atoms are in 72.5 g of isopropanol (rubbing alcohol), C3H8O?
EXAMPLE 3.6
Methane (CH4) is the principal component of natural gas. How many moles of CH4 are present
in 6.07 g of CH4?
Solution
m 6.07 g
n=M= g g = 0.378 mol
1 × 12.01 + 4 × 1.008
mol mol
Practice Exercise 3.6
Calculate the number of moles of chloroform (CHCl3) in 198 g of CHCl3.
EXAMPLE 3.7
g
Calculate the molar masses (in mol) of the following compounds:
A) Sulfur dioxide (SO2) B) Caffeine (C8H10N4O2).
Solution
g g g
A) MSO2 = 1 × 32.07 mol + 2 × 16.00 mol= 64.07 mol
g g g g
B) MC8H10N4 O2 = (8 × 12.01 mol) + (10 × 1.008 mol) + (4 × 14.01 mol) + 2 × 16.00 mol =
g
194.20 mol
Practice Exercise 3.7
g
Calculate the molar mass (in ) of methanol (CH4O).
mol
3.4 The mass spectrometer
The most direct and accurate method for determining atomic and molecular masses is
mass spectrometry
In a mass spectrometer, a gaseous sample is bombarded by a stream of high-energy
electrons
Collisions between the electrons and the gaseous atoms (or molecules) produce positive
ions by dislodging an electron from each atom or molecule
These positive ions (of mass m and charge e) are accelerated by two oppositely charged
plates as they pass through the plates
The emerging ions are deflected into a circular path by a magnet
e
The radius of the path depends on the charge-to-mass ratio (that is, m)
e e
Ions of smaller m ratio trace a wider curve than those having a larger m ratio, so that
ions with equal charges but different masses are separated from one another
The mass of each ion (and hence its parent atom or molecule) is determined from the
magnitude of its deflection
Eventually the ions arrive at the detector, which registers a current for each type of ion
32
The amount of current generated is directly proportional to the number of ions, so it
enables us to determine the relative abundance of isotopes
The first mass spectrometer, developed in the 1920s by the English physicist F. W.
Aston, was crude by today’s standards. Nevertheless, it provided indisputable evidence
of the existence of isotopes—neon-20 (atomic mass 19.9924 amu and natural
abundance 90.92%) and neon-22 (atomic mass 21.9914 amu and natural abundance
8.82%)
When more sophisticated and sensitive mass spectrometers became available, scientists
were surprised to discover that neon has a third stable isotope with an atomic mass of
20.9940 amu and natural abundance 0.257 percent
This example illustrates how important experimental accuracy is to a quantitative
science like chemistry. Early experiments failed to detect neon-21 because its natural
abundance is just 0.257%. In other words, only 26 in 10,000 Ne atoms are neon-21
The masses of molecules can be determined in a similar manner by the mass
spectrometer
3.5 Percent composition of elements in compounds
Any compound is composed of two elements or more
The mass percent of any element in the compound is called the “percent composition
of the element in a compound” and is obtained by dividing the mass of the element
in 1 mole of the compound by the molar mass of the compound and multiplying by
100:
n × molar mass of element
percent composition of an element = molar mass of compound × 100
Where “n” is the number of moles of the element in 1 mole of the compound. For
example, in 1 mole of hydrogen peroxide (H2O2) there are 2 moles of H atoms and 2
g g
moles of O atoms. The molar masses of H2O2, H, and O are 34.02 mol, 1.008 mol, and
g
16.00 mol, respectively. Therefore, the percent composition of H and O in H2O2 is
calculated as follows:
g
2 × 1.008
mol
percent composition of H = g × 100 = 5.927%
34.016
mol
g
2 × 16.00
mol
percent composition of O = g × 100 = 94.073%
34.02
mol
EXAMPLE 3.8
Phosphoric acid (H3PO4) is a colorless liquid used in detergents, fertilizers, toothpastes, and in
carbonated beverages. Calculate the percent composition of H, P, and O in this compound.
Solution
The molar mass of H3PO4 is 97.99 g/mol
g
3 × 1.008
mol
percent composition of H = g × 100 = 3.086%
97.99
mol
g
1 × 30.97
mol
percent composition of P = g × 100 = 31.61%
97.99
mol
g
4 × 16.00
mol
percent composition of O = g × 100 = 65.31%
97.99
mol
Practice Exercise 3.8
Calculate the percent composition by mass of each of the elements in sulfuric acid (H2SO4).
33
3.6 Experimental determination of empirical formula
(Empirical and molecular formulas)
First: The empirical formulas
The empirical formula of a compound is the formula which tells us the numerical ratios of
the elements in the formula. Usually we seek the ratios that consists of the simplest
(smallest) whole numbers. The procedure to determine the empirical formula is as follows.
The procedure to determine the empirical formula is as follows
First, from qualitative chemical analysis we know the elements of the compound
Second, from quantitative chemical analysis, we know the mass of each element
present in a given mass of the compound (or the mass percent of each element)
Third, we convert the masses to number of moles of each element
Forth, we obtain the mole ratio of elements to each other
Finally, we find the empirical formula of the compound
EXAMPLE 3.9
Ascorbic acid is composed of 40.92 percent carbon (C), 4.58 percent hydrogen (H), and 54.50
percent oxygen (O) by mass. Determine its empirical formula.
Solution
C : H : O
40.92 g 4.58 g 54.50 g
g : g : g
12.01 1.008 16.00
mol mol mol
3.407 : 4.54 : 3.406
3.407 4.54 3.406
: :
3.406 3.406 3.406
1 : 1.33 : 1
3 : 4 : 3
The result indicates that C, H and O are in the ratio 3:4:3 and the simplest (smallest) empirical
formula for ascorbic acid C3H4O3 is.
Practice Exercise 3.9
Determine the empirical formula of a compound having the following percent composition by
mass: K: 24.75%; Mn: 34.77%; O: 40.51%.
Second: The molecular formulas
The molecular formula shows the exact number of atoms of each element in the
molecule
Any multiple of the simplest (smallest) empirical formula is an empirical formula
The molecular formula is the empirical formula with the actual number of each
element’s atom in the compound
To determine which empirical formula is the molecular formula we need, in addition
to its simplest empirical formula, to know the actual or the approximate molar mass
of the compound
The molar mass of a compound must be the molar mass of the simplest (smallest)
empirical formula or its multiples
EXAMPLE 3.10
A sample of a compound contains 1.52 g of nitrogen (N) and 3.47 g of oxygen (O). The molar
mass of this compound is between 90 g and 95 g. Determine the molecular formula and the
accurate molar mass of the compound.
Solution
34
m
n=M
1.52 g
nN = g = 0.108 mol
14.01
mol
3.47 g
nO = g = 0.217 mol
16.00
mol
N : O
0.108 : 0.217
0.108 0.217
:
0.108 0.108
1 : 2
NO2 is the simplest (smallest) empirical formula for compound.
g
Empirical formula molar mass = 1 × 14.01 + 2 × 16.00 = 46 mol
g
actual molar mass 90
: mol
g ≈2
emperical molar mass 46
mol
The actual molar mass is twice the empirical molar mass. This means that molecular formula is
2 × NO2
The molecular formula is N2O4.
Practice Exercise 3.10
A sample of a compound consisting of boron (B) and hydrogen (H) contains 6.444 g of B and
1.803 g of H. The molar mass of the compound is about 30 g. What is its molecular formula?
3.7 Chemical reactions and chemical equations
A chemical reaction is a process in which a substance (or substances) is changed into
one or more new substances
The chemical-reaction equation, or simply the chemical equation is the chemists’
way to represent what happens to atoms and molecules in a chemical reaction
The chemical equation uses symbols and formulas to show what happens during a
chemical reaction
Writing chemical equations: The chemical equation consists of three parts. The first
part is the most important and, unfortunately, the most to be forgotten and ignored.
The first part is the arrow “”
The second part is “the reactants” at the left of the arrow “”
The third part is the “products” at the right of the arrow “”
The arrow is the “official speaker” or the “narrator” of the equation. It tells us what
and how much we had at the beginning and what and how much we had at the end
Producing water from the combustion of hydrogen gas (H2) in oxygen (O2) of air
is represented by the chemical equation as:
H2 + O2 H2O
The “plus” sign means “reacts with” and the arrow tells us the story as follows:
“water is produced on the expense of consuming hydrogen and oxygen” or
“Molecular hydrogen reacts with molecular oxygen to produce water”
looking at the previous equation reveals that it violates the law of conservation of
matter. However, this violation can be simply prevented by ensuring that number
of atoms of any element on the right and on the left sides of the arrow are equal.
This is done by balancing the equation. The balanced equation of the previous
reaction is:
1
H2 + 2O2 H2O
35
Usually, we prefer that equation is balanced in a way that gives whole correct
numbers without fractions. So, although the last equation is correct, we prefer the
following:
2H2 + O2 2H2O
To provide additional information, chemists often indicate the physical states of the
reactants and products by using the letters g, l, and s to denote gas, liquid, and solid,
respectively. For example:
2CO(g) + O2(g) 2CO2(g)
2HgO(s) 2Hg(l) + O2(g)
To represent what happens when the solid sodium chloride (NaCl) is added to liquid
water, we write:
H2 O
NaCl(s) → NaCl(aq)
where “aq” denotes the aqueous environment. (“aqua” means “water”). Writing
H2O above the arrow symbolizes the physical process of dissolving a substance in
water, although it is sometimes left out for simplicity.
EXAMPLE 3.11
When aluminum metal is exposed to air, a protective layer of aluminum oxide (Al2O3) forms on
its surface. This layer prevents further reaction between aluminum and oxygen, and it is the
reason that aluminum beverage cans do not corrode. Write a balanced equation for the formation
of Al2O3.
Solution
The unbalanced equation is:
Al + O2 Al2O3
We see that there is one Al atom on the reactants side and there are two Al atoms on the
product side. We can balance the Al atoms by placing a coefficient of 2 in front of Al on the
reactants side:
2Al + O2 Al2O3
There are two O atoms on the reactants, and three O atoms on the product of the equation.
3
We can balance the O atoms by placing a coefficient of 2 in front of O2 on the reactants side:
3
2Al + 2O2 Al2O3
This is a balanced equation. However, we prefer equations with the smallest set of whole
number. Multiplying both sides of the equation by 2 gives whole number coefficients:
4Al + 3O2 2Al2O3
Practice Exercise 3.11
Balance the equation representing the reaction between iron(III)oxide, Fe2O3, and carbon
monoxide (CO) to yield iron (Fe) and carbon dioxide (CO2).
3.8 Amounts of reactants and products in chemical reactions
(Stoichiometry)
The word “stoichiometry” came from two Greek words: “stoikhein” which means
“element” and “metron” which means “measure”
stoichiometry concerns with measuring and calculating quantities of substances
consumed and produced in chemical reactions
Stoichiometry answers questions such as:
36
“How much product will be formed as a result of the reaction of a specific amount
of a reactant?”
“How much reactant must be used in a reaction to obtain a specific amount of a
product?”
To interpret a reaction quantitatively, we need to apply our knowledge of molar masses
and the mole concept
Whether the units given for reactants (or products) are grams, liters, or any other
units, we only use the “mole method” in which the “mole” is the unit used to carry
out calculations in any reaction
For example, industrially ammonia is synthesized as follows:
N2(g) + 3H2(g) 2NH3(g)
The stoichiometric coefficients show that 1 mole of N2 reacts with 3 moles of H2 to
produce 2 moles of NH3
Suppose 16.0 g of H2 reacted completely with N2 to form NH3, and we need to know
number of grams of NH3 formed.
We do this calculation using the “mole method”. So, we need to convert grams of
H2 to moles of H2
m
n= M
16 g
number of moles of H2 = g = 7.94 mol H2
2.016
mol
Then we construct a table as follows:
Equation N2(g) + 3H2(g) 2NH3(g)
Equation moles 3 mol 2 mol
Question moles 7.94 mol X
Then we do our calculations:
7.94 mol H
X = 2 mol NH3 × 3 mol H 2 = 5.29 mol NH3
2
m=n×M
g
mass of NH3 = 5.29 mol × 17.03 mol = 90.1 g NH3
Similarly, we can calculate the mass in grams of N2 consumed
The general approach for the table of solving stoichiometry problems is as follows:
1) Write a balanced equation for the reaction
2) Write number of moles as appeared in the equation
3) Write number of moles as given or as calculated
4) Carry on your calculation using the mole method
5) Convert your result to any other unit you like
EXAMPLE 3.12
The food we eat is degraded in our bodies to provide energy. The degradation of glucose (C6H12O6)
to carbon dioxide (CO2) and water (H2O) is as follows:
C6H12O6 + 6O2 6CO2 + 6H2O
If 856 g of C6H12O6 is consumed what is the mass of CO2 produced?
Solution
m 856 g
Number of moles of C6H12O6 = M = g = 4.750 mol C6H12O6
180.2
mol
C6H12O6 + 6O2 6CO2 + 6H2O
Equation moles 1 mole 6 mol
37
Question moles 4.750 mol X
X = nCO2 = 6 × nC6 H12O6 = 6 × 4.750 mol = 28.50 mol
g
mCO2 = nCO2 × MCO2 = 28.50 mol × 44.01 mol = 1.25 × 103 g
Practice Exercise 3.12
Methanol (CH3OH) burns in air according to the equation
2CH3OH + 3O2 2CO2 + 4H2O
If 209 g of methanol are a combusted, what is the mass of H2O produced?
EXAMPLE 3.13
A typical reaction of alkali metals with water is that between lithium and water:
2Li(s) + 2H2O(l) 2LiOH(aq) + H2(g)
How many grams of Li are needed to produce 9.89 g of H2?
Solution
m 9.89 g
Number of moles of H2 = = g = 5 mol H2
M 2 × 1.008
mol
2Li + 2H2O 2LiOH + H2
Equation moles 2 mol 1 mol
Question moles X 5 mol
5 mol H
X = nLi = 2 mol of Li × 1 mol H2 = 10 mol
2
g
mLi = nLi × MLi = 10 mol × 6.941 mol = 69.41 g
Practice Exercise 3.13
A key step in photochemical smog formation is the following reaction between nitric oxide (NO)
and oxygen to form nitrogen dioxide (NO2):
2NO(g) + O2(g) 2NO2(g)
How many grams of O2 are consumed to produce 2.21 g of NO2?
3.9 Limiting reactants (reagents)
Let’s imagine that a person has 11 toast breads and 4 slices of cheese.
To make a sandwich two toasts and one cheese slice is needed.
If we symbolize the toast as “Ts” and the cheese as “Ch”, the formula of the sandwich
will be “Ts2Ch”:
2Ts + Ch Ts2Ch
We know that number “Ch” available is enough to produce only 4 “Ts2Ch” while some
of the “Ts” will remain “unreacted” because it is present in access.
We say that “Ch” is the “reactant” which limits the quantity of “products” because it
is the one which is consumed completely, and we call it “the limiting reactant”.
We say that “Ts” is the “in-access reactant” because some of it will be will remain
“unreacted”.
When a chemist carries out a reaction, the reactants are usually not present in exact
stoichiometric amounts as the balanced equation requires.
Frequently a large excess of one reactant is supplied to ensure that the more expensive
reactant is completely converted to the desired product. Consequently, some reactant
will be left over at the end of the reaction.
38
In a reaction, the reactant consumed totally with no left over is called the limiting
reactant or the limiting reagent because the maximum amount of product formed is
limited by its amount, and once this reactant is used up, no more product can be formed.
Any reactant presents in a quantity greater than necessary to react with the quantity of
the limiting reactant is called excess reactant or excess reagent
To determine which reactant is the limiting reactant we follow the steps below for the
industrial synthesis of methanol (CH3OH) from 4 moles of carbon monoxide and 6
moles hydrogen:
1) Write the balanced chemical equation of the reaction
CO + 2H2 CH3OH
2) Divide the number of moles of each reactant by its coefficient in the chemical
equation:
4 6
For CO: 1 = 4 and For H2: 2 = 3
3) The reactant with the least quotient is the limiting reactant, the other is the excess
reactant. Therefore, in this reaction H2 is the limiting reactant, and CO is the excess
reactant.
4) After the limiting reagent has been identified, the rest of the problem can be solved.
EXAMPLE 3.14
637.2 g of NH3 are treated with 1142 g of CO2 to produce urea (NH2)2CO:
2NH3 (g) + CO2(g) (NH2)2CO(aq) + H2O(l)
A) Which reactants is the limiting reagent?
B) Calculate the mass of (NH2)2CO formed
C) How much excess reagent (in grams) is left at the end of the reaction?
Solution
m 637.2 g
A) number of moles of NH3 = M = g = 37.416 mol
17.03
mol
m 1142 g
number of moles of CO2 = = g = 25.943 mol
M 44.02
mol
39
Equation moles 2 mol 1 mol
Question moles 37.416 mole Y
37.416 mol × 1 mol
Y = number of moles of CO2 reacted = = 18.708 mol
2 mol
number of moles of CO2 remains = 25.943 mol – 18.708 mol = 7.235 mol
mass of CO2 remains = n × M = 7.235 mol × 44.02 g/mol = 318.5 g
Practice Exercise 3.14
The reaction between Al and Fe2O3 can generate temperatures approaching 3000 °C and is used in
welding metals:
2Al(g) + Fe2O3 Al2O3 + 2Fe
In one process, 124 g of Al are reacted with 601 g of Fe2O3. (a) Calculate the mass (in grams) of
Al2O3 formed. (b) How much of the excess reagent is left at the end of the reaction?
3.10 Reaction yield (Yield percentage)
The amount of a product that should be produced in a chemical reaction can be
calculated theoretically.
This calculated amount of product is called “the theoretical yield” of the reaction.
The theoretical yield is, the amount of product that would result if all the limiting
reagent reacted. It is the maximum obtainable yield and is known by calculations on
the balanced equation.
The amount of a product that is really (not theoretically) produced is different from the
theoretical yield and is called “the actual yield”.
For many reasons, the actual yield is always less than the theoretical yield.
Chemists have created a criterion that could be a measure of their efficiency and success
in production of chemicals. This criterion is called “the yield percent”, or “the yield
percentage”
actual yield
yield% = theoretical yield × 100
EXAMPLE 3.15
In an industrial operation 3.54 × 107 g of TiCl4 reacted with 1.13 × 107 g of Mg:
TiCl4(g) + 2Mg(g) Ti(s) + 2MgCl2(l)
A) Calculate the theoretical yield of Ti
B) Calculate the percent yield if 7.91 × 106 g of Ti actually are obtained
Solution
mTiCl4 3.54 × 107 g mMg 1.13 × 107 g
A) nTiCl4 = = g = 1.87 × 105 mol AND nMg = = g = 4.65 × 105 mol
MTiCl4 189.9 MMg 24.31
mol mol
TiCl4 + 2Mg Ti + 2MgCl2
Equation moles 1 mol 2 mol
Question moles 1.87 × 105 4.65 × 105
Question moles
1.87 × 105 2.325 × 105
Equation moles
It is clear from the last row that TiCl4 is the limiting reagent.
TiCl4 + 2Mg Ti + 2MgCl2
Equation moles 1 mol 1 mol
Question moles 1.87 × 105 mole n
1.87 × 105 mol × 1 mol
Theoretical yield of Ti = = 1.87 × 105 mol
1 mol
40
m = n × M = 1.87 × 105 mol × 47.88 g/mol = 8.95 × 106 g
actual yield 7.91 × 106 g
C) %yield = theoretical yield × 100 = 8.95 × 106 g × 100 = 88.37%
Practice Exercise 3.15
Industrially, vanadium metal, which is used in steel alloys, can be obtained by reacting
vanadium(V) oxide with calcium at high temperatures:
5Ca + V2O5 5CaO + 2V
In one process, 1.54 × 103 g of V2O5 react with 1.96 × 103 g of Ca. (a) Calculate the theoretical
yield of V. (b) Calculate the percent yield if 803 g of V are obtained.
41
4. REACTIONS IN AQUEOUS SOLUTIONS
4.1 General properties of aqueous solutions
A solution is a homogeneous mixture of two or more substances
The solute is the substance present in a smaller amount, and the solvent is the substance
present in a larger amount
We will discuss only aqueous solutions of a liquid or a solid
4.2 Electrolytic properties
All solutes that dissolve in water are either electrolytes or nonelectrolytes
An electrolyte is a substance that, when dissolved in water, results in a solution that
can conduct electricity
A nonelectrolyte does not conduct electricity when dissolved in water
A characteristic of strong electrolytes is that the solute is assumed to be 100 percent
dissociated. Thus, we can represent dissolving 0f sodium chloride in water as:
H2 O
NaCl (s) → Na+ (aq) + Cl− (aq)
Electrolytes are two kinds
strong (i.e. ionic compounds that are 100% dissociated into its ions when dissolved
in water). NaCl is an example:
This equation says that all dissolved sodium chloride ends up as Na+ and Cl− ions
and no undissociated NaCl units in solution:
H2 O
NaCl (s) → Na+ (aq) + Cl− (aq)
Acids and bases are also electrolytes. Some acids, including hydrochloric acid
(HCl) and nitric acid (HNO3 ) are strong electrolytes: These acids are assumed to
ionize completely in water:
H2 O
HCl (g) → H + (aq) + Cl− (aq)
weak (i.e. molecular compounds that partially ionized into cations and anions when
dissolved in water). Acetic acid is an example:
CH3 COOH(aq) ⇌ H + (aq) + CH3 COO− (aq)
This equation says that some dissolved acetic acid ends up as H + and CH3 COO−
ions and the rest of it remains as CH3 COOH units in solution
Strong acids (bases) and weak acids (and bases) are the most common types of
electrolytes. The following table shows that:
Electrolyte
Nonelectrolyte
Strong Weak
HCl HF (NH2 )2 CO, urea
HNO3 HNO2 CH3 OH, methanol
HClO4 NH3 CH3 CH2 OH ethanol
H2 SO4 H2 O (extremely weak) C6 H12 O6 , glucose
NaOH HCOOH C12 H22 O11 , sucrose
BaOH2 CH3 COOH C3 H5 OH3 , glycerol
4.3 Precipitation reactions
4.3.1 Solubility
Precipitation reaction is the formation of an insoluble product, or precipitate
A precipitate is an insoluble solid that separates from the solution
42
Precipitation reactions usually involve ionic compounds.
Example: Adding an aqueous solution of lead(II) nitrate, to an aqueous solution of
potassium iodide, a yellow precipitate of lead(II) iodide ,𝑃𝑏𝑙2 , is formed:
Pb(NO3 )2 (aq) + 2KI(aq) → PbI2 (s) + 2KNO3 (𝑎𝑞)
This reaction is an example of a metathesis reaction (also called a double-displacement
reaction), a reaction that involves the exchange of parts between the two compounds
Solubility: predicting whether a precipitate will form when a compound is added to a
solution or when two solutions are mixed depends on the solubility of the solute
The solubility of the solute is the maximum amount of solute that will dissolve in a
given quantity of solvent at a specific temperature
A soluble substance is the substance if a fair amount of it visibly dissolves in water
A slightly soluble or an insoluble substance that a fair amount of it is not visibly
dissolves in water
All ionic compounds are strong electrolytes, but they are not equally soluble
The following table classifies common ionic compounds as soluble or insoluble
SOLUBLE COMPOUND INSOLUBLE EXEPTIONS
+
Compounds containing alkali metals ions (Li ,
Na+ , K + , Rb+ , Cs + ) and mmonium (NH4+ )
Nitrates (NO− −
3 ), bicarbonates (HCO3 ), and
−
chlorates (ClO3 ),
Halides (Cl− , Br − , l− ) Halides of Ag + , Hg 2−
2 , Pb
2+
43
Pb(NO3 )2 (aq) + 2KI(aq) → PbI2 (s) + 2KNO3 (aq)
This equation called a molecular equation because the formulas of the compounds are
written as though all species existed as molecules or whole units
A molecular equation is useful because it identifies the reagents (lead(II) nitrate and
potassium iodide)
However, a molecular equation does not describe in detail what really is happening in
solution
When ionic compounds dissolve in water, they break apart into their component cations
and anions
The equations should show the dissociation of dissolved ionic compounds into ions.
Therefore, it’s better to write it as follows:
Pb2+ + 2NO− + −
3 + 2K + 2I → PbI2 (s) + 2K + 2NO3
+ −
44
Write the net ionic equation for the reaction an Al(NO3 )3 (s) solution with a NaOH solution.
4.3 Acid-base reactions
Acids and bases are as familiar as acetylsalicylic acid (aspirin) and magnesium
hydroxide (milk of magnesia)
Acid-base chemistry is important in industrial processes and essential in sustaining
biological systems
4.3.1 General properties of acids and bases
Definitions
Arrhenius Acids and Bases: Arrhenius defined acids as substances that ionize in
water to produce H + ions and bases as substances that ionize in water to produce
OH − ions
Brønsted Acids and Bases: Brønsted defined acids as substances that donates H +
ions and bases as substances that accepts H + ions (Note: Brønsted’s definitions do
not require acids and bases to be in aqueous solution)
Acids have a sour taste; vinegar owes its sourness to acetic acid, and lemons and other
citrus fruits contain citric acid
Acids cause color changes in plant dyes, they change the color of litmus from blue to
red
Acids react with certain metals, such as zinc, magnesium, and iron, to produce
hydrogen gas. A typical reaction is that between hydrochloric acid and magnesium:
2H + (aq) + Mg(s) → 𝑀𝑔𝐶𝑙2 (s) + 𝐻2 (g)
Aqueous acid solutions conduct electricity
Bases have a bitter taste
Bases feel slippery; soaps, which contain bases, exhibit this property
Bases cause color changes in plant dyes; they change the color of litmus from red to
blue
Aqueous base solutions conduct electricity
Hydrochloric acid is a Brønsted acid because it donates a proton in water:
HCl(aq) → H + (aq) + Cl− (aq)
H + (aq) ion is just a bare proton. This exceedingly small charged particle cannot exist
as a separate entity in aqueous solution owing to its strong attraction for the negative
pole of 𝐻2 𝑂 to form hydronium ion H3 O+ (aq)
For convenience, we generally use H + (aq) to represent the hydrated proton, but
H3 O+ (aq) is closer to reality
Keep in mind that both notations represent the same species in aqueous solution
Acids commonly used in the laboratory are hydrochloric acid (HCl), nitric acid
(HNO3 ), acetic acid (CH3 COOH), sulfuric acid (H2 SO4 ), and phosphoric acid (H3 PO4 ).
Monoprotic acids: is an acid that when each unit yields one hydrogen ion upon
ionization it examples are:
HCl(aq) → H + (aq) + Cl− (aq)
HNO3 (aq) → H + (aq) + NO3 − (aq)
CH3 COOH(aq) ⇌ H + (aq) + CH3 COO− (aq)
Because the ionization of acetic acid is incomplete (note the double arrows), it is a
weak electrolyte. For this reason, it is called a weak acid. On the other hand, HCl
and HNO3 are strong acids that completely ionized in solution (single arrows)
45
Diprotic acids: is an acid that when each unit yields two hydrogen ions upon
ionization it example is:
H2 SO4 (𝑎𝑞) → H + (aq) + HSO− 4 (aq)
− (aq) + (aq) 2− (aq)
HSO4 ⇌ H + SO4
H2 SO4 is a strong electrolyte or strong acid (the first step of ionization is complete),
but HSO− 4 is a weak acid or weak electrolyte, and we need a double arrow to
represent its incomplete ionization
Triprotic acids, is an acid that when each unit yields three hydrogen ions upon
ionization it examples is:
H3 PO4 (𝑎𝑞) ⇌ H + (aq) + H2 PO− 4 (aq)
− (aq) + (aq) 2− (aq)
H2 PO4 ⇌ H + HPO4
HPO2−
4 (aq) ⇌ H + (aq)
+ PO3−4 (aq)
− −
H2 PO4 and H2 PO4 are weak acids (the double arrows represent its incomplete
ionization) found in aqueous solutions of phosphates such as NaH2 PO4 and
Na2 HPO4
The following table lists several common strong and weak acids:
Strong acids Weak acids
Hydrochloric acid HCl Hydrofluoric acid HF
Hydrobromic acid HBr Nitrous acid HNO2
Hydroiodic acid HI Phosphoric acid H3 PO4
Nitric acid HNO3 Acetic acid CH3 COOH
Sulfuric acid H2 SO4
Perchloric acid HClO4
Some hydroxides, such as NaOH, are strong electrolytes. they are completely ionized
in water:
H2 O
NaOH(g) → Na+ (aq) + OH − (aq)
−
The OH ion can accept a proton as follows:
OH − (aq) + H + (aq) → H2 O(𝑙)
−
Thus, OH is a Brønsted base
After ammonia gas, (NH3 (𝑔)) dissolves in water it is classified as a Brønsted base
because it can accept H + from H2 O:
NH3 (aq) + H + (aq) → 𝑁𝐻4+ (aq) + OH − (aq)
Ammonia is a weak base) because only a small fraction of dissolved NH3 (𝑔 molecules
react with water to form 𝑁𝐻4+ and ions OH − .
All the alkali metal hydroxides are soluble, the most commonly used strong base in the
laboratory is the cheap and soluble NaOH
The most commonly used weak base is aqueous ammonia solution, it is sometimes
erroneously called ammonium hydroxide. The species 𝑁𝐻4 OH do notexists
All the alkali earth metal hydroxides elements form hydroxides. Ba(OH)2. Magnesium
and calcium hydroxides are used in medicine and industry
Hydroxides of other metals, such as Al(OH)3 and Zn(OH)2 are insoluble and are not
used as bases
Example 4.3
Classify each of the following species in aqueous solution as a Brønsted acid or base:
A) HBr B) NO− 2 C) HCO− 3
46
Solution
A) HBr(aq) → H + (aq) + Br − (aq)
HBr is a Brønsted acid
B) NO− +
2 + H (aq) → HNO2 (aq)
−
NO2 is a Brønsted base
C) HCO− +
3 (aq) → H (aq) + CO3 (aq)
2−
−
HCO3 is a Brønsted acid
HCO− +
3 (aq) → H (aq) + H2 CO3 (aq)
−
HCO3 is a Brønsted base
HCO− 3 (aq) is an amphoteric substance
An amphoteric substance a substance that has the ability to act either as an acid or a base
Practice exercise 4.3
Classify each of the following species in aqueous solution as a Brønsted acid or base:
A) SO2−
4 B) HI
4.3.2 Acid-Base Neutralization
A neutralization reaction is a reaction between an acid and a base
Generally, aqueous acid-base reactions produce water and a salt, which is an ionic
compound made up of a cation other than H + and an anion other than OH − or O2− :
acid + base → salt + water
The following example is the typical neutralization reaction:
HCl(aq) + NaOH(aq) → NaCl(aq) + H2 O(𝑙)
H (aq) + Cl (aq) + Na+ (aq) + OH − (aq) → Na+ (aq) + Cl− (aq) + H2 O(𝑙)
+ −
47
Carbonic acid is unstable and if present in solution in sufficient concentrations
decomposes as follows:
H2 CO3 (aq) → CO2 (g) + H2 O(𝑙)
Other examples are:
NaHCO3 (aq) + HCl → CO2 (g) + H2 O(𝑙) + NaCl(aq)
Na2 SO3 (aq) + 2HCl → SO2 (g) + H2 O(𝑙) + 2NaCl(aq)
K 2 S(aq) + 2HCl → H2 S(g) + 2KCl
4.4 Oxidation-reduction reactions
4.4.1 The concept
Let us carefully see and inspect the following equation:
2Mg(s) + O2 (g) → 2MgO(s)
MgO is an ionic compound made up of one Mg 2+ ion and one O2− ion
Forming one MgO compound is a result of transferring two electrons from an Mg atom
to an O atom. This transfer usually is split into two steps each of which is called half-
reaction:
2Mg → 2Mg 2+ + 4e−
2O + 4e− → 2O2−
The sum of these two halves is:
2Mg(s) + O2 (g) + 4e− → 2MgO(s) + 4e−
2Mg(s) + O2 (g) → 2MgO(s)
NOTE: From the previous points we may think that transfer of electrons is limited to
formation ionic compounds. However, the truth is not; formation of some nonionic
compound involves this transfer, in other words involves oxidation and reduction.
These cases will be discussed in the next section titled “Oxidation numbers”
4.4.2 Terminology
The oxidation reaction is the half reaction "2Mg → 2Mg 2+ + 4e− “ which involves
electron loss (or donation). The substance that loses (donates) electrons is called the
reductant (or the reducing agent) and
The reduction reaction is the half reaction "2O + 4e− → 2O2− " which involves
electron gain (or acceptance). The substance that gains (accepts) electrons is called the
oxidant (or the oxidizing agent) and we say: “the oxidizing agent is reduced”
The reducing agent is oxidized, and the oxidizing agent is reduced
Other examples of oxidation-reduction reactions are:
Zn(s) + CuSO4 (aq) → ZnSO4 (aq) + Cu(s)
Its half-reactions are
Zn → Zn2+ + 2e−
Cu2+ + 2e− → Cu
Cu(s) + AgNO3 (aq) → CU(NO3 )2 (aq) + 2Ag(s)
Its half-reactions are
Cu → Cu2+ + 2e−
2Ag + (aq) + 2e− → 2Ag(s)
4.4.3 Oxidation number
the formation of nonionic compounds such as hydrogen chloride (HCl) and sulfur
dioxide (SO2 ):
H2 (g) + Cl2 (g) → 2HCl(g)
48
S(s) + O2 (g) → SO2 (g)
Because HCl and SO2 are molecular compounds, no electrons are transferred in their
formation of these compounds
Chemists find it convenient to treat these reactions as redox reactions because
experimental measurements show that there is a partial transfer of electrons (from H to
Cl in HCl and from S to O in SO2 )
To keep track of electrons in redox reactions, it is useful to assign oxidation numbers
to the reactants and products. An atom’s oxidation number, also called oxidation state,
signifies the number of charges the atom would have in a molecule (or an ionic
compound) if electrons were transferred completely
For example, we can rewrite the previous equations for the formation of HCl and SO2
as follows:
0 0 +1 -1
H2 (g) + Cl2 (g) → 2HCl(𝑔)
0 0 +4 -2
S(s) + O2 (g) → SO2 (g)
The numbers above the element symbols are the oxidation numbers
In both reactions shown, there is no charge on the atoms in the reactant molecules.
Thus, their oxidation number is zero
For the product molecules, however, it is assumed that complete electron transfer has
taken place and that atoms have gained or lost electrons.
The oxidation numbers reflect the number of electrons “transferred”
Oxidation numbers enable us to identify elements that are oxidized and reduced at a
glance
The elements that show an increase in oxidation number, hydrogen and sulfur are
oxidized, so their oxidation numbers increase
The elements that show a decrease in oxidation number, chlorine and oxygen are
reduced, so their oxidation numbers decrease
Note that the sum of the oxidation numbers of H and Cl in HCl (+1 and −1) is zero and
the sum of the oxidation numbers of S and two atoms of O [+4 and 2 × (−2)] is zero
4.4.4 Rules to assign oxidation numbers
1) In free elements (that is, in the uncombined state), each atom has an oxidation number
of zero
2) For ions composed of only one atom (that is, monatomic ions), the oxidation number
is equal to the charge on the ion
3) All metallic elements have only positive oxidation numbers, whereas nonmetallic
elements may have either positive or negative oxidation numbers
4) All alkali metals have an oxidation number of +1 and all alkaline earth metals have an
oxidation number of +2 in their compounds. Aluminum has an oxidation number of +3
in all its compounds
5) The oxidation number of oxygen in most compounds (for example, MgO and H2 O) is
+2, but −1 in hydrogen peroxide (H2 O2 ) and peroxide ion (O−22 )
6) The oxidation number of hydrogen is +1, but −1 when it is bonded to metals in binary
compounds. In these cases (for example, LiH, NaH, 𝐶𝑎𝐻2)
7) Fluorine has an oxidation number of −1 in all its compounds. Other halogens (Cl, Br,
and I) have negative oxidation numbers when they occur as halide ions in their
49
compounds. When combined with oxygen, for example in oxoacids and oxoanions,
they have positive oxidation numbers
8) In a neutral molecule, the sum of the oxidation numbers of all the atoms must be zero.
In a polyatomic ion, the sum of oxidation numbers of all the elements in the ion must
be equal to the net charge of the ion. For example, in the ammonium ion, 𝑁𝐻4+ , the
oxidation number of N is −3 and that of H is +1. Thus, the sum of the oxidation numbers
is (– 3) + (4 × + 1) = + 1
9) Oxidation numbers do not have to be integers. For example, in the superoxides ion, 𝑂2− ,
1
the oxidation number of O is 2
Example 4.4
Assign oxidation numbers to all the elements in the following compounds and ion:
A) Li2 O B) HNO3 C) Cr2 O2−
7
Solution
A) Li = + 1 and O = − 2
B) We can write HNO3 as H +1 Nx O−2 3
(+ 1) + (x) + (3 × −2) = 0
The oxidation number of N = x = + 5
−y
C) We can write 𝐶𝑟2 𝑂72− as [Cr2x O7 ]−2
The oxidation number of O = y = − 2
(2 × x) + (7 × − 2) = − 2
The oxidation number of Cr = x = + 6
Practice exercise 4.4
Assign oxidation numbers to all the elements in the following compound and ion: (a) PF 3 , (b)
MnO4:
A) PF3 B) MnO− 4
4.4.5 Types of redox reactions
Combination reactions: A combination reaction is a reaction in which two or more
substances combine to form a single product. For example:
0 0 +4 -2
S(s) + O2 (g) → SO2 (g)
0 0 +3 -1
2Al(s) + Br2 (𝑙) → 2AlBr3 (s)
Decomposition reactions: A decomposition reaction is the breakdown of a compound
into two or more components. Thy are the opposite of combination reaction. For
example:
+2 -2 0 0
2HgO(s) → 2Hg + O2 (g)
+1 +7 -2 +1 -1 0
2KClO4 (s) → 2KCl(𝑠) + 3O2 (g)
+1 -1 0 0
2NaH(s) → 2Na(s) + H2 (g)
Combustion reactions: A combustion reaction is a reaction in which a substance
reacts with oxygen, usually with the release of heat and light to produce a flame. The
reactions between magnesium and sulfur with oxygen described earlier are combustion
reactions. Another example is the burning of propane (C3 H8 ), a component of natural
gas that is used for domestic heating and cooking:
C3 H8 (g) + 5O2 (g) → 3CO2 (g) + 4H2 O(𝑙)
50
Displacement reactions: A displacement reaction is a reaction in which an ion (or
atom) in a compound is replaced by an ion (or atom) of another element. Displacement
reactions are several subcategories:
1) Hydrogen displacement: All alkali metals and some alkaline earth metals (Ca, Sr,
and Ba), which are the most reactive of the metallic elements, displace hydrogen
from cold water:
0 +1 -1 +1 -2 +1 0
2Na(s) + 2H2 O(𝑙) → 2NaOH(aq) + H2 (g)
0 +1 -1 +2 -2 +1 0
Ca(s) + 2H2 O(𝑙) → Ca(OH)2 (s) + H2 (g)
Also, many metals displace hydrogen from acids:
0 +1 -1 +2 -1 0
Zn(s) + 2HCl(aq) → ZnCl2 (aq) + H2 (g)
0 +1 -1 +2 -1 0
Mg(s) + 2HCl(aq) → MgCl2 (aq) + H2 (g)
2) Metal displacement: A metal in a compound can be displaced by another metal in
the elemental state. An easy way to predict whether a metal or hydrogen
displacement reaction will occur is to refer to an activity series (the
electrochemical series):
According to this series, any metal above hydrogen will displace it from water or
from an acid, but metals below hydrogen will not react with either water or an acid.
In fact, any metal listed in the series will react with any metal (in a compound)
below it. For example, Zn is above Cu, so zinc metal will displace copper ions from
copper sulfate. For example:
Vanadium is obtained by treating vanadium oxide with metallic calcium:
+5 -2 0 0 +2 -2
V2 O5 (s) + 5Ca(l) → 2V(l) + 5CaO(s)
Ca is above V. Ca reduces V +5 in V2 O5 to V
51
Titanium is obtained from titanium(IV) chloride according to the reaction
+4 -1 0 0 +2 -1
TiCl4 (s) + 2Mg(𝑙) → Ti(s) + 2MgCl2 (𝑙)
Mg is above Ti. Mg reduces Ti+4 in TiCl4 to Ti
3) Halogen displacement: The halogens as a group are the most reactive of the
nonmetallic elements. They are all strong oxidizing agents. As a result, they are
found in nature in the combined state (with metals) as halides and never as free
elements. Activity series of the halogens’ in halogen displacement reactions is as
follows:
F2 > Cl2 > Br2 > I2
F2 is the strongest oxidizing halogen and I2 is the weakest oxidizing halogen. For
example, F2 can replace Cl− , Br − or I − in their solutions as shown below:
0 +1 -1 +1 -1 0
Cl2 (g) + 2KBr(aq) → 2KCl(aq) + Br2 (𝑙)
0 -1 -1 0
Cl2 (g) + 2Br − (aq) → 2Cl− (aq) + Br2 (𝑙)
0 +1 -1 +1 -1 0
Cl2 (g) + 2NaI(aq) → 2NaCl(aq) + I2 (s)
0 -1 -1 0
− −
Cl2 (g) + 2I (aq) → 2Cl (aq) + I2 (s)
0 -1 -1 0
− −
Br2 (𝑙) + 2I (aq) → 2Br (aq) + I2 (s)
4) Disproportionation reactions: In a disproportionation reaction, an element in one
oxidation state is simultaneously oxidized and reduced. One reactant in a
disproportionation reaction always contains an element that can have at least three
oxidation states. The element itself is in an intermediate oxidation state; that is, both
higher and lower oxidation states exist for that element in the products. The
following are examples:
+1 -1 +1 -2 0
2H2 O2 (aq) → 2H2 O(l) + O2 (g)
0 -1 +1 +1 -2 -1 +1 -2
Cl2 (g) + 2OH − (aq) → 2ClO− (aq) + Cl− (aq) + H2 O(s)
Example 4.5
Classify the following redox reactions and indicate changes in the oxidation numbers of the
elements:
A) 2N2 O(g) → 2N2 (g) + O2 (g)
B) 6Li(g) + N2 (g) → 2Li3 N(s)
C) Ni(s) + Pb(NO3 )2 (aq) → Pb + Ni(NO3 )2 (aq)
D) 2NO2 (g) + H2 O(𝑙) → HNO2 (aq) + HNO3 (aq)
Solution
A) This is a decomposition reaction because one reactant is converted to two different products.
The oxidation number of N changes from +1 to 0, while that of O changes from −2 to 0.
B) This is a combination reaction (two reactants form a single product). The oxidation number
of Li changes from 0 to +1 while that of N changes from 0 to −3.
C) This is a metal displacement reaction. The Ni metal replaces (reduces) the Pb2+ ion. The
oxidation number of Ni increases from 0 to +2 while that of Pb decreases from +2 to 0.
D) The oxidation number of N is +4 in NO2 and it is +3 in HNO2 and +5 in HNO3 .Because the
oxidation number of the same element both increases and decreases, this is a
disproportionation reaction.
52
Practice exercise 4.5
Identify the following redox reactions by type:
A) Fe + H2 SO4 → FeSO4 + H2
B) S + 3F2 (aq) → SF6
C) 2CuCl → Cu + CuCl2 (aq)
D) 2Ag + PtCl2 → 2AgCl + Pt
4.5 Concentration of solutions
The concentration of a solution is the amount of solute present in a given amount of
solvent, or a given amount of solution
The concentration of a solution can be expressed in different ways
Here we will consider one of the most commonly used units in chemistry, molarity
(M), or molar concentration, which is the number of moles of solute per liter of
solution:
moles of solvent
moloarity =
liters of solution
nsolte
M =
Vsolution (L)
A 1.46 molar glucose (C6 H12 O6) solution, written as 1.46 M C6 H12 O6 , contains 1.46
moles of glucose in 1 L of the solution. Of course, we do not always work with solution
volumes of 1 L. Thus, a 500-mL solution containing 0.73 mole of glucose also has a
concentration of 1.46 M
0.73 mole of glucose
M = = 1.46 M C6 H12 O6
0.5 L
When a sample of (KCl) is dissolved in enough water to make a 1 M solution:
H2 O
KCl(s) → K + (aq) + Cl− (aq)
Because KCl is a strong electrolyte, it is completely dissociated in solution. Thus, a 1
M KCl solution contains 1 mole of K + and 1 mole of Cl− , and no KCl units are present.
The molarity can be expressed using square brackets [ ]. Therefore, [K + ] = 1 M and
[Cl− ] = 1 M.
When a sample of (Ba(NO3 )2 ) is dissolved in enough water to make a 1 M solution:
H2 O
Ba(NO3 )2 → Ba2+ (aq) + 2NO− 3 (aq)
Because Ba(NO3 )2 is a strong electrolyte, it is completely dissociated in solution. Thus,
a 1 M Ba(NO3 )2 solution contains 1 mole of K + and 2 moles of NO− 3 , and no Ba(NO3 )2
units are present. The molarity can be expressed using square brackets [ ]. Therefore,
[Ba2+ ] = 1 M and [NO3− ] = 2 M.
The procedure for preparing a solution of known molarity is as follows:
First, the solute is weighed and transferred to a volumetric flask through a funnel.
Next, water is added to the flask the is carefully swirled to dissolve the solid
After all the solid has dissolved, more water is added slowly to bring the level of
solution exactly to the volume mark
Knowing the volume of the solution in the flask and the number of moles dissolved,
we can calculate the molarity of the solution
Example 4.6
Calculate the mass, in grams, of potassium dichromate K 2 Cr2 O7 required to prepare a 250 mL
of a its solution in water whose concentration is 2.16 M?
53
Solution
n
M = V solte (L)
solution
nK2 Cr2 O7 = M × Vsolution (L) = 2.16 M × 0.25 L = 0.54 mol K 2 Cr2 O7
g
mK2 Cr2 O7 = nK2 Cr2 O7 × MK2 Cr2 O7 = 0.54 mol × 294.2 mol = 159 g
Practice exercise 4.6
Calculate the molarity of an 85.0-mL ethanol (C2 H5 OH) solution containing 1.77 g of ethanol?
Example 4.7
Calculate the volume, in mL, of a solution of 3.81 g of glucose in water if the solution molarity
g
equals 2.53 M. (molar mass og glucose = 180.2 mol)
Solution
msolte 3.81 g
g
nsolte Msolte 180.2
mol
V = = = mol = 0.00836 L = 8.36 mL
M M 2.53
L
Practice exercise 4.7
Calculate the volume, in mL, of a 0.315 M NaOH solution containing 6.22 g of NaOH?
Dilution law:
initial moles of slute = final moles of slute
Minitial × Vinitial = Mfinal × Vfinal
Solutions stored in laboratories stock rooms are very concentrated solutions. We
dilute these “stock” solutions to perform experiments
Dilution is the procedure for preparing a less concentrated solution from a more
concentrated one
Suppose that we want to prepare 1 L of a 0.400 M KMnO4 solution from a solution
of 1.00 M KMnO4
Minitial × Vinitial = Mfinal × Vfinal
1 M × Vinitial = 0.4 M × 1 L
0.4 M × 1 L
Vinitial = = 0.4 L
1M
We need to take 0.400 mL of the 1.00 m KMnO4 and dilute it to 1000 mL by water
This method gives us 1 L of the desired solution of 0.400 M KMnO4
Example 4.8
Describe how you would prepare 500 mL of a 1.75 M H2 SO4 solution, starting with an 8.61 M
stock solution of H2 SO4 .
Solution
Minitial × Vinitial = Mfinal × Vfinal
8.61 M × Vinitial = 1.75 M × 500 mL
1.75 M× 500 mL
Vinitial = = 102 mL
8.61 M
Thus, we must take 102 mL of the 8.61 M H2 SO4 solution and dilute it with water to 500 mL.
Practice exercise 4.8
How would you prepare 200 mL of a 0.866 M NaOH solution, starting with a 5.07 M stock
solution?
4.6 Gravimetric analysis
Gravimetric analysis is an analytical technique based on the measurement of mass
54
One of the famous gravimetric analysis experiment involves the formation, isolation,
and mass determination of a precipitate of an ionic compound
A sample an ionic compound of unknown composition is dissolved in water and
allowed to react with another ionic compound to form a precipitate
The precipitate is filtered off, dried, and weighed
Knowing the mass and chemical formula of the precipitate formed, we can calculate
the mass of the particular chemical component (the anion or cation) of the original
sample
From the mass of the component and the mass of the original sample, we can
determine the percent composition by mass of the component in the original
compound
A reaction that is often studied in gravimetric analysis is:
AgNO3 + NaCl(aq) → NaNO3 + AgCl(s)
Ag + (aq) + Cl− (aq) → AgCl(s)
Let us imagine that we know that the elements which constitute table salt are Na and
Cl but we do not know their mass percentage and consequently do not know how many
Na atom and Cl atom in each unit of the table salt. This means that we imagine that we
do not know that the chemical formula of table salt is NaCl or Na2 Cl2 or any other
If we add an excess mass of AgNO3 to a table salt solution we insure that all Cl in
table salt solution will produce silver chloride as a precipitate (solid)
We know that formula of silver chloride is AgCl. Therefore, the mass percent of
Ag in AgCl can be simply calculated, then the mass of Ag in AgCl can be calculated
Subtraction of Ag mass from the mass of AgCl gives the mass of Cl present in the
original mass of table salt, and subtraction of this mass of Cl from the original mass
of table salt gives us the mass of Na in the reacted table salt
Knowing masses of Na and Cl in a given mass of table salt enables us to calculate the
mass percentage of both Na and Cl in the salt
Example 4.9
A 0.5662-g sample of an ionic compound containing chloride ions and an unknown metal is
dissolved in water and treated with an excess of AgNO3 . If 1.0882 g of AgCl precipitate forms,
what is the percent by mass of Cl in the original compound?
Solution
g g
Molar massCl = 35.45 mol and Molar massAgCl = 143.4 mol
Therefore, the percent by mass of Cl in AgCl is given by:
g
35.45
mol
Cl% in AgCl = g × 100 = 24.72%
143.4
mol
mass of Cl in AgCl = 0.2472 × 1.0882 g = 0.2690 g
0.2690 g
Cl% in the compound = 0.5662 g × 100 = 47.51%
Practice exercise 4.9
A sample of 0.3220 g of an ionic compound containing the bromide ion (Br − ) is dissolved in
water and treated with an excess of AgNO3 . If the mass of the AgBr precipitate that forms is
0.6964 g, what is the percent by mass of Br in the original compound?
4.7 Acid-base titration
Acid-base titration is a technique used for quantitative studies of acid-base
neutralization reactions
55
In titration, a solution of accurately known concentration, called a standard solution,
is added gradually to another solution of unknown concentration, until the chemical
reaction between the two solutions is complete
If we know the volumes of the standard and unknown solutions used in the titration,
along with the concentration of the standard solution, we can calculate the
concentration of the unknown solution
The procedure for the titration is shown in the figure below
In acid-base titrations, indicators are substances that have distinctly different colors in
acidic and basic media
One commonly used indicator is phenolphthalein, which is colorless in acidic and
neutral solutions but reddish pink in basic solutions
At the equivalence point, all the KHP present has been neutralized by the added NaOH
and the solution is still colorless
However, if we add just one more drop of NaOH solution from the burette, the solution
will immediately turn pink because the solution is now basic. Example 4.10 illustrates
Suppose we wanted to use a diprotic acid such as H2 SO4 for the titration:
2NaOH(aq) + H2 SO4 (aq) → Na2 SO4 (aq) + 2H2 O(𝑙)
Because 2NaOH(aq) ≡ H2 SO4 (aq), we need twice as much NaOH to react
completely with a H2 SO4 solution of the same molar concentration. On the other hand,
we would need twice the amount of HCl to neutralize a Ba(OH)2 solution compared to
a NaOH solution having the same concentration and volume because 1 mole of
Ba(OH)2 yields 2 moles of OH − ions:
2HCl(aq) + Ba(OH)2 (aq) → Ba(Cl)2 (aq) + 2H2 O(𝑙)
In calculations involving acid-base titrations, regardless of the acid or base that takes
place in the reaction, keep in mind that the total number of moles of H + ions that have
reacted at the equivalence point must be equal to the total number of moles of OH −
ions that have reacted.
Example 4.10
How many milliliters (mL) of a 0.610 M NaOH solution are needed to neutralize 20.0 mL of a
0.245 M H2 SO4 solution?
Solution
0.245 mol × 20 mL,solution
nH2 SO4 = = 4.90 × 10−3 mol
1000 mL,solution
Because 1 mol H2 SO4 ≡ 2 mol NaOH, there must be 2 × 4.90 × 10−3 mol of NaOH
56
9.80 × 10−3 mol
volume of NaOH = mol = 0.0161 L = 16.1 mL
0.610
1 L,solution
Practice exercise 4.10
Calculate the volume of a 1.28 M H2 SO4 solution needed to neutralize 60.2 mL of a 0.427 M
KOH solution.
4.8 Redox titration
We can titrate a solution containing an oxidizing agent by a solution containing a
reducing agent
Two common oxidizing agents are potassium permanganate (𝐾𝑀𝑛𝑂4 ) and potassium
dichromate (𝐾2 𝐶𝑟2 𝑂7 )
The following is an example
5Fe2+ + MnO− 4 + 8H
+
→ Mn2+ + 5Fe3+ + H2 O
Example 4.11
A 16.42-mL volume of 0.1327 M KMnO4 solution is needed to oxidize 25.00 mL of FeSO4
solution in an acidic medium. What is the concentration of the FeSO4 solution in molarity? The
net ionic equation is:
5Fe2+ + MnO− 4 + 8H
+
→ Mn2+ + 5Fe3+ + H2 O
Solution
0.1327 mol × 16.42 mL,solution
nKMnO4 = = 2.179 × 10−3 mol
1000 mL,solution
Because 5 mol FeSO4 ≡ 1 mol MnO−
4 , nFeO4 can be calculated:
2.179 × 10−3 mol KMnO4 × 5 mol FeSO4
nFeO4 = = 1.090 × 10−2 mol FeSO4
1 mol KMnO4
1.090 × 10−2 mol FeSO4
molarityFeO4 = 1000 mL,solution = 0.340 M
25 mL,solution ×
1 L,solution
Practice exercise 4.11
How many milliliters of a 0.206 M HI solution are needed to reduce 22.5 mL of a 0.374 M
KMnO4 solution according to the following equation:
10HI + 2KMnO4 + 3H2 SO4 → 5I2 + 2MnSO4 + 2K 2 SO4 + 8H2 O
57
5. GASES
5.1 Substances that exist as gases
We live at the bottom of an ocean of air whose composition by volume is roughly 78%
N2, 21 percent O2, and 1 percent of CO2 and other gases
We will focus on the behavior of substances that exist as gases under normal
atmospheric conditions which are defined as 25 °C and 1 atm (atmosphere)
5.1.1 Elements that exist as gases
All the elements in Group 18, the noble gases except Og, exist as monatomic gases:
He, Ne, Ar, Kr, Xe, Rn
The elements of hydrogen, nitrogen, oxygen, fluorine, and chlorine exist as diatomic
molecules: H2, N2, O2, F2, and Cl2
Ozone is another form of oxygen that exist as triatomic molecules, O3
58
5.2.1 The four important properties in studying gases
The following table gives the four properties of gases that are so important to know while
studying or dealing with gases:
UNITS
PROPERTY SYMBOL
SI Units Non-SI Units
Amount n Mole (mol) --------------
Temperature T Kelvin (K) --------------
Pressure P Pascal (Pa) atm
Volume V 3 Liter (L)
Cubic meter (m )
5.2.2 Atmospheric pressure and standard atmospheric pressure and temperature (STP)
Atmospheric pressure
The pressure of the earth atmosphere is the effect of the force (weight) of the Earth’s
atmosphere on a specified area of the Earth’s surface
If the chosen area on the surface of our Earth that equals 1 m2, there will be above
it a column of air extending all the way up to the far end of the Earth atmosphere
Its height from the sea level is more than from Everest peak (8850 m above sea
level) and less than from the level of the dead sea (423 m below sea level)
59
P×V=n×R×T
R is the gas constant
P×V
=R
n×T
This means that:
P ×V P ×V P ×V
R = n1 × T1 = n2 × T2 = n3 × T3 = …
1 1 2 2 3 3
If we have a gas with n = 1 mole, T = 273 K, P = 101325 Pa = 1 atm it will occupy a
volume (V) that equals 22.4 × 10–3 m3 = 22.4 L. We calculate the value of R as follows:
1) Using the SI units:
101325 Pa × 22.4 × 10−3 m3 Pa m3
R= = 8.314
1 mol × 273 K mol K
Knowing here that:
Pascal unit × Cubic meter unit = Joule unit
The value of R is as follows:
𝐉
R = 8.314 𝐦𝐨𝐥 𝐊
2) Using the non-SI units:
1 atm × 22.4 L atm L
R = 1 mol × 273 K = 0.0821 mol K
𝐚𝐭𝐦 𝐋
R = 0.0821 𝐦𝐨𝐥 𝐊
The main conclusion here is that the numerical value of the gas constant, R, depends
on the units of the gas pressure and volume
5.3.2 Boyle’s law
Boyle’s law is the gas law at constant quantity and temperature: Boyle studied the relation
between the gas pressure and volume when its quantity and temperature are kept constant
(n1 = n2 and T1 = T2 ):
P1 × V1 P2 × V2
=
n ×T1 1n ×T 2 2
P1 × V1 = P2 × V2
P × V = constant
1
P∝V
The figures below show the relationship between the gas P and V at constant n and T.
60
V1 V
= T2
T1 2
V
= constant
T
V∝T
The figure below shows this relation and that the minimum temperature that can be
reached is – 273.16 °C which equals 0 K
61
n1 × T1 = n2 × T2 (at constant P and V)
P1 × V1 P2 × V2
= (at constant T)
n1 n2
P1 P2
=n (at constant V)
n1 × T1 2 × T2
V1 V2
=T (at constant P)
n1 × T1 2
EXAMPLE 5.1
Calculate the pressure (in atm) exerted by 1.82 moles of sulfur hexafluoride gas (SF6) in a steel
vessel of volume 5.43 L at 69.5 °C.
Solution
L atm
n×R×T 1.82 mol × 0.0821 × (69.5 °C + 273) K
K mol
P= = = 9.42 atm
V 5.43 L
Practice Exercise 5.1
Calculate the volume, in L, occupied by 2.12 moles of nitric oxide (NO) at 6.54 atm and 76 °C.
EXAMPLE 5.2
Calculate the volume (in liters) occupied by 7.40 g of NH3 at STP.
Solution
m 7.4 g
n=M= g = 0.435 mol
17.03
mol
L atm
n×R×T 0.435 mol × 0.0821 × 273 K
K mol
V= = = 9.75 L
P 1 atm
Practice Exercise 5.2
What is the volume (in liters) occupied by 49.8 g of HCl at STP?
EXAMPLE 5.3
An inflated helium balloon with a volume of 0.55 L at sea level (1.0 atm) is allowed to rise to a
height of 6.5 km, where the pressure is about 0.40 atm. Assuming that the temperature remains
constant, what is the final volume of the balloon?
Solution
P1 × V1 = P2 × V2
1 atm × 0.55 L = 0.4 atm × V2
V2 = 1.4 L
Practice Exercise 5.3
A sample of Cl2 (g) occupies 946 mL at a pressure of 726 mmHg. Calculate the pressure of the
gas (in mmHg) if the volume is reduced at constant temperature to 154 mL.
EXAMPLE 5.4
A certain lightbulb containing argon gs (Ar) at 1.20 atm and 18 °C is heated to 85 °C at constant
volume. Calculate its final pressure.
Solution
P1 P
= T2
T1 2
1.2 atm P2
1K = 1K
(18 °C + 273 °C) × (85 °C +273 °C) ×
1 °C 1 °C
P2 = 1.48 atm
Practice Exercise 5.4
62
A sample of O2(g) initially at 0.97 atm is heated from 21 °C to 268 °C at constant volume. What
is its final pressure?
EXAMPLE 5.5
A small bubble rises from the bottom of a lake, where the temperature and pressure are 8 °C and
6.4 atm, to the water’s surface, where the temperature is 25 °C and the pressure is 1.0 atm.
Calculate the final volume of the bubble if its initial volume was 2.1 mL.
Solution
P1 × V1 P2 × V2
=
T 1 T 2
6.4 atm × 2.1 mL 1 atm × V2
1K = 1K
(8 °C + 273 °C) × (25 °C + 273 °C) ×
1 °C 1 °C
6.4 atm × 2.1 mL × 298 K
V2 = 281 K ×1 atm
V2 = 14.3 mL
Practice Exercise 5.5
A gas initially at 4.0 L, 1.2 atm, and 66 °C undergoes a change so that its final volume and
temperature are 1.7 L and 42 °C. What is its final pressure? Assume the number of moles
remains unchanged.
5.4 The relation between the gas density and molar mass
From the gas law, P × V = n × R × T, and from the equation “m= n × M” we can relate
the gas density to its molar mass:
m m
P×V=M×R×T and P×M= V ×R×T
P×M=d×R×T
Unlike molecules in liquids and solids, gaseous molecules are separated by distances
that are large compared with their size. Consequently, the density of gases is very small
g g
and are expressed in grams per liter (L) rather than in grams per milliliter (mL)
EXAMPLE 5.6
Calculate the density of carbon dioxide (CO2) in grams per liter (g/L) at 0.990 atm and 55 °C.
Solution
P×M=d×R×T
0.99 atm × 44.1 g/mol = d × 0.0821 atm L/mol K × (55 °C + 273) K
d = 1.62 g/L
Practice Exercise 5.6
What is the density (in g/L) of uranium hexafluoride (UF6) at 779 mmHg and 62 °C?
EXAMPLE 5.7
A chemist has synthesized a greenish-yellow gaseous compound of chlorine and oxygen and
finds that its density is 7.71 g/L at 36 °C and 2.88 atm. Calculate the molar mass of the
compound.
Solution
To calculate gas molar mass, we need the density, temperature and pressure.
P×M=d×R×T
2.88 atm × M = 7.71 g/L × 0.0821 atm L/mol K × (36 °C + 273) K
M = 67.9 g/mol
Practice Exercise 5.7
63
The density of a gaseous compound is 3.38 g/L at 40 °C and 1.97 atm. What is its molar mass?
EXAMPLE 5.8
Chemical analysis of a gaseous compound showed that it contained 33.0% by mass silicon (Si)
and 67.0% by mass fluorine (F). At 35 °C, 0.210 L the compound pressure is 1.70 atm. If the
mass of 0.210 L of the compound was 2.38 g, calculate the molecular formula of the compound.
Solution
First, we find the empirical formula and its molar mass
Si : F
33 g 67 g
g : g
28.09 19
mol mol
1.17 mol : 3.53 mol
1.17 mol 3.53 mol
: 1.17 mol
1.17 mol
1 : 3
Therefore, the empirical formula is SiF3
Molar mass of the empirical formula SiF3 = 85.09 g/mol
Second, we find the actual molar mass (molar mass of molecular formula)
m
P×M= V ×R×T
2.38 g
1.7 atm × M = 0.21 L × 0.0821 atm L/mol K × (35 °C + 273) K
M = 169 g/mol
Third, we divide actual molar mass by the empirical molar mass,
g
m 169
mol
= g = 1.99 = 2
V 85.09
mol
The molecular formula = 2 × The empirical formula = 2 × SiF3 = Si2F6
Practice Exercise 5.8
A gaseous compound is, by mass, 78.14% boron (B) and 21.86% hydrogen (H) and its pressure
at 27 °C, 74.3 mL is 1.12 atm. If the mass of the gas was 0.0934 g, what is its molecular formula?
5.5 Gas stoichiometry
We show in chapter 3 , (section 3.3), that the method used for calculations on chemical
equations is the “mole method”
Here, we show that, if the reactants and/or products are gases, calculations on chemical
equations can use the “volume method”
Justification for using the volume method for reactions involving gases comes from the
𝐑×𝐓
relationship between “V” of the gas and its “n” at constant T and P, “𝐕 = 𝐏 ” which
that V is becomes constant and is proportional to its number of moles “n”:
R×T
V = n × P AND V ∝ n
Example 5.9
Calculate the volume of O2 (in liters) required for the complete combustion of 7.64 L of
acetylene (C2H2) measured at the same T and P.
2C2H2 (g) + 5O2(g) → 4CO2(g) + 2H2O(l)
Solution
2C2H2 (g) + 5O2(g) → 4CO2(g) + 2H2O(l)
2L 5L
7.64 L Voxyg
64
5 L × 7.64 L
Voxyg = = 19.1 L
2L
Practice exercise 5.9
The equation of the reaction between nitric oxide and oxygen is:
2NO(g) + O2(g) → 2NO2(g)
If 9.0 L of NO reacted with excess O2 at certain T and P, calculate the volume and the
number of moles of the NO2 produced?
Example 5.10
Assuming no change in T and P, calculate the 𝑉𝑂2 (in liters) required for the complete
combustion of 14.9 L of butane (C4H10):
2C4H10 (g) + 13O2(g) → 8CO2(g) + 10H2O(l)
Solution
2C4H10 (g) + 13O2(g) → 8CO2(g) + 10H2O(l)
2L 13 L
14.9 L Voxyg
13 L × 14.9 L
Voxyg = = 96.85 L
2L
Practice exercise 5.10
Sodium azide (NaN3), used in some automobile air bags, decomposes as follows:
2NaN3(g) → 2Na(s) + 3N2(g)
The nitrogen gas produced quickly inflates the bag. Calculate the volume of N2 generated
at 80°C and 823 mmHg by the decomposition of 60.0 g of NaN3.
Example 5.11
The equation for the metabolic breakdown of glucose (C6H12O6) is:
C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(l)
Calculate the volume of CO2 produced at 37 °C and 1.00 atm when 5.60 g of glucose is
used up in the reaction.
Solution
5.6 g
nCO2 = 6 × nC6 H12 O6 = 6 × g = 0.1865 mol
180.156
mol
atm L
n×R×T 0.1865 mol × 0.0821 ×(37 + 273)K
mol K
V= = = 4.75 L
P 1 atm
Practice exercise 5.11
The combustion equation of methane is:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
If 15.0 moles of methane are reacted, calculate the volume of CO2 produced at 23.0 °C
and 0.985 atm?
5.6 Dalton’s law of partial pressures
MOLE FRACTION
Before we discuss this law, we need to know what the term “mole fraction” means.
When more than one substance (for example, two substances “A” and “B”) are present
together, and we know the number of moles of each “nA and nB ”, this means that we
know the total number of moles “nTotal ”.
Now, if we divide nA or nB by nTotal the quotient will have no unit
65
This quotient is the mole fraction of each “XA and XB ”.
Therefore, we write:
𝐧𝐀 𝐧𝐁
𝐗𝐀 = 𝐧 and 𝐗 𝐁 = 𝐧
𝐓𝐨𝐭𝐚𝐥 𝐓𝐨𝐭𝐚𝐥
1) In mixtures of gases, the total gas pressure is related to their partial pressures
2) partial pressure is the pressures of individual gas components in the mixture
3) In 1801, Dalton formulated a law, now known as Dalton’s law of partial pressures,
which states that the total pressure of a mixture of gases is the sum of the pressures that
each gas would exert if it were present alone
4) Consider a case in which two gases, A and B, are in a container of volume V at
temperature T
5) According to the ideal gas equation, the pressure exerted by gas are:
RT RT
PA = nA × V AND PB = nB × V
6) Because the two gases are mixed in the same container at the same temperature, the
total pressure PTotal is:
PTotal = PA + PB
RT RT RT RT
PTotal = (nA × V ) + (nB × V ) = (nA + nB ) × V = nTotal × V
PA nA PB nB
=n = XA AND P =n = XB
PTotal Total Total Total
PA = XA × PTotal AND PB = XB × PTota
EXAMPLE 5.12
A mixture of 4.46 mol of Ne gas, 0.74 mol of Ar gas, and 2.15 mol of Xe gas has a total pressure
of 2.00 atm. What are the partial pressures of each?
Solution
number of total moles of all substances = 4.46 mol + 0.74 mol + 2.15 mol = 7.35 mol
number of moles of the substance
Mole fraction of a substance = number of total moles of all substances
4.46 mol 0.74 mol 2.15 mol
XNe = 7.35 mol = 0.607, XAr = 7.35 mol = 0.1, XXe = 7.35 mol = 0.29
Pressure of any gas in the mixture = its mole fraction × total pressure
PNe = 0.607 × 2 atm = 1.21 atm
PAr = 0.1 × 2 atm = 0.2 atm
PXe = 0.29 × 2 atm = 0.586 atm
Practice Exercise 5.12
A sample of natural gas contains 8.24 moles of methane (CH4), 0.421 mole of ethane (C2H6),
and 0.116 mole of propane (C3H8). If the total pressure of the mixture is 1.37 atm, what are the
partial pressures of each gas?
7) Collecting a gas over water
Frequently, chemists need to collect gases over water
They use a devise like the one below in which oxygen gas is produced from the
decomposition of potassium chlorate (KClO3):
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Potassium chlorate (KClO3) is thermally decomposed:
2KClO3(s) → 2KCl(s) + 3O2(g)
The produced oxygen escapes through the hose immersed in water and a flask is
rises above water surface as shown in the figure
Of course, oxygen will not be alone in the space above water surface; water vapor
too is occupying this space, (They become roommates) and the pressure above
water is the pressure of both:
PTotal = Poxygen + Pwater vapor
EXAMPLE 5.13
O2 (g) generated from potassium chlorate is collected as shown in the previous figure. The
volume above surface became128 mL at 297 K and pressure of 762 mmHg is. Calculate
the mass of KClO3 consumed. The pressure of the water vapor at 297 K is 22.4 mmHg.
Solution
Poxygen = PTotal – Pwater vapor = 762 mmHg – 22.4 mmHg = 740 mmHg
1 atm 1L
P×V 740 mmHg × × 128 mL ×
= 5.11 × 10−5 mol
760 mmHg 1000 mL
n = R×T = atm L
0.0821 × 297 K
mol K
2KClO3 2KCl + 3O2
Equation moles 2 3
Question moles X 5.11 × 10−5
5.11 × 10–5 mol
X = number of mol KClO3 = 2 mol × = 3.41 × 10−5 mol
3 mol
g
Mass of KClO3 = n × M = 3.41 × 10−5 mol × 123.427 mol = 4.21 × 10−5 g
Practice Exercise 5.13
Hydrogen gas generated when calcium metal reacts with water is collected as shown in the
previous figure. The volume of gas collected at 30°C and 988 mmHg is 641 mL. What is
the mass of the H2(g) obtained? The pressure of water vapor at 30°C is 31.82 mmHg.
5.7 The kinetic molecular theory of gases
The gas laws help us to predict their behavior, but they do not explain what happens at
the molecular level to cause the changes we observe in the macroscopic world
It became so clear to physicists and chemists that this macroscopic and sensible
behavior of gases is a reflect of the behavior of its atomic and molecular microscopic
behavior
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In the nineteenth century, several physicists, notably Ludwig Boltzmann and James
Clerk Maxwell, found that the physical properties of gases can be explained in terms
of the motion of individual molecules
This molecular movement is a kinetic energy (KE)
Maxwell, Boltzmann, and others concluded several generalizations about gas behavior
that have since been known as the kinetic molecular theory of gases, or simply the
kinetic theory of gases
5.7.1 The five hypotheses of the theory
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 “points”; that is, they possess
mass, but their volume is negligible
2) Attractive or repulsive forces on one another gas molecule is negligible
3) Gas molecules are in constant motion in random directions
4) Gas molecules collide with one another and with the walls of the container they occupy.
These collisions are perfectly elastic, this means that energy is transferred from one
molecule to another but the total energy of all the molecules remains the same
5) The average kinetic energy of the molecules is proportional to its absolute temperature.
This means that any two equal-quantity gases at the same temperature will have the
same average kinetic energy
The average kinetic energy of a molecule with a mass equals “m” is given by the
following equation:
1
KE = 2 m U 2
U is the speed of the molecule but U 2 is the mean square speed; the bar over U2 means
that it is the average of the square of the speeds of all the molecules and is usually given
the symbol Urms which means the root-mean-square speed of all molecules. The value
of Urms can be obtained using the following equation:
3RT
Urms = √ M
Example 5.14
m
Calculate the root-mean-square speeds of helium atoms and nitrogen molecules in s at 25°C.
Solution
J
3RT 3 × 8.314 × 298 K m
mol K
Urms,He = √M =√ g 1 kg = 1362.6
He 4.003 × s
mol 1000 g
J
3RT 3 × 8.314 × 298 K m
mol K
Urms,N2 = √M =√ g 1 kg = 515.1
N2 28.014 × s
mol 1000 g
68
This equation enables us to calculate the average kinetic energy of only one molecules
“ke” by dividing the equation by Avogadro’s number:
KE R
ke = N = 1.5 × N × 𝑇 = 1.5 × k × T
A A
“k” is Boltzmann constant, Both equations of kinetic energy of one mole or of only one
molecule of the gas, indicate that the kinetic energy of a specified quantity is the
same for all gases if their amounts and temperatures are the same
5.7.2 Application of kinetic theory to the gas laws
Boyle’s Law
The P exerted by a gas results from impacts of its molecules collisions on the walls
The number of collisions with the walls per second is proportional to the number
of molecules per unit volume
Decreasing the volume of the gas increases the number of molecules per unit
volume and hence increases number of collisions
The pressure of a gas is inversely proportional to the volume it occupies.
Charles’s Law
The average kinetic energy of molecules is proportional to its absolute temperature
Increasing the temperature increases the speed, the kinetic energy, the number of
collisions, and the pressure. so, to keep “P” constant the volume of the gas increases
Avogadro’s Law
In Avogadro’s law, the pressure of a gas is directly proportional to the amount of
the gas at constant temperature and pressure
If we increase the amount of the gas the pressure will remain constant only if the
volume increase
Dalton’s Law of Partial Pressures
The pressure of one type of molecule is unaffected by the presence of another type
The total pressure is given by the sum of individual gas pressures.
5.7.3 Distribution of molecular speeds
The average kinetic energy of molecules and the mean square speed remain constant at
constant temperature. How many molecules are moving at particular speed? The
following figure show Maxwell speed distribution curves for nitrogen gas at three
different temperatures:
The peak of any curve represents the most probable speed, that is, the speed of the
largest number of molecules at the specified temperature
The most probable speed increases as temperature increases
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The curve begins to flatten out with increasing temperature, indicating as temperature
increases a larger numbers of molecules are moving at greater speed
The following figure shows the speed distributions of three gases at the same
temperature.
70
Although effusion differs from diffusion in nature, the rate of effusion of a gas has the
same form as Graham’s law of diffusion
A He-filled rubber balloon deflates faster than an air-filled one because the rate of
effusion through the pores is faster for the lhelium atoms than for the air molecules
Third: Graham’s law
In 1832 the Scottish chemist Thomas Graham found that under the same conditions of
temperature and pressure, rates of diffusion for gases (r) are inversely proportional to
the square roots of their molar masses or densities:
r1 M d
= √M2 = √d2
r2 1 1
Example 5.15
A gas made up only of C and H atoms effuses through a porous wall in 1.50 min. Under the
same conditions of T and P, it takes an equal volume of Br2 vapor 4.73 min to effuse through
the same wall. Calculate the molar mass of the unknown gas and suggest its molecular formula.
Solution
r1 M
= √M2
r2 1
V1
V1 V2 Time1 Time M
r1 = Time and r2 = Time but V1 = V2 therefore, V1 = Time2 = √M2
1 2 1 1
Time2
4.73 min 159.808
=√
1.50 min M1
g
M1 = 16.07 mol
g
This gas is methane, because its molar mass is 16.04 mol, and is formed from C and H
Practice exercise 6.15
A gas evolved from the fermentation of glucose effuses through a porous wall in 15.0 min.
Under the same T and P, it takes 12.0 min for an equal volume of N2 to effuse through the same
wall. Calculate the molar mass of the gas and suggest what the gas might be.
5.8 Deviation from ideal behavior
The gas laws and the kinetic molecular theory assume that:
1) Attractive and repulsive forces between molecules of the gas are negligible
2) The volume occupied by the molecules of the gas is negligible
These two assumptions are in fact not true and cannot be accepted except under strict
conditions
When a gas obeys these conditions, it is honored as the “perfect gas” and rewarded
with an equation bearing its name “the perfect gas equation”: P × V = n × R × T
The question now is: “Under what conditions will not real gases exhibit perfect
behavior?”
PV
The following curves shows “RT” plotted against “P” for one mole of each of the four
real gases and the ideal gas all at the same temperature
PV
For the one mole of the ideal gas RT = 1 at all pressures, but for one mole of any of the
PV
the other gases, RT = 1 only at zero or extremely small pressures
Significant deviations occur as pressure increases. The following is the interpretation
to these observations:
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The following is the interpretation to these observations:
Attractive forces operate among molecules at short distances. therefore, at
low pressures the molecules in a gas are far apart and they experience no
attractive or repulsive forces. At high pressures, the molecules are much
closer to one another and intermolecular forces are enough to affect the
motion of the molecules, and the gas will not behave perfectly. This
nonerections is much significant at lower temperature because cooling a
gas decreases the molecules’ average kinetic energy, which makes
molecules movement less freely.
In 1873, the physicist van der Waals studied real gases accurately, he modified the ideal
gas equation to consider intermolecular forces and tiny molecular volumes. The
following is his logic:
1) The intermolecular attractions exerted between a molecule and its neighbors softens
its collisions against the wall which makes the gas pressure lowers than if it is ideal.
To correct thi deviation, resulting from lowering the pressure, a certain correction
𝐧𝟐
value must be added to the real pressure. This value is “a × 𝐕 𝟐”. This means that the
𝐧𝟐
gas pressure must be corrected to be (P + a × 𝐕 𝟐). “a” is constant for each gas, and
it is related to the strength of the forces between its molecules
2) Volume in the perfect gas equation, “V”, represents the volume of the container as
a free space that is occupied by nothing. However, each molecule occupys a finite,
although small, volume, so the effective volume of the gas is less than the volume
of the container by a certain value equals to “n × b”. This means that the gas volume
must be corrected to be (V − n × b). “b” is constant for each gas, and it is related to
the volume occupied by the molecules of the gas.
3) From the previous two corrections the law of the real gas is written as:
n2
(P + a × V2 ) × (V − n × b) = n × R × T
This equation is called the “van der Waals or real gas equation”
4) If the gas is a perfect gas the values of “a” and “b” are zero.
Example 5.16
Given that 3.50 moles of NH3 occupy 5.20 L at 47° C, calculate the pressure of the gas (in
atm) using (A) the ideal gas equation and (B) the van der Waals equation. (a = 4.17 atm
L2/mol2, b = 0.0371 L/mol)
72
Solution
atm L
n×R×T 3.5 mol × 0.0821 × 320 K
mol K
A) P = = = 17.7 atm
V 5.2 L
n×R×T n2
B) P = (V − n × b) – (a × V2 )
atm L
3.5 mol × 0.0821 × 320 K atm L2 (3.5 mol)2
P=( mol K
L ) – (4.17 × ) = 16.2 atm
5.2 L − 3.5 mol × 0.0371 mol2 (5.2 L)2
mol
Practice exercise 5.16
At 27°C, 10.0 moles of a gas in a 1.50-L container exert a pressure of 130 atm. Is this an
ideal gas?
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6. THERMOCHEMISTRY
6.1 The nature of energy and types of energy
Energy is usually defined as the capacity to do work which is “force × distance.
All forms of energy are capable of doing work but not all of them are equally relevant to
chemistry. Thermochemistry is the study of heat transfer in chemical reactions.
6.1.1 Types of energy
Chemists define work as directed energy change resulting from a process. Kinetic
energy, the energy produced by a moving object, is one form of energy that is of interest
to chemists. Others include radiant energy, thermal energy, chemical energy, and
potential energy
Radiant energy, or solar energy, comes from the sun and is Earth’s primary energy
source. Solar energy heats the atmosphere and Earth’s surface, stimulates the
growth of vegetation through photosynthesis, and influences global climate patterns
Thermal energy is the energy associated with the random motion of atoms and
molecules. In general, thermal energy can be calculated from temperature
measurements. The more vigorous the motion of the atoms and molecules in a
sample of matter, the hotter the sample is and the greater its thermal energy. It is
important to understand the distinction between thermal energy and heat. Heat is
the transfer of thermal energy between two bodies that are at different
temperatures. Also, we need to distinguish carefully between thermal energy, heat
and temperature
Chemical energy is stored within the structural units of chemical substances; its
quantity is determined by the type and arrangement of constituent atoms. When
substances participate in chemical reactions, chemical energy is released, stored, or
converted to other forms of energy
Potential energy is energy available by virtue of an object’s position. For instance,
because of its altitude, a rock at the top of a cliff has more potential energy and will
make a bigger splash if it falls into the water below than a similar rock located
partway down the cliff. Chemical energy can be considered a form of potential
energy because it is associated with the relative positions and arrangements of
atoms within a given substance.
All forms of energy can be converted from one form to another
We feel warm when we stand in sunlight because radiant energy is converted to
thermal energy
When we exercise, chemical energy in our bodies is used to produce kinetic energy
When a ball falls downhill, its potential energy is converted to kinetic energy
6.1.2 The law of conservation of energy
Energy can be neither destroyed nor created. When one form of energy disappears, some
other form of energy (of equal magnitude) must appear, and vice versa. This principle is
the law of conservation of energy: the total quantity of energy in the universe is constant
6.2 Energy change in chemical reactions
Combustion reactions involving fuels in daily life aim for heat released more than for
their products, which are water and carbon dioxide
Almost all chemical reactions absorb release energy in the form of heat. We speak of
the “heat flow” from a hot object to a cold one. Although the term “heat” by itself
74
implies the transfer of energy, we customarily talk of “heat absorbed” or “heat
released” when describing the energy changes that occur during a process
6.3 The system the surroundings and the universe
The system, which is the specific part of the universe that is of interest to us. For
chemists, systems usually include substances involved in chemical and physical
changes. For example, in an acid-base neutralization experiment, the system may be a
beaker containing 50 mL of HCl to which 50 mL of NaOH is added
The surroundings which are the rest of the universe outside the system
There are three types of systems:
An open system can exchange mass and energy, usually in the form of heat with its
surroundings. For example, an open system may consist of a quantity of water in
an open container
A closed system can exchange mass with its surroundings but not energy. For
example, a closed system may consist of a quantity of water in a closed container
that does not allow any substance to leave or enter but may absorb or release heat
An isolated system cannot exchange mass and energy with its surroundings. For
example, an isolated system may consist of a quantity of water in an isolated
container that does not allow any substance or energy to leave or enter
Chemical reactions either release or absorb energy. examples are:
2H2(g) + O2(g) → 2H2O(l) + energy
energy + 2HgO(s) → 2Hg(l) + O2(g)
6.4 Introduction to thermodynamics
6.4.1 Work and heat
First work
Work is many kinds (mechanical work, electrical work, surface work) and others
Work is a way of transferring energy from a place to another. It is not a property of the
system. We can say: the temperature of a substance is 25° C, but we cannot say: the
work of the system is 250 J
We will concentrate only on the work of expansion and compression of gases
The work done by or on the gas is given by the following equation:
w = – P × (Vfinal – Vinitial)
w = – P × ΔV
The negative sign is to make the sign of work negative in cases of expansion and
positive in cases of compression
Units of the PV-work:
units of w = Pascal × m3 = kg m–1 s–2 × m3 = kg m2 s–2 = J
units of w = atm × L = atm L
1 atm L = 101.325 J
The figure below shows a gas in a cylinder fitted with a weightless, frictionless movable
piston at a certain temperature, pressure, and volume. The gas expanded against a
constant opposing external atmospheric pressure.
The work done by the gas has a negative quantity indicating that its energy is decreased
The work done on the gas has a negative quantity indicating that its energy is increased
75
EXAMPLE 6.1
A gas expands from 2.0 L to 6.0 L at constant T. Calculate “w” if the expansion is against:
A) a vacuum B) a constant pressure of 1.2 atm
Solution
A) w = – PΔV = – (0 × ΔV) = 0
Pa m3
B) w = – PΔV = – {1.2 atm × 101325 } × {(6 – 2) L } = – 4.86 × 10–2 J
atm 1000 L
Practice Exercise 6.1
A gas expands from 264 mL to 971 mL at constant temperature. Calculate the work done by the
gas if it expands against a constant pressure of 4.00 atm.
Second: Heat
Heat is a way of transferring energy from a place to another. It is not a property of the
system. We can say: the temperature of a substance is 25° C, but we cannot say: the
heat of the system is 250 J
For example, it takes 4184 J of energy to raise the temperature of 100 g of water from
20°C to 30°C. This energy can be gained in different ways such as:
Directly as heat energy from burner, without doing any work
By work as in stirring the water with a magnetic stir bar
By some combination of the procedures described in above
Heat needed to increase the substance temperature defers from substance to another,
for the same substance it depends on its mass, and and for the same mass of the same
substance it depends on number of Celsius (or Kelvin) degrees is to be increased
First: specific heat (s)
The specific heat of a substance is the quantity of heat required to raise the
J
temperature of one gram of the substance by one degree Celsius. Its units are g °C.
The specific heat of a substances are measured, calculated and listed in tables
Second: heat capacity (C)
The heat capacity of a substance is the quantity of heat required to raise the
temperature of any given mass, (m), of the substance by one degree Celsius. Its
J
units are °C. The relationship between the heat capacity and the specific heat of is:
C=m×s
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Third: quantity of heat (q)
The quantity of heat is the amount of heat required to raise the temperature of any
given mass, (m), of the substance by any Celsius degrees. Its unit is J. The
equation relating the quantity of heat, heat capacity and the specific heat is:
q = C × Δt = m × s × Δt
EXAMPLE 6.2
A sample of water has a mass equals to 466 g is heated from 8.50 °C to 74.60 °C. Calculate the
𝐉
amount of heat absorbed (in kilojoules) by the water. (𝐬𝐇𝟐 𝐎 = 4.184 𝐠 °𝐂)
Solution
J
q = m × s × Δt = 466 g × 4.184 g °C × (74.60 °C – 8.50 °C) = 129000 J
1 kJ
q = 129000 J × 1000 J = 129 kJ
Practice Exercise 6.2
An iron bar (s = 0.45 J/g °C) of mass 869 g cools from 94°C to 5°C. Calculate the heat released
(in kilojoules) by the metal.
6.4.2 The first law of thermodynamics
The first law of thermodynamics is based on the law of conservation of energy:
“energy can be converted from one form to another but cannot be created or destroyed”
The change in internal energy, ΔE, is given by the following equation:
ΔE = Efinal – Einitial
where Einitial and Efinal are the initial and the final internal energies of the system
ΔE may be positive, negative or zero
The internal energy of a system has two components:
1) The kinetic energy component which consists of various types of molecular
motion and the movement of electrons within molecules
2) The potential energy component which is determined by the attractive
interactions between electrons and nuclei, the repulsive interactions between
electrons and by interaction between molecules
Internal energy of a system cannot be determined but changes in internal energy can be
The first law of thermodynamic is:
ΔE = q + w
The sign conventions for "q" and "w" are as follows:
q is positive for an endothermic process but negative for an exothermic process
w is positive for work done on the system by the surroundings but negative if done
by the system on the surroundings
Internal energy is a property of the system and therefore is a state function
Heat and work are not properties of a system and therefore are not state functions
EXAMPLE 6.3
If the work done on a gas is 462 J and the heat released by the gas is 128 J, calculate the change
in the gas internal energy.
Solution
ΔE = q + w = (–128 J) + (+ 462 J) = + 334 J
Practice Exercise 6.3
A gas expands and does P-V work on the surroundings equal to 279 J. At the same time, it
absorbs 216 J of heat from the surroundings. What is the change in energy of the system?
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6.5 Enthalpy of chemical reactions
The heat absorbed or released by a system, at constant temperature, as result of a change
in the state of the system is called heat of reaction:
If also the volume is constant, it is named “change in internal energy” (ΔE)
If also the pressure is constant, it is named “change enthalpy” (ΔH)
Our concern is about changes in enthalpy rather than changes in internal energy
For any reaction of the type:
Reactants products
Enthalpy of reaction is:
ΔH = Hproducts – Hreactants
There is no way to measure t Hproducts and Hreactants and we do not need to know its value
because what we care about only is the increase or decrease in its value, (ΔH)
For an endothermic process, ΔH is positive (ΔH > 0)
For an exothermic process ΔH is negative (ΔH < 0)
6.6 Thermochemical equations
At 0°C and a pressure of 1 atm, ice melts to form liquid water
H2O(s) H2O(l) ΔH = 6.01 kJ
That is, 6.01 kJ of heat must be absorbed to covert 1 mole of ice to 1 mole of liquid
water at constant temperature and pressure
Another example is the combustion of methane (CH4) at constant T and P:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l). ΔH = – 2890.4 kJ
That is 2980 kJ of heat must be released to as a result of combusting 1 mole of methane
ΔH value does not refer to a reactant or a product. But all the following are true for the
previous reaction:
1) ΔH = – 2890.4 kJ/ mol CH4
2) ΔH = – 2890.4 kJ/ 2 mol O2
3) ΔH = – 2890.4 kJ/ mol CO2
4) ΔH = – 2890.4 kJ/ 2 mol H2O
5) ΔH = – 2890.4 kJ
A thermochemical equation cannot be called so unless it satisfies the following:
1) It must be balanced
2) The states of all substances must be specified
3) The value of ΔH must be written
Thermochemical equations can be manipulated with as follows:
1) Multiplying a thermochemical equation by a number or a fraction gives a correct
thermochemical equation only if the value of ΔH is multiplied by the same number
2) Reversing a thermochemical equation gives a correct thermochemical equation if
the sign of ΔH is changed to its opposite
3) Adding several thermochemical equations together gives a correct thermochemical
equation if all values of ΔH are added together (This is called Hess’s law).
EXAMPLE 6.4
Given the thermochemical equation
2SO2(g) + O2 (g) 2SO3(g) ΔH = –198.2 kJ
calculate the heat evolved when 87.9 g of SO2 (molar mass = 64.07 g/mol) is converted to SO3.
Solution
78
87.9 g
Given moles of SO2 = g = 1.372 mol
64.07
mol
2SO2 + O2 2SO3 ΔH
Equation moles 2 mol − 198.2 kJ
Givnen moles 1.372 mol X
− 198.2 kJ × 1.372 mol SO2
X= = – 135.97 kJ
2 mol SO2
Practice Exercise 6.4
Calculate the heat released when 266 g of phosphorus (P4) burns in air according to the equation
P4(s) + 5O2(g) P4O10(s) ΔH = – 3013 kJ/mol
6.7 Relationship between ΔH and ΔE
We know that:
ΔE = ΔH – P × ΔV
ΔE = ΔH – R × T × Δng
It is very important not to forget that the subscript “g” is to emphasize that when
calculating Δn only gases count:
Δng = ngases produced – ngases reacted
Let’s consider the reaction between sodium metal and water at 1 atm and 298 K is:
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g) ΔH = – 367.5 kJ
When 2 moles of solid Na react with 2 moles of liquid water, 367.5 kJ of heat
is released
H2 gas produced needs a space to occupy. Therefore, it pushes the air toward
the atmosphere which means that some of heat produced is used to do work,
against atmospheric pressure, P
To calculate the change in internal energy, we apply the previous equation:
ΔE = ΔH +w = ΔH – R × T × Δng
kJ
ΔE = (– 367.5 kJ) – (8.314 × 10–3 mol K × 298 K × 1 mol) = – 369.98 kJ
EXAMPLE 6.5
Calculate ΔE for the following reaction at 1 atm and 25°C:
2CO(g) + O2(g) 2CO2(g) ΔH = – 566.0 kJ
Solution
ΔE = ΔH – R × T × Δng
Δng = (2 mol) – (3 mol) = – 1 mol
kJ
ΔE = (– 566.0 kJ) – (8.314 × 10–3 mol K × 298 K × – 1 mol) = – 563.5 kJ
Practice Exercise 6.5
What is ΔE for the formation of 1 mole of CO at 1 atm and 258C?
1
C(graphite) + 2O2(g) CO(g) ΔH = –110.5 kJ
6.8 Calorimetry
calorimetry is the measurement of heat changes and a calorimeter is a closed container
designed specifically for determining ΔH
Constant-volume calorimetry
Constant-volume bomb calorimeter is an isolated steel container (a bomb) we put
inside the substance that we need to determine its enthalpy of combustion, and is
filled by oxygen gas
79
The isolated bomb is immersed in a known amount of water, and the sample is
ignited electrically
The heat produced by the combustion reaction can be calculated accurately by
recording the rise in temperature of the water
Because the heat is released at constant volume:
q v = ΔE
We can calculate ΔH using the equation “ΔH = ΔE + R × T × Δng”
q v = − q calorimeter = − Ccalorimeter × 𝛥T:
Ccalorimeter is the heat capacity of the bomb and the water around and it is given
𝛥T is the rise in temperature which the thermometer reads
EXAMPLE 6.6
A quantity of 1.435 g of naphthalene (C10H8) was burned in a constant-volume bomb calorimeter.
The temperature of the water rose from 20.28 °C to 25.95 °C. Calculate the molar heat of combustion
of naphthalene.
(Heat capacity of the bomb plus water = 10.17 kJ/°C), (molar mass of naphthalene = 128.2 g/mol)
Solution
q v = Cv × ΔT
kJ kJ
q v = − q calorimeter = − 10.17 °C × (25.95 °C − 20.28 °C) = − 57.66 1.435 g
kJ g kJ
q v = = − 57.66 × 128.2 = − 5151
1.435 g mol mol
Practice Exercise 6.6
A quantity of 1.922 g of methanol (CH3OH) was burned in a constant-volume bomb calorimeter. The
temperature of the water rose by 4.20 °C. Calculate the molar heat of combustion of methanol.
(Heat capacity of the bomb plus water = 10.4 kJ/°C), (molar mass of methane = 32 g/mol)
Constant-pressure calorimetry
The constant-pressure calorimeter is used to determine the heat changes for
noncombustion reactions
80
A crude constant-pressure calorimeter can be constructed from two Styrofoam
coffee cups
Because the pressure is constant, the heat change for the process is equal to the
enthalpy change (ΔH)
The calorimeter as an isolated system and we neglect the small heat capacity of the
coffee cups in our calculations. Table 6.3 lists some reactions that have been studied
with the constant-pressure calorimeter.
EXAMPLE 6.7
A lead (Pb) pellet having a mass of 26.47 g at 89.98°C was placed in a constant-pressure calorimeter
of negligible heat capacity containing 100.0 mL of water. The water temperature rose from 22.50°C
to 23.17°C. What is the specific heat of the lead pellet?
Solution
q water = Cwater × ΔT = swater × mwater × ΔTwater
J
q water = 4.184 g °C × 100 g × (23.17 °C − 22.50 °C) = 280.3 J
q lead = Clead × ΔT = slead × mlead × ΔTwater
− 280.3 J = slead × 26.47 g × (23.17 °C − 89.98 °C) = 280.3 J
J
slead = 0.158 g °C
Practice Exercise 6.7
A stainless steel-ball with mass of 30.14 g at 117.82°C was placed in a constant-pressure calorimeter
of negligible heat capacity containing = 120.0 mL of water at 18.44°C. If the specific heat of the ball
J
is 0.474 g °C, calculate the final temperature of the water.
EXAMPLE6.8
A 100 mL of 0.5 M HCl was mixed with 100 mL of 0.500 M NaOH in a constant-pressure calorimeter
of negligible heat capacity. The initial temperature of both solutions was the same at 22.50°C, and
the final temperature of the mixed solution was 25.86°C. Calculate the heat change for the
neutralization reaction on a molar basis:
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)
81
Assume that the densities and specific heats of the solutions are the same as for water (1.00 g/mL
and 4.184 J/g °C, respectively).
Solution
𝐻 + (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞) + 𝑁𝑎 + (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞) → 𝑁𝑎+ (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞) + 𝐻2 𝑂(𝑙)
𝐻 + (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞) → 𝐻2 𝑂(𝑙)
q reaction = − q solution = − ssolution × msolution × ΔTsolution
J
q reaction = − 4.184 × (100 g + 100 g) × (25.86 °C − 22.50 °C) = − 2810 J
g °C
0.5 mol ×0.1 L
Number of mles of HCl = Number of mles of NaOH = = 0.05 mol
1L
− 2810 J J kJ
Heat of neutralization = = − 56200 = − 56.200
0.05 mol mol mol
kJ
𝐻 + (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞) → 𝐻2 𝑂(𝑙)∆H = − 56.200 mol
Practice Exercise 6.8
A 400 mL of 0.6 M HNO3 was mixed with 400 mL of 0.3 M Ba(OH)2 in a constant-pressure
calorimeter of negligible heat capacity. The initial temperature of both solutions is the same at
18.46°C. What is the final temperature of the solution? Assume that the densities and specific heats
of the solutions are the same as for water (1.00 g/mL and 4.184 J/g °C, respectively)
6.9 Standard enthalpy of formation and reaction
A formation reaction is the reaction in which one substance is produced as a result of
the reaction of its elements in their standard states
The quantity of heat released or absorbed at standard pressure (1 atm) because of the
formation of one mole of a substance from the reaction between its elements in their
standard states is called standard molar enthalpy of formation (Δ𝐇𝐟° )
This means that if the substance we have is an element in its standard state, it has no
formation reaction. Therefore, its standard enthalpy of formation equals zero.
When any element is in its standard state its Δ𝐇𝐟° = 0
The following reaction equations are examples of formation reactions:
S(s) + O2(g) SO2(g) ΔH = – 296.84 kJ
1
Mg(s) + 2O2(g) MgO(g) ΔH = – 601.6 kJ
(Note: both reactions can also be called a combustion reaction)
1
2C(graphite) + 3H2(g) + 2O2(g) CH3CH2OH(l) ΔH = – 277.6 kJ
3C(graphite) + 4H2(g) C3H8(g) ΔH = – 104.7 kJ
6C(graphite) + 6H2(g) + 3O2 C6H12O6(s) ΔH = – 1271 kJ
Enthalpy of reaction by direct method: The standard enthalpies of formation are one
of the most important tools for determining the standard enthalpy of any physical or
°
chemical change, ΔHrxn . This can be accomplished simply by the following equation:
° ° °
ΔHrxn = ΣΔHf,products – ΣΔHf,reactants
This equation says that the standard enthalpy of any change equals the sum of the
standard enthalpies of formation of products minus the sum of the standard enthalpies
of formation of reactants
EXAMPLE 6.9
The thermite reaction involves aluminum and iron(III) oxide
2Al(s) + Fe2O3(s) Al2O3(s) + 2Fe(l)
82
This reaction is highly exothermic, and the liquid iron formed is used to weld metals. Calculate
the heat released in kilojoules per gram of Al reacted with Fe2O3.
° kJ ° kJ ° kJ
ΔHf,Al 2 O3 (s)
= – 1669.8 mol, ΔHf,Fe(𝑙) = 12.40 mol, ΔHf,Fe2 O3 (s)
= − 822.2 mol
Solution
° ° °
ΔHrxn = ΣΔHf,products – ΣΔHf,reactants
°
ΔHrxn = [ΔHf° (Al2O3) + 2ΔHf° (Fe)] – [2ΔHf° (Al) + ΔHf° (Fe2O3)]
°
ΔHrxn = [(– 1669.8 kJ/mol) + (2 mol × 12.40 kJ/mol)]
– [(2 mol × 0) + (– 822.2 kJ/mol)]
°
ΔHrxn = – 822.8 kJ/2 mol of Al reacted
Mass of Al reacted = n × M = 2 mol × 26.98 g/mol = 53.96 g
– 822.8 kJ per 53.96 g Al
X kJ per 1 g Al
– 822.8 kJ ×1 g
X = 53.96 g = – 15.25 kJ/g
Practice Exercise 6.9
Benzene (C6H6) burns in air to produce carbon dioxide gas and liquid water. Calculate the heat
°
released (in kilojoules) per gram of the compound reacted with oxygen. ∆Hf,CO 2 (g)
= − 393.5
kJ ° kJ ° kJ
, ∆Hf,H 2 O(𝑙)
= − 285.8 mol, and ∆Hf,C 6 H6 (𝑙)
= 49.04 mol
mol
The following table gives some.
𝐤𝐉 𝐤𝐉 𝐤𝐉
Compound Δ𝐇𝐟° ( ) Compound Δ𝐇𝐟° ( ) Compound Δ𝐇𝐟° ( )
𝐦𝐨𝐥 𝐦𝐨𝐥 𝐦𝐨𝐥
AgBr(s) – 99.5 KClO3(s) – 391.4 HBr(g) – 36.2
AgCl(s) – 127.0 KF(s) – 562.6 HCl(g) – 92.3
AgI(s) – 62.4 MgCl2(s) – 641.8 HI(g) + 25.9
Ag2O(s) – 30.6 MgCO3(s) – 1113 HNO3(l) – 173.2
Ag2S(s) – 31.8 MgO(s) – 601.8 H2O(g) – 241.8
Al2O3(s) – 1669.8 Mg(OH)2(s) – 924.7 NH4Cl(s) – 315.4
BaCl2(s) – 860.1 MgSO4(s) – 1278.2 NH4NO3(s) – 365.1
BaCO3(s) – 1218.8 MnO(s) – 384.9 NO(g) + 90.4
BaO(s) – 558.1 MnO2(s) – 519.7 NO2(g) + 33.9
BaSO4(s) – 1465.2 NaCl(s) – 411.0 NiO(s) – 244.3
CaCl2(s) – 795.0 NaF(s) – 569.0 PbBr2(s) – 277.0
CaCO3 – 1207.0 NaOH(s) – 426.7 PbCl2(s) – 359.2
CaO(s) – 635.5 NH3(g) – 46.2 PbO(s) – 217.9
Ca(OH)2(s) – 986.6 C2H2(g) + 226.7 PbO2(s) – 276.6
CaSO4(s) – 1432.7 C2H4(g) + 52.3 Pb3O4(s) – 734.7
CCl4(l) – 139.5 C2H6(g) – 84.7 PCl3(g) – 306.4
CH4(g) – 74.8 C3H8(g) – 103.8 PCl5(g) – 398.9
CH3OH(l) – 238.6 n– C4H10(g) – 124.7 SiO2(s) – 859.4
CO(g) – 110.5 n– C5H12(l) – 173.1 SnCl2(s) – 349.8
CO2(g) – 393.5 C2H5OH(l) – 277.6 SnCl4(l) – 545.2
H2O(l) – 285.8 CoO(s) – 239.3 SnO(s) – 286.2
H2O2(l) – 187.6 Cr2O3(s) – 1128.4 SnO2(s) – 580.7
H2S(g) – 20.1 CuO(s) – 155.2 SO2(g) – 296.1
H2SO4(l) – 811.3 Cu2O(s) – 166.7 So3(g) – 395.2
HgO(s) – 90.7 CuS(s) – 48.5 ZnO(s) – 348.0
HgS(s) – 58.2 CuSO4(s) – 769.9 ZnS(s) – 202.9
KBr(s) – 392.2 Fe2O3(s) – 822.2
KCl(s) – 435.9 Fe3O4(s) – 1120.9
Enthalpy of reaction by indirect method (Hess’s law of heat summation)
Hess’s law says “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”
The general rule in applying Hess’s law is to arrange a series of chemical equations
(steps) in such a way that, when added together, all species will cancel except for
83
the reactants and products that appear in the overall reaction. This means that we
want the reactants on the left and the products on the right of the arrow
Sometimes, we need to multiply one or more of the given equations by appropriate
coefficients, and need to reverse one or more of them
From the following equations we can obtain the enthalpy of formation of CO(g):
C(graphite) + O2(g) CO2(g) °
ΔHrxn = – 393.5 kJ
1
CO(g) + 2O2(g) CO2(g) °
ΔHrxn = – 283.0 kJ
The second equation should be reversed then added to the first:
C(graphite) + O2(g) CO2(g) °
ΔHrxn = – 393.5 kJ
1
CO2(g) CO(g) + 2O2(g) °
ΔHrxn = + 283.0 kJ
1
C(graphite) + 2O2(g) CO(g) °
ΔHrxn = – 110.5 kJ
EXAMPLE 6.10
Calculate the standard enthalpy of formation of acetylene (C2H2) from its elements:
2C(graphite) + H2(g) C2H2(g)
The equations for each step and the corresponding enthalpy changes are:
A) C(graphite) + O2(g) CO2(g) °
ΔHrxn = – 393.5 kJ/mol
1
B) H2(g) + 2O2(g) H2O(l) °
ΔHrxn = – 285.8 kJ/mol
C) 2C2H2(g) + 5O2(g) 4CO2(g) + 2H2O(l) °
ΔHrxn = – 2598.8 kJ/mol
Solution
1
The first equation is multiplied by 2; and the third equation is revered and multiplied by 2:
2C(graphite) + 2O2(g) 2CO2(g) °
ΔHrxn = – 787.0 kJ
1
H2(g) + 2O2(g) H2O(l) °
ΔHrxn = – 285.8 kJ
2CO2(g) + H2O(l) C2H2(g) + 2.5O2(g) °
ΔHrxn = + 1299.4 kJ
2C(graphite) + H2(g) C2H2(g) °
Δ𝐇𝐫𝐱𝐧 = + 226.6 kJ
Practice Exercise 6.10
Calculate the standard enthalpy of formation of carbon disulfide (CS2) from its elements, given that:
A) C(graphite) + O2(g) CO2(g) °
ΔHrxn = – 393.5 kJ
B) S(rhombic) + O2(g) SO2(g) °
ΔHrxn = – 296.4 kJ
C) CS2(l) + 3O2(g) CO2(g) + 2SO2(g) °
ΔHrxn = – 1073.6 kJ
EXAMPLE 6.11
Calculate the standard enthalpy of formation of acetylene (C2H2) from its elements:
2C(graphite) + H2(g) C2H2(g)
The equations for each step and the corresponding enthalpy changes are:
A) C(graphite) + O2(g) CO2(g) ΔHrxn°
= – 393.5 kJ/mol
1
b) H2(g) + 2O2(g) H2O(l) °
ΔHrxn = – 285.8 kJ/mol
C) 2C2H2(g) + 5O2(g) 4CO2(g) + 2H2O(l) ΔHrxn°
= – 2598.8 kJ/mol
Solution
Careful look at the desired equation indicates that the first equation must be multiplied by 2; and the
1
third equation must be revered and multiplied by 2. So we will have
2C(graphite) + 2O2(g) 2CO2(g) ΔHrxn°
= – 787.0 kJ
84
1
H2(g) + 2O2(g) H2O(l) °
ΔHrxn = – 285.8 kJ
2CO2(g) + H2O(l) C2H2(g) + 2.5O2(g) °
ΔHrxn = + 1299.4 kJ
2C(graphite) + H2(g) C2H2(g) °
ΔHrxn = + 226.6 kJ
Practice Exercise 6.11
°
From the following reactions, calculate ∆𝐻𝑓,𝐶𝐻 4 (𝑔)
:
°
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔHrxn = − 890.34 kJ
1 °
H2(g) + 2O2(g) → H2O(l) ΔHrxn = – 285.84 kJ
°
C(graphite) + O2(g) → CO2(g) ΔHrxn = – 393.5 kJ
6.10 Heat or enthalpy of solution and dilution
The heat (or enthalpy) of solution, ΔHsoln, is the heat released (ΔHsoln is negative and
the process is exothermic) or absorbed (ΔHsoln is positive and the process is exothermic)
In solid NaCl, the Na+ and Cl− ions are held together by strong electrostatic forces.
When a small crystal of NaCl dissolves in water, the three-dimensional network of
ions breaks into Na+(g) and Cl−(g) ions
NaCl(s) → Na+(g) + Cl−(g) ΔH = + 788 kJ
These ions are stabilized in solution by hydration
H2 O
Na+(g) + Cl−(g) → Na+(aq) + Cl−(aq) ΔH = − 784 kJ
85
7. QUANTUM THEORY AND THE ELECTRONIC
STRUCTURE OF ATOMS
7.1 From classical physics to quantum theory
The new era in physics started in 1900 with a young Max Planck
While analyzing the data on radiation emitted by solids heated to various temperatures,
Planck discovered that atoms and molecules emit energy only in certain discrete
quantities, or quanta
Physicists had always assumed that energy is continuous and that any amount of energy
could be released in a radiation process
Planck’s quantum theory turned physics upside down and altered our concept of nature
First: Properties of waves
A wave can be thought of as a vibrating disturbance by which energy is transmitted
The fundamental properties of a wave are illustrated by the following figure:
The regular variation of the peaks and troughs enable us to sense the propagation of the
waves
Waves are characterized by their length (λ), amplitude, frequency (ν), wave number (k)
and speed (u)
The wave length (λ) is the distance between identical points on successive waves
The wave amplitude (A) is the vertical distance from the midline of a wave to the
peak or trough
The wave frequency (ν) is the number of waves that pass through a certain point
in one second
The wave number (k) is the number waves in unit length
The wave speed (c) is the product of its wavelength and its frequency
7.2 The electromagnetic radiation
In 1873 Maxwell proposed that visible light consists of electromagnetic waves
An electromagnetic wave has an electric field and a magnetic field components
These two components have the same wavelength, frequency, and speed, but they travel
in mutually perpendicular planes
87
that is sensed by eye. The warmth of the same iron bar represents another portion of its
emission spectrum (the infrared region)
A feature common to the emission spectra of the sun and of a heated solid is that both
are continuous; that is, all wavelengths of visible light are represented in the spectra
The emission spectra of atoms in the gas phase, on the other hand, do not show a
continuous spread of wavelengths from red to violet; rather, the atoms produce bright
lines in different parts of the visible spectrum
These line spectra are the light emission only at specific wavelengths
Every element has a unique emission spectrum. The following figure shows the color
emitted by hydrogen atoms in a discharge tube
The characteristic lines in atomic spectra can be used in chemical analysis to identify
unknown atoms, much as fingerprints are used to identify people
When the lines of the emission spectrum of a known element matches the lines of the
emission spectrum of an unknown sample, the identity of the sample is established
Although the utility of this procedure was recognized some time ago in chemical
analysis, the origin of these lines was unknown until early in the twentieth century
7.4 Emission spectrum of the hydrogen atom
In 1913, a theoretical explanation of the emission spectrum of the hydrogen atom was
presented by the Danish physicist Niels Bohr
Bohr’s treatment is very complex and is no longer considered to be correct in all its
details. Thus, we will concentrate only on his important assumptions and final result
When Bohr first tackled this problem, physicists already knew that the atom contains
electrons and protons, but they thought that electrons whirled around the nucleus in
circular orbits at high velocities
In the hydrogen atom, it was believed that the electrostatic attraction between the
positive “solar” proton and the negative “planetary” electron pulls the electron inward
and that this force is balanced exactly by the centrifuge force
According to classical physics, an electron moving in an orbit of a H atom would
experience an acceleration toward the nucleus and radiating electromagnetic waves
88
Such an electron would quickly spiral into the nucleus and annihilate itself with the
proton, but this does not happen, Bohr postulated that the electron is allowed to occupy
only certain orbits of specific energies (the energies of the electron are quantized). An
electron in any of them will not spiral into the nucleus and will not radiate energy
Bohr attributed the emission of radiation by an energized H atom to the electron
dropping from a higher-energy orbit to a lower one and emitting a quantum of energy
He showed that the energies that an electron in H atom can occupy are given by
1
Ea = − R H × (n2 )
R H , the Rydberg constant, has for the hydrogen atom the value 2.18 × 10 −18 J and
“n” is an integer called the principal quantum number; it has the values 1, 2, 3, . . . .
The negative sign in the previous equation is an arbitrary convention, signifying that
the energy of the electron in the atom is lower than the energy of a free electron, which
is infinitely far from the nucleus; so is assigned arbitrarily a value of zero
Mathematically, this corresponds to setting “n” equal to infinity. So, E∞ = 0
As the electron gets closer to the nucleus (as n decreases), En becomes larger in
absolute value, but also more negative
The most negative value is reached when n = 1, which corresponds to the most stable
energy state which is called the ground state, or the ground level referring to the lowest
energy state of a system (which is an atom in our discussion)
The stability of the electron diminishes for n = 2, 3, 4 ··· . Each of these levels is called
an excited state, or excited level, which is higher in energy than the ground state
A hydrogen electron for which n is greater than 1 is said to be in an excited state
The radius of each circular orbit in Bohr’s model depends on n2 . Thus, as n increases
from 1 to 2 to 3, the orbit radius increases very rapidly
The higher the excited state, the farther away the electron is from the nucleus (and the
less tightly it is held by the nucleus)
Bohr’s theory enables us to explain the line spectrum of the hydrogen atom
Radiant energy absorbed by the atom causes the electron to move from a lower-energy
state (smaller n value) to a higher-energy state (larger n value). Conversely, radiant
energy (in the form of a photon) is emitted when the electron moves from a higher-
energy state to a lower-energy state
The quantized movement of the electron from one energy state to another is analogous
to the movement of a tennis ball either up or down a set of stairs
The ball can be on any of the steps but never between them
The journey from a lower step to a higher one is an energy-requiring process, whereas
movement from a higher step to a lower step is an energy-releasing process
89
The quantity of energy involved in either type of change is determined by the distance
between the beginning and ending steps
Similarly, the amount of energy needed to move an electron in the Bohr atom depends
on the difference in energy levels between the initial and final states
To apply that previous equation to the emission process in a hydrogen atom, we
suppose that the electron is initially in an excited state characterized by the principal
quantum number ninitial
During emission, the electron drops to a lower energy state characterized by the
principal quantum number nfinal (either a less excited state or the ground state)
The difference between the energies of the initial and final states is
∆E = Efinal − Einitial
1 1
∆E = h × 𝜈 = R H × ( 2 − 2 )
ninitial nfinal
When a photon is emitted, ninitial > Efinal the term in parentheses is negative and
∆E is negative (energy is lost to the surroundings)
When photon is absorbed, nfinal > ninitial, the term in parentheses is positive and
∆E is positive (energy is gained by the atom)
Each spectral line in the spectrum corresponds to a particular transition in a H atom
When we study a large number of H atoms, we observe all possible transitions and
hence the corresponding spectral lines
The brightness of a line depends on number of photons having same wavelength
The emission spectrum of H includes a wide range of wavelengths from the infrared to
the ultraviolet.
The following table lists the series of transitions in the hydrogen spectrum; they are
named after their discoverers
series ninitial nfinal Spectral region
Layman 1 2,3... UV
Balmer 2 3,4... Visible
Paschen 3 4,5... IR
Bracket 4 5,6... IR
Pfund 5 6,7... IR
The following figure shows the energy levels in the hydrogen atom and the various
emission series
The Balmer series was particularly easy to study because some of its lines fall in
the visible range
90
EXAMPLE 7.2
Calculate the wavelength of a photon (in nanometers) emitted as a result of transition from the
ninitial = 5 state to the ninitial = 2 state in the hydrogen atom.
Solution
1 1 1 1
∆E = R H × (n2 − n2 ) = 2.18 × 10−18 J × (25 − 4) = − 4.58 × 10−19 J
initial final
m
c ch 3 × 108 × 6.63 × 10−34 Js
λ = = = s
= 4.34 × 10−7 m
ν ∆E 4.58 × 10−19 J
1 × 109 nm
λ = 4.34 × 10−7 m × = 434 nm
1m
Practice Exercise 7.2
Calculate the wavelength (in nanometers) of a photon emitted during a transition from 𝑛𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 6
state to the 𝑛𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 4 state in the hydrogen atom
7.5 The dual nature of the electron
Why is the electron in a Bohr atom restricted to orbit the at certain fixed distances?
De Broglie reasoned that if light waves can behave like a stream of particles (photons),
then perhaps particles (such as electrons) can behave like waves
According to de Broglie, an electron bound to the nucleus behaves like a standing wave
The greater the frequency the shorter the wavelength of the standing wave
If an electron behaves like a standing wave in the hydrogen atom, the length of the
wave must fit the circumference of the orbit exactly. Otherwise the wave would
partially cancel itself on each successive orbit and the amplitude of the wave would be
reduced to zero, and the wave would not exist. Ttwo following figure show this
The relation between the circumference of an allowed orbit (2πr) and the wavelength
(λ) of the electron is given by
2πr = nλ
where r is the radius of the orbit, and n = 1, 2, 3, . . . .
Because n is an integer, it follows that r can have only certain values as n increases
from 1 to 2 to 3 and so on
Because the energy of the electron depends on the size of the orbit (the value of r), its
value must be quantized
De Broglie’s reasoning led to the conclusion that waves can behave like particles and
particles can behave wave like waves. De Broglie deduced that the particle and wave
properties are related by the expression
h h
λ = m𝑢 or (λ = mc)
λ, m, and u are the wavelengths associated with a moving particle, its mass
(Note that the left side of the equation involves the wave property “wavelength”,
whereas the right side involves the particle property “mass”)
EXAMPLE 7.3
Calculate the wavelength of the “particle” in the following two cases (𝐡 = 𝟔. 𝟔𝟑 × 𝟏𝟎−𝟑𝟒 𝐉 𝐬):
91
𝑚
a) The fastest serve of a tennis ball is about 68 𝑠 . if its mass is 6 × 10−2 kg, calculate the
wavelength associated with this serve
m
b) The speed of an electron is 68 s . if its mass is 9.1049 × 10−31 kg, calculate the wavelength
associated with this electron
Solution
kg m2
h 6.63 × 10−34 J s 6.63 × 10−34 s
s2
a) λ = = m = m = 1.6 × 10−34 m
mu 6 × 10−3 kg × 68 −2
6 × 10 kg × 68
s s
kg m2
h 6.63 × 10−34 J s 6.63 × 10−34 s
s2
b) λ = = m = m = 1.1 × 10−5 m
mu 9.1049 × 10−31 kg × 68 9.1049 × 10−31 kg × 68
s s
Practice Exercise 7.3
Calculate the wavelength (in nanometers) of a H atom (mass = 1.674 × 10−27 kg) moving at
cm
speed = 7.00 × 102 s . (𝐡 = 𝟔. 𝟔𝟑 × 𝟏𝟎−𝟑𝟒 𝐉 𝐬)
7.6 Quantum mechanics
Although Bohr’s theory was a spectacular success it was followed by a series of failure
It did not account for the spectra of atoms containing more than one electron
It did it explain why extra lines in the H spectrum when a magnetic field is applied
If wave extends in space, how can the “position” of a wave be specified?
To describe the problem of trying to locate a subatomic particle that behaves like a
wave Heisenberg formulated what is now known as the Heisenberg uncertainty
principle which states that “it is impossible to know simultaneously both the momentum
p (defined as mass times velocity) and the position of a particle with certainty
Heisenberg uncertainty principle is stated mathematically as:
ℎ
∆𝑥 × ∆𝑝 ≥
4𝜋
∆𝑥 and ∆𝑝 are the uncertainties in measuring the position and momentum of the
particle, respectively
The ≥ signs have the following meaning: “If the measured uncertainties of position
ℎ
and momentum are large, their product can be greater than 4𝜋 (hence the “>” sign)
The significance of the previous equation is that even in the most favorable
conditions for measuring position and momentum, the product of the uncertainties
ℎ
can never be less than 4𝜋 (hence the “=” sign). Thus, making measurement of the
momentum of a particle more precise (that is, making ∆𝑝 a small quantity) means
that the position must become correspondingly less precise (that is, ∆𝑝 will become
larger)
Similarly, if the position of the particle is known more precisely, its momentum
measurement must become less precise
Applying the Heisenberg uncertainty principle to the H atom, we see that its
electron does not orbit the nucleus in a well-defined path, as Bohr thought
If it orbits in a well-defined path (a violation of the uncertainty principle), we could
determine precisely both the position of the electron (from its location on a
particular orbit) and its momentum (from its kinetic energy) at the same time
92
Bohr made a significant contribution to understand atoms, and his suggestion that
the energy of an electron in an atom is quantized remains unchallenged. But he did
not provide a complete description of electronic behavior in atoms
Schrödinger formulated an equation called “Schrödinger equation”
It describes the behavior and energies of submicroscopic particles
We will not discuss it because requires advanced calculus
It incorporates both particle behavior (mass, “m”), and wave behavior (wave
function “ψ”), which depends on the location in space of the electron in an atom
ψ itself has no direct physical meaning. However, the probability of finding the
electron in a certain region in space is proportional to ψ2
The idea of relating ψ2 to probability stemmed from the fact that “the intensity of
light is proportional to the square of the amplitude of the wave, or ψ2 ”
The most likely place to find a photon is where the intensity is greatest, that is,
where the value of ψ2 is greatest. A similar argument associates ψ2 with the
likelihood of finding an electron in regions surrounding the nucleus
The Quantum mechanical description of the hydrogen atom
The Schrödinger equation specifies the possible energy states the electron can
occupy in a H atom and identifies the corresponding wave functions (ψ)
These energy states and wave functions are characterized by a set of quantum
numbers (to be discussed shortly), with which we can construct a
comprehensive model of the H atom
Although quantum mechanics tells us that we cannot pinpoint an electron in an
atom, it does define the region where the electron might be at a given time
A new called concept “electron density” gives the probability that an electron
will be found in a particular region of an atom
“ψ2 ”, defines the distribution of electron density in space around the nucleus
Regions of high electron density represent a high probability of locating the
electron, whereas the opposite holds for regions of low electron density
93
Chemists and physicists have learned to get around this kind of difficulty by
approximation. For example, although the behavior of electrons in many-
electron atoms is not the same as in the hydrogen atom, we assume that the
difference is probably not too great
We can use the energies and wave functions obtained from the hydrogen atom
as good approximations of the behavior of electrons in more complex atoms
This approach gives descriptions of electronic behavior in many-electron atoms
7.7 Quantum Numbers
In quantum mechanics, solving Schrödinger equation gives three quantum numbers
that are required to describe the distribution of electrons in H atom and other atoms
They are called: the principal quantum number, the angular momentum quantum
number, and the magnetic quantum number
These quantum numbers will be used to describe atomic orbitals and to label electrons
that reside in them
A fourth quantum number (the spin quantum number) describes the behavior of a
specific electron and completes the description of electrons in atoms
7.7.1 The principal quantum number (n)
The principal quantum number “n” can have integral values 1, 2, 3, and so forth; it
1
corresponds to the quantum number in the equation “Ea = − R H × (n2 )”
In a H atom, the value of “n” determines the energy of an orbital. (this is not the case
for a many-electron atom)
The larger “n” is, the greater the average distance of an electron in the orbital from the
nucleus and therefore the larger the orbital
The principal quantum number is called “the shell”
7.7.2 The angular momentum quantum number (l)
The angular momentum quantum number “l” tells us the “shape” of the orbitals. The
values of “l” depend on the value of the principal quantum number, “n”
For a given value of “n”, has possible integral values from “l = 0” to “l = n – 1”. The
values of “l” designated by the letters as follows:
l 0 1 2 3
Given letter s p d f
These letters are the first letters of the words describing observed spectral lines which
are: sharp, principal, diffused and fundamental
The angular momentum quantum number is called “the subshell”
7.7.3 The magnetic quantum number (𝒎𝒍 )
The magnetic quantum number (m𝑙 ) describes the orientation of the orbital in space.
the value of m𝑙 depends on the value of l
For a certain value of l, there are (2l + 1) integral values of m𝑙 as follows:
− l, (− l + 1),· · ·0· · ·(+ l − 1), + l
7.7.4 The spin quantum number, 𝐦𝐬
The spin quantum number (ms ) describes the direction of an electron spin in its orbital.
Spinning can be either clockwise or anticlockwise with no third option:
1 1
ms = + 2 or ms = – 2
The table in the next page gives the four quantum numbers of each electron in any orbital
94
n l 𝐦𝒍 𝐦𝐬 n l 𝐦𝒍 𝐦𝐬 n l 𝐦𝒍 𝐦𝐬 n l 𝐦𝒍 𝐦𝐬
1 1 1 1
+ + + +
2 2 2 2
1 0 0 1 0 0 1 0 0 1 0 0 1
– – – –
2 2 2 2
1 1 1
+ + +
−1 2
1 −1 2
1 −1 2
1
– – –
2 2 2
2 1 1 1
+ + +
2 2 2
1 0 1 1 0 1 1 0 1
– – –
2 2 2
1 1 1
+ + +
2 2 2
+1 1 +1 1 +1 1
– – –
2 2 2
1 1
+ +
3 −2 2
1 −2 2
1
– –
2 2
1 1
+ +
−1 2
1 −1 2
1
– –
2 2
1 1
+ +
2 2
2 0 1 2 0 1
– –
2 2
1 1
+ +
2 2
+1 1 +1 1
– –
2 2
1 4 1
+ +
2 2
+2 1 +2 1
– –
2 2
1
+
−3 2
1
–
2
1
+
−2 2
1
–
2
1
+
−1 2
1
–
2
1
+
2
3 0 1
–
2
1
+
2
+1 1
–
2
1
+
2
+2 1
–
2
1
+
2
+3 1
–
2
7.8 Atomic orbitals
The “s” subshell has only one orbital
The “p” subshell has three orbitals that are equal in energy
The “d” subshell has five orbitals that are equal in energy
The “f” subshell has seven orbitals that are equal in energy
95
Electron occupies all space it moves within. So, it is impossible to draw an orbital.
Although, in principle an electron can be found anywhere, we know that during most of
the time it is as close as possible to the nucleus. The shapes of the space which includes
the electron most of its time, say 95% is as follows:
Shape of the “s” Orbitals
The following figure shows the distribution of electron density in the hydrogen 1s orbital
moving outward from the nucleus. The electron density decreases as the distance from the
nucleus increases. There is a 90 percent probability of finding the electron within a sphere
of radius 100 pm around the nucleus.
The following figure shows boundary surface diagrams for the 1s, 2s, and 3s atomic
orbitals. All s orbitals are spherical in shape but differ in size, which increases as the
principal quantum number increases.
Shape of the “p” Orbitals: The p orbitals start with n = 2. When l = 1, its magnetic
quantum number have values of − 1, 0 and + 1. Therefore, there are three p orbitals: px
, py and pz as shown by the following figure.
These three p orbitals differ from one another only in orientation. The boundary surface
diagrams of p orbitals in the previous figure show that each p orbital can be thought of
as two lobes on opposite sides of the nucleus. Like s orbitals, p orbitals increase in size
from 2p to 3p to 4p orbital and so on.
Shape of the “d” Orbitals: When l = 2, there are five d orbitals 3dxy, 3dyz, 3dxz,
3dx2 −x2 and 3dz2 . These orbitals are equal in energy and shown in the following figure.
96
Shape of the “f” Orbitals: The f orbitals are important in elements with atomic
numbers greater than 57. In this general chemistry course, we are not concerned with
elements having greater than 57 electrons.
7.9 The rules of electronic distribution
First: The “Aufbau principle” or The “n + l” principle
This rule states that electrons occupy the lowest-energy subshell before any other
higher-energy subshell
Determining which subshell is lower or higher in energy is achieved by the sum of the
values of “n” and “l” as shown in the following table
n l n+l
1 0 (s) 1
0 (s) 2
2
1 (p) 3
0 (s) 3
3 1 (p) 4
2 (d) 5
0 (s) 4
1 (p) 5
4
2 (d) 6
3 (f) 7
The lowest sum “n + l” is the lower energy
Some higher-energy subshells precede other subshells that are lower in energy. In these
cases of subshells having the same value of “n + I”, the lowest subshell is the one
having the lowest value of “n”. The above table is rearranged as follows:
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p
We know that any subshell has several orientations in the magnetic field. These
orientations do not differ in energy. Therefore, they are shown in the following manner:
“s” subshell has only one orientation which is represented as:
s
𝐦𝒍 = 0
“p” subshell has three orientations which are represented as:
p
𝐦𝒍 = − 1 𝐦𝒍 = 0 𝐦𝒍 = + 1
“d” subshell has five orientations which are represented as:
d
𝐦𝒍 = − 2 𝐦𝒍 = − 1 𝐦𝒍 = 0 𝐦𝒍 = + 1 𝐦𝒍 = + 2
“f” subshell has seven orientations which are represented as:
f
𝐦𝒍 = − 3 𝐦𝒍 = − 2 𝐦𝒍 = − 1 𝐦𝒍 = 0 𝐦𝒍 = + 1 𝐦𝒍 = + 2 𝐦𝒍 = + 3
97
Second: The Pauli principle
This second rule states that when an electron occupies an orbital it is impossible for
another electron to occupy it unless it spins in an opposite direction of the first electron
This rule means that, in the same atom, no two electrons can have the same four
quantum number (each electron has its own “address”)
Third: The Hund’s rule
Number of orientation in the magnetic field (orbital) are one In the “s” subshell, three
“p” subshell, five in the “d” subshell and seven in the “f” subshell
Hund’s rule states that when electrons occupy a subshell which has more than one
orientation in the magnetic field (p, d or f) they will not pair in the same orbital as long
as other orbitals are empty and the unpaired electrons spins in the same direction
Fourth: The rule of half-filled and fully-filled subshells
Half-filled and fully-filled subshells add more stability to electrons and atoms
Starting from the energy level where n = 4 and higher, the difference in energy between
subsequent subshells is so small
When two consecutive subshells are energetically close to each other, they will seek to
be half or fully filled even if this requires an electron to be in the slightly-higher energy
subshell rather than the slightly lower energy subshell
The following configurations illustrates how electrons distribute themselves within an
atom. It shows this distribution for the first 36 elements in the periodic table of elements.
1
H
1s1
2
He (Note: its upper shell is full, and its electron configuration is symbolized as [He])
𝟏𝐬 𝟐
3
Li
2s1
[He]
4
Be
2s 2
[He]
5
B
2s 2 2p1
[He]
6
C
2s 2 2p2
[He]
7
N
2s 2 2p3
[He]
8
O
2s 2 2p4
[He]
9
F
2s 2 2p5
[He]
98
10
Ne (Note: its upper shell is full, and its electron configuration is symbolized as [Ne])
2s 2 2p5
[He]
11
Na
3s1
[Ne]
12
Mg
3s 2
[Ne]
13
Al
3s 2 3p1
[Ne]
14
Si
3s 2 3p2
[Ne]
15
P
3s 2 3p3
[Ne]
16
S
3s 2 3p4
[Ne]
17
Cl
3s 2 3p5
[Ne]
18
Ar (Note: its upper shell is full, and its electron configuration is symbolized as [Ar])
3s 2 3p6
[Ne]
19
K
4s1
[Ar]
20
Ca
4s 2
[Ar]
21
Sc
4s 2 3d1
[Ar]
22
Ti
4s 2 3d2
[Ar]
23
V
4s 2 3d3
[Ar]
24
Cr
4s1 3d5
[Ar]
25
Mn
4s 2 3d5
[Ar]
99
26
Fe
4s 2 3d6
[Ar]
27
Co
4s 2 3d7
[Ar]
28
Ni
4s 2 3d8
[Ar]
29
Cu
4s1 3d10
[Ar]
30
Zn
4s 2 3d10
[Ar]
31
Ga
4s 2 3d10 4p1
[Ar]
32
Ge
4s 2 3d10 4p2
[Ar]
33
As
4s 2 3d10 4p3
[Ar]
34
Se
4s 2 3d10 4p4
[Ar]
35
Br
4s 2 3d10 4p5
[Ar]
36
Kr (Note: its upper shell is full, and its electron configuration is symbolized as [Kr])
4s 2 3d10 4p6
[Ar]
From the above configurations, it appears that noble-gases shells are full of electrons, and
any element comes after a noble gas has the configuration of this noble gas as its core
electrons plus the extra electrons in the following shell.
Example 7.4
Give the four quantum numbers for the two electrons in a 6s orbital of an atom.
Solution
Quantum number n l 𝐦𝒍 𝐦𝐬
1
First electron 6 0 0 +2
1
Second electron 6 0 0 –2
Practice exercise 7.4
Give the four quantum numbers for the six electrons in a 3p orbital of an atom
100
Example 7.5
Why aren’t correct the following quantum numbers for the electrons in the “p” subshell of 7N?
Quantum number n l 𝐦𝒍 𝐦𝐬
1
First electron 2 0 0 +2
1
Second electron 2 1 0 –2
Third electron 2 1 –1 +1
Solution
Electron distribution of nitrogen is as follows:
2s 2 2p3
[He]
The “n” quantum numbers: they are correct for all the three electrons
“l” quantum numbers: they are correct for the second and the third electrons but wrong for
first electron because it is in the second subshell, p, which has l = 1
The “m𝑙 ” quantum numbers: according to Hund’s rule, all of the electrons must be unpaired
and their quantum numbers must be “– 1”, “0” and “+ 1”
1 1
The “ms ” quantum numbers: according to Pauli’s principle, can be either + 2 or + 2; and
1 1
according to Hund’s rule, they all must be either + 2 or − 2
Practice exercise 7.5
A person gave the four quantum numbers for the six electrons in the 3p orbitals of an atom.
Judge the answer.
Quantum number n l 𝐦𝒍 𝐦𝐬
1
First electron 3 1 –1 +2
1
Second electron 3 1 –1 +2
1
Third electron 3 0 0 –2
1
Fourth electron 3 0 0 –2
1
Fifth electron 3 –1 +1 +2
1
Sixth electron 4 –1 +1 +2
7.10 Electron configurations of anions and cations
1) First: Anions
Anions are atoms having one or more than one electron more than its original electrons.
Their electrons are distributed using the same rules used for neutral atoms electrons.
Consider the following examples:
H: 1s1 H−: 1s2 or [He]
2 2
F: 1s 2s 2p 5
F−: 1s2 2s2 2p6 or [Ne]
O: 1s2 2s2 2p4 O2−: 1s2 2s2 2p6 or [Ne]
2 2
N: 1s 2s 2p 3
N3−: 1s2 2s2 2p6or [Ne]
All these anions have stable noble gas configurations. Notice that F−, Na+, and Ne (and
Al3+, O2−, and N3−) have the same electron configuration. They are said to be
101
isoelectronic because they have the same number of electrons, and hence the same
electron configuration. Thus, H− and He are also isoelectronic.
2) Second: Cations
Cations are atoms having one or more than one electron less than its original electrons.
Knowing its electron distributions requires writing the distributions of the original
atom, then removing electron or electrons as explained below:
Cations derived from elements that its upper subshell is “s” or “p”
Electrons of cations formed from atoms having “s” or “p” as its upper subshell are
removed from the upper subshell and its configuration can be known easily. The
electron configurations of some atoms of this kind and their corresponding cations
are as follows:
Na: [Ne]3s1 Na+: [Ne]
2
Ca: [Ar]4s Ca2+: [Ar]
Al: [Ne]3s2 3p1 Al3+: [Ne]
As it appears, all configuration becomes like the previous noble gas configuration.
Cations derived from elements that its upper subshell is “d”
In this case electrons are removed from the upper subshell having the bigger
principle quantum number as, for example, Ti, Fe, and Zn show below:
Ti: [Ar]4s2 3d2→Ti2+: [Ar]3d2
Fe: [Ar] 4s2 3d6→Fe3+: [Ar]3d5
Zn: [Ne]4s2 3d10→Zn2+: [Ne]3d10
Example 7.6
Write the electron configuration of the following:
A) 16S 2– B) 26Fe3+
Solution
A) 16S 2– has 18 electrons, (16 electrons + 2 electrons):
1s2 2s 2 2p6 3s 2 3p6
B) 26Fe3+ has 23 electrons, (26 electrons – 3 electrons):
First: we write the electron configuration of the Fe atom:
1s2 2s 2 2p6 3s 2 3p6 4s 2 3d6
Second: we find that 4s is the subshell having highest “n” quantum number. Its electrons and
a third one from the 3d electrons are removed to form Fe3+ . The electron configuration is:
1s2 2s 2 2p6 3s 2 3p6 3d5
Practice exercise 7.6
Write the electron configuration of the following:
A) 15P 3– B) 31Ga3+
7.11 The electron configurations and the location of elements in the periodic table
In chapter 2 we gave a simplified and brief introduction to the periodic table of elements
(see page 18). Now, we will see how we can specify the location of any elements in the
periodic table. First, we must make the electron configuration, then we can specify its
block, period and group as follows:
Determining the block:
The last subshell (s, p, d or f) in its electron configuration is its block
Determining the period:
The highest principle quantum number (1, 2, 3, 4, 5, 6 or 7) in its electron configuration
is its period
102
Determining the group of an element in the “s”, “p” or “d” block:
If the element is in block “s” the number of electrons in its last “s” subshell is its
group number
If the element is in block “p” we add 10 to the number of electrons in its last “s”
and “p” subshell and the resultant is its group number or add 10 to the number of
electrons in its last “p” subshell
If the element is in block “d” we add 2 to the number of electrons in its last “d”
subshell and the resultant is its group number
Determining the group of an element in the “f” block:
If it is in period “6” it is one of the lanthanide group
If it is in period “7” it is one of the actinide group
Example 7.7
For each of the four elements having the following atom numbers, determine the block, the
period, the group and the group name:
A) 9 B) 10 C) 12 D) 30
Solution
Answering the question requires writing the electron configuration of each:
A) 1s2 2s 2 2p5
B) 1s2 2s 2 2p6
C) 1s2 2s 2 2p6 3s 2
D) 1s2 2s 2 2p6 3s 2 3p6 4s 2 3d10
A B C D
Block p p s d
Period 2 2 3 4
Group 17 18 2 12
Group name Halogen Noble gases Alkali earth No group name
Practice exercise 7.7
For each of the four elements having the following atom numbers, determine the block, the
period, the group and the group name:
A) 8 B) 17 C) 19 D) 40
103
8. PHYSICAL PROPERTIES OF SOLUTIONS
(NOTE: CHAPTER 12 IN THE TEXTBOOK)
104
Because breaking attractive forces requires energy (ΔH1 > 0 and ΔH2 > 0) the first and
the second actions are endothermic
Because forming attractive forces releases energy (ΔH3 < 0) the third action is
exothermic
The enthalpy of solution ΔHsoln is given by:
ΔHsoln = ΔH1 + ΔH2 + ΔH3
There are three distinguished cases:
First case (ΔHsoln = 0): If the solute-solvent attractions are equal to the solvent-solvent
and the solute-solute attractions, the solution process is not
endothermic or exothermic and the solution is an ideal
solution.
Second case (ΔHsoln < 0): If the solute-solvent attractions are stronger than the
solvent-solvent and the solute-solute attractions, the solution
process is exothermic, and the solution is a non- ideal solution
Thitd case (ΔHsoln > 0): If the solute-solvent attractions are weaker than the solvent-
solvent and the solute-solute attractions, the solution process
is endothermic, and the solution is a non- ideal solution
8.2.2 The “like dissolve like” proverb
The “Like dissolve like” means that “the solute can dissolve in the solvent if the
attractive forces between its particles are like those in the solvent particles, but if
they are not, the solute cannot dissolve in the solvent”
The attractive forces of the solvent are so many
We will not consider the two famous types
The first is called “polar solvents” which dissolve any ionic or polar solute but
cannot dissolve any nonionic or nonpolar solute
The second is called “nonpolar solvents” in which any nonionic or nonpolar solute
can dissolve any nonpolar solute but cannot dissolve any ionic or polar solute
The following table gives some of the important polar and nonpolar solvents that
are widely used:
POLAR SOLVENTS NONPOLAR SOLVENTS
Water H2O Hexane CH3CH2CH2CH2CH2CH3
Formic acid HCO2H Benzene C6H6
Acetic acid CH3CO2H Toluene C6H5CH3
Methanol CH3OH 1,4-dioxene (CH3CH2O)2
Ethanol CH3CH2OH Chloroform CHCl3
n-butanol CH3CH2CH2CH2OH Diethyl ether (CH3CH2)2O
105
EXAMPLE 8.1
Knowing that:
A) Molecules of Br2, C6H6, CCl4, and CS2 are nonpolar
B) Molecules of H2O, CH2O and liquid NH3 are polar
C) KCl is an ionic compound
Predict the solubility in the following cases:
A) Bromine (Br2) in benzene (C6H6) and in water (H2O)
B) Potassium chloride (KCl) in (CCl4) and in liquid ammonia (NH3)
C) Formaldehyde (CH2O) in carbon disulfide (CS2) and in water (H2O)
Solution
A) Br2 is soluble C6H6 not in H2O
B) KCl is soluble in NH3 not in CCl4
C) CH2O is soluble in H2O not in CS2.
Practice Exercise 8.1
Knowing that I2 and CS2 are nonpolar and H2O is polar, Is iodine (I2) more soluble in water or
in carbon disulfide (CS2)?
8.3 Concentration units
The term “concentration” is used to compare the amount of the solute with the amount
of the solvent. The greater the amount of solute, the more concentrated the solution is
Remember that “Molarity” was previously explained in chapter 4
8.3.1 Mass percent of solute (Solute%)
The mass percent of the solute in a solution (Solute%) is given by:
𝐦
Solute% = 𝐭𝐨𝐭𝐚𝐥 𝐦𝐚𝐬𝐬𝐬𝐨𝐥𝐮𝐭𝐞 × 𝟏𝟎𝟎
𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧
Solute% has no unit
If we have a 25% C6H12O6 aqueous solution, we conclude that:
1) Water is the solvent and glucose is the solute
2) msolution = 100 g, msolute = 25 g and msolvent = 75 g
3) nsolvent, nsolute and ntotal can be calculated
4) Vsolution can be calculated if density of the solution (dsolution) is given
Example 8.2
A solution contains 131.4 g of glucose in 0.5 kg of water. Calculate glucose mass%.
Solution
mglucose 131.4 g
Glucose mass% = total mass × 102 = 2
g × 10 = 20.81%
of solution 131.4 g + 0.5 kg × 1000
kg
Practice Exercise 8.2
A solution contains 8.74 g NaNO3 in 75 g of water. Calculate the NaNO3 %.
8.3.2 Mole fraction (X)
Mole fraction of a component of a solution (Xcomponent) is given by:
𝐧𝐜𝐨𝐦𝐩𝐨𝐧𝐞𝐧𝐭 𝐧𝐜𝐨𝐦𝐩𝐨𝐧𝐞𝐧𝐭
Xcomponent = 𝐭𝐨𝐭𝐚𝐥 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐜𝐨𝐦𝐩𝐨𝐧𝐚𝐧𝐭𝐬 = 𝐧 𝐭
Mole fraction has no unit
If the mole fraction of C6H12O6 in an aqueous solution is 0.25, we conclude that:
1) Water is the solvent and glucose is the solute
2) nsolute = 0.25 mol and nsolvent = 0.75 mol
3) msolute , msolvent and msolution can be calculated
106
4) Vsolution can be calculated if density of the solution (dsolution) is given
Example 8.3
Calculate the mole fraction of 281 g of glucose (C6H12O6) in 450 mL aqueous solution (dsolution =
g
0.998 mL).
solution
g
Mass of solution = density × volume = 0.998 mL × 450 mL = 449.1 g
Mass of water = 449.1 g – 281 g = 168.1 g
m 281 g m 168.1 g
nglucose = Mglucose = g = 1.56 mol AND nwater = Mwater = g = 9.34 mol
glucose 180 water 18
mol mol
nt = nglucose + nwater = 1.56 mol + 9.34 mol = 10.9 mol
n 1.56
Xglucose = glucose = 10.9 = 0.143
t n
Practice Exercise 8.3
A solution is made by dissolving 8.74 g sodium nitrate (NaNO3) in 75.0 g of water. Calculate the
mole fraction of sodium nitrate in the solution.
8.3.3 Molality (m)
Molality (m) expresses the concentration of a solution as the number of moles of solute
(nsolute) in one kilogram of the solvent:
𝐧
Molality (m) = 𝐦𝐚𝐬𝐬 𝐬𝐨𝐥𝐮𝐭𝐞 (𝐤𝐠)
𝐬𝐨𝐥𝐯𝐞𝐧𝐭
mol
The molality units are which is usually called “molal” and is abbreviated as “m”
kg
If we have a 0.25 molal C6H12O6 aqueous solution, we conclude that:
1) Solvent is water and solute is glucose
2) nC6 H12 O6 = 0.25 mol, and msolute can be calculated
3) msolvent = 1 kg = 1000 g. nsolvent and msolution can be calculated
4) Vsolution can be calculated if density of the solution (dsolution) is given.
Example 8.4
A solution is made by dissolving 4.35 g glucose (C6H12O6) in 25.0 mL of water. Calculate the
molality of glucose in the solution. Water has a density of 1 g/mL.
Solution
g
msolvent = dsolvent × Vsolvent = 25 mL × 1 mL = 25 g = 0.025 kg
4.35 g
g
nsolute 180
mol mol
molality = mass = = 0.097 = 0.097 molal = 0.097 m
solv (kg) 0.025 kg kg
Practice Exercise 8.4
A solution is made by dissolving 8.74 g sodium nitrate (NaNO3) in 75.0 g of water. Calculate
the molality of sodium nitrate in the solution.
8.3.4 Interconversion between concentration’s units
The above discussion was an illustration to the main four types of concentration units:
solute mass%, mole fraction, molality and molarity
It was mentioned that knowing any one of them enables us to determine the other three.
The following exercises shows how this can be done
Example 8.5
An aqueous solution of hydrochloric acid contains 36% HCl by mass:
A) Calculate the mole fraction of HCl
B) Calculate the molality of HCl
107
Solution
m 36 g
A) nsolute = Msolute = g = 0.988 mol
solute 36.45
mol
msolvent = 100 g – 36 g = 64 g
m 64 g
nsolvent = Msolvent = g = 3.556 mol
solvent 18
mol
nsolute 0.988 mol
Xsolute = = (0.988 mol + 3.556 mol) = 0.217
nt
n 0.988 mol
B) molality = masssolute(kg) = = 15.44 molal
solv 0.064 kg
Practice Exercise 8.5
Calculate the molality of a sodium nitrate (NaNO3) aqueous solution in which the mass percent of
NaNO3 is 43%.
Example 8.6
A solution with a density of 0.876 g/mL contains 5 g of toluene (C7H8) dissolved in 225 g of
benzene. Calculate the molality and molarity of the toluene solution.
Solution
m 5g
nsolute = Msolute = g = 0.054 mol
solute 92
mol
nsolute 0.054 mol
m = mass = = 0.34 molal
solv (kg) 0.225 kg
mson 5 g + 225 g
Vsoln = = g = 262.56 mL = 0.263 L
dsoln 0.876
mL
nsolute 0.054 mol
Molarity = V = = 0.205 molar
soln (L) 0.263 L
Practice Exercise 8.6
A solution with a density of 0.998 g/mL contains 281 g of glucose (C6H12O6) and 168.1 g of water.
Calculate the molality and molarity of the glucose solution.
Example 8.7
Calculate the glucose mass% in a 0.73 molal solution of glucose in water.
Solution
mglucose
Glucose% = total mass of solution × 100
nglucose = 0.73 mol ,, mwater = 1 kg = 1000 g
mglucose = nglucopse × Mglucose = 0.73 × 180 = 131.4 g
msolution = mglucose + mwater = 131.4 + 1000 = 1131.4 g
131.4 g
Solute% = 1131.4 g × 102 = 11.61%
Practice Exercise 8.7
If the molality of a solution of urea (NH2CONH2) in water is 0.14 mol/kg, calculate the mass percent
of urea in the solution.
8.4 The effect of temperature on solubility
8.4.1 Solid solubility and temperature
The following figure clearly shows that solubility in water increases as temperature
increases for most ionic solid salts, decreases for a few ionic solid salts in water increases
as temperature decreases and is rarely the same at all temperature
108
EXAMPLE 8.8
Using the above curves answer the following questions:
1) At 40 °C, which is more soluble KCl or K2Cr2O7?
2) At 90 °C, which is more soluble KCl or K2Cr2O7?
Solution
1) At 40 °C, KCl is more soluble than K2Cr2O7
2) At 90 °C, K2Cr2O7 is more soluble than KCl
Practice Exercise 8.8
Using the curves of the solubility versus temperature,
1) At what temperature will the solubility of KCl equalizes that of KClO3?
2) At 47 °C, the solubility of KNO3 is 80 g/100 g of water. At what temperature would the
solubility of NaNO3 be the same?
8.4.2 Gas solubility and temperature
The following figure shows n all cases, the solubility of any gas decreases as temperature
increases but differs from a gas to another
109
8.5 The effect of pressure on the solubility of gases
Due to the spacing between particles of gases, pressure has a great effect on the
solubility of gases. Let’s look at the following figure:
The figure shows that as we increase the pressure of the gas above the liquid it is forced
to dissolve more of the gas.
The quantitative relation between gas solubility and its pressure is given by Henry’s
law: “the solubility of a gas in a liquid is proportional to its pressure over the
solution”. It is presented by the following equation:
c = kP
”c” is the molar concentration (the number of moles of gas in one liter of the solution
“P” is the pressure (in atm) of the gas over the solution
“k” is a constant for each gas and is called Henry’s constant
mol
Henry’s constant differs from a gas to another and its units are L × atm
The amount of gas that will dissolve in the liquid depends on how frequently the gas
molecules collide with the liquid surface and become trapped. We can understand this
matter when we think about a bottle of a refreshment drink:
1) The bottle is sealed at high pressure of CO2. This means that amount of CO2
dissolved in these drinks is many times the amount dissolved under normal
atmospheric pressure
2) When the cap of the bottle is removed the excess dissolved CO2 comes out of
solution, causing the effervescence, and the pressure in the bottle finally falls to
atmospheric pressure and the amount of CO2 remaining in the beverage inside the
bottle is then determined only by the normal atmospheric partial pressure of CO2,
0.0003 atm.
EXAMPLE 8.9
mol
The solubility of N2(g) in water at 25 °C and 1 atm is 6.8 × 10–4 L . What is its molarity if
dissolved at atmospheric conditions? (𝐏𝐍𝟐 in the atmosphere = 0.78 atm).
Solution
c=k×P and 6.8 × 10–4 mol/L = k × 1 atm
mol
6.8 × 10–4
k= L
= 6.8 × 10–4 mol/L atm
1 atm
mol
c = 6.8 × 10–4 L × atm × 0.78 atm = 5.3 × 10–4 mol/L
Practice Exercise 8.9
Calculate the molar concentration of oxygen in water at 25°C for a partial pressure of 0.22 atm.
The Henry’s constant for oxygen is 1.3 × 10–3 mol/L atm.
110
THE PROPERTIES OF A PURE LIQUID CHANGE AFTER IT BECOMES NOT PURE
Vapor pressures, boiling points, and freezing points of pure liquids
First: Vapor pressures of pure liquids
The liquid molecules that evaporate become gaseous molecules and are called “vapor”
Vapor exert a pressure called “vapor pressure”
Only liquid molecules that reach the surface of the liquid with the highest energies and
speeds can free themselves from its liquid state and become gaseous (vapor)
Any liquid molecule that does not have high energy and speed will not vaporize even if it
is at the surface of the liquid
Any liquid molecule that does not satisfy these two conditions will not vaporize
Let’s look carefully to the following figure:
The above figure shows that before the evaporation process starts, the mercury levels in the
U-shaped manometer tube are equal
As soon as some molecules leave the liquid, a vapor phase is established, and its pressure
is called the vapor pressure.
Eventually, the mercury levels stabilize and no further changes in pressure are seen
As the concentration of molecules in the vapor phase increases, some molecules start to
condense from the gas phase to the liquid phase
Vapor molecules differ in their energies and speeds. The only vapor molecules that can
condense back to liquid (trapped by the liquid molecules at the liquid surface) are those
colliding the surface of the liquid with the lowest energies and speeds
Any vapor molecule that does not satisfy these two conditions will not condense
As condensation rate rises evaporation rate decreases until the two rates become equal
When the two rates become equal, we say that a state of dynamic equilibrium is reached
The vapor pressure measured when this dynamic equilibrium exists between condensation
and evaporation is called “equilibrium vapor pressure” or simply “vapor pressure”
The equilibrium vapor pressure is the maximum vapor pressure of a liquid at a given
temperature and it is constant at a constant temperature
Increasing temperature increases not only the energy and speed of molecules but also
increases the number of molecules having high energy and speed
As temperature increases vapor pressure increases
Vapor pressure of many liquids at different temperatures are available in tables achieved
by physicists and chemists.
Second: Boiling points of pure liquids
111
When liquid temperature increases, its vapor pressure increases and equalize the external
pressure at a certain temperature
At this certain temperature the whole liquid molecules become in a situation of transition
from the liquid state to the gaseous state, and the surface of the liquid disappears
This particular situation of evaporation at this particular temperature is called boiling
The temperature at which this happens is called “the boiling point” and if the external
pressure is the normal pressure (1 atm) it is called “the normal boiling point”. For
example, the boiling point of water is 100 °C only at 1 atm
If the external pressure is higher than standard pressure the boiling point becomes higher
than standard boiling point (for example, at 1.5 atm water will boil at 110.5 °C)
If the external pressure is lower than standard pressure the boiling point becomes lower
than standard boiling point (for example, at 0.4 atm water will boil at 84 °C)
Off course, the value of this particular temperature differs from liquid to liquid and the
liquid which vaporizes easier has the lesser boiling point and vice versa
Third: Freezing points of pure liquids
Decreasing the temperature of liquid molecules will decrease their energies and speeds and
consequently the attractive forces between them increase
At a certain temperature, the liquid molecules start to be tightly bonded to their
neighboring molecules and cannot leave their positions and we say: the liquid freezes
We call the temperature at which the liquid freezes “the freezing point”. If the pressure at
which liquid freezes is 1 atm this temperature is called “the normal freezing point”. For
example, the standard freezing point of water is 0 °C
8.6 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, regardless of whether
they are atoms, ions, or molecules. The colligative properties are vapor-pressure
lowering, boiling-point elevation, freezing-point depression, and osmotic pressure
For our discussion of colligative properties of nonelectrolyte solutions, it is important
to keep in mind that we are talking about relatively dilute solutions, that is, solutions
whose concentrations ≤ 0.2 mol/Lsolution
8.6.1 Vapor pressures lowering
First: the solute is not volatile:
The pure solvent vapor pressure is Psolvent
°
The vapor above the solution is the vapor of only the solvent
We can calculate the molar fractions (Xsolvent and Xsolute)
After dissolving solute, its particles become attached to the solute particles
These attachments hinder the evaporation of the solvent particles which in turn makes
°
the vapor pressure of the liquid lower than Psolvent by an amount of ΔP which is called
“vapor pressure lowering”
According to Raoult’s law:
°
Psolvent = Xsolvent × Psolvent
Because the vapor pressure of the solution belongs only to the solvent, Psolution is given
as follows:
°
Psolution = Xsolvent × Psolvent
112
°
ΔP = Xsolute × Psolvent
EXAMPLE 8.10
Calculate the vapor pressure and the vapor-pressure lowering of a solution made by dissolving
218 g of glucose in 460 mL of water at 30 °C. Assume the density of the solution is 1.00 g/mL.
°
(Mglucose = 180.15 g/mol, 𝐏𝐰𝐚𝐭𝐞𝐫,𝟑𝟎 °𝐂 = 𝟑𝟏. 𝟖𝟐 𝐭𝐨𝐫𝐫)
Solution
460 g 218 g 25.5 mol
nwater = g = 25.53 mol nglucose = g = 1.21 mol Xwater = = 0.995
18.016 180.15 25.5 mol + 1.21 mol
mol mol
°
Psolution = Xsolvent × Psolvent
Psolution = 0.995 × 31.82 mmHg = 30.4 mmHg
°
ΔP = Psolvent – Psolution = 31.82 mmHg – 30.4 mmHg = 1.42 mmHg
Practice Exercise 8.10
Calculate the vapor pressure and the vapor-pressure lowering at 35°C of a solution of 82.4 g of
°
urea in 212 mL of water. (𝐏𝐰𝐚𝐭𝐞𝐫,𝟑𝟓 °𝐂 = 42.2 mmHg)
Second: Vapor pressures of mixed liquids (Raoult’s law)
Here we have two pure liquid, liquid “A” and liquid “B” with vapor pressure PA° and
PB°
Their number of moles are “nA and “nB ”
After they are mixed, their vapor pressure in the mixture are PA and PB
If we mix the nA mole of A with nB mole of B, we will get a liquid solution with a
known molar fraction of each, XA and XB
Raoul’s law for this mixture is:
Psolution = PA + PB
(PA = XA × PA° ) AND (PB = XB × PB° )
Psolution = (XA × PA° ) + (X B × PB° )
Because XA + XB = 1, the last equation can be modified to be:
Psolution = XA × (PA° – PB° ) + PB° OR Psolution = XB ×(PB° – PA° ) + PA°
All these previous equations are known as Raoul’s law
Raoul’s law is applicable only if the forces of attractions between the particles of
the mixed liquids are of the same type
Any solution obeys Raoul’s law is called “ideal solution”; if not it is called “nonideal
solution”
Example 8.11
Calculate the vapor pressure of a solution of 252 g of pentane(l) and 1400 g of heptane(l) at 20 oC.
g °
(Mpentane = 72 mol and Ppentane,20 oC = 420 mmHg)
°g
(Mheptane = 100 mol and Pheptane,20 oC = 36 mmHg)
Solution
° °
Psolution = (Xpentane × Ppentane ) + (Xheptane × Pheptane )
mpentane 252 g
npentane = = g = 3.5 mol
Mpentane 72
mol
mheptane 1400 g
nheptane = M = g = 14 mol
heptane 100
mol
npentane 3.5
Xpentane = n = 3.5 + 14 = 0.2
pentane + nheptane
113
Xheptane = 1 – Xpentane = 1 – 0.2 = 0.8
Psolution = (0.2 × 420 mmHg) + (0.8 × 36 mmHg) = 112.8 mmHg
Practice Exercise 8.11
Calculate the vapor pressure of a solution of 50 g of methanol and 50 g of ethanol at 20oC.
𝐠 ° 𝐠 °
(𝐌𝐦𝐞𝐭𝐡𝐚𝐧𝐨𝐥 = 32 𝐦𝐨𝐥 and 𝐏𝐦𝐞𝐭𝐡𝐚𝐧𝐨𝐥 = 94 mmHg) (𝐌𝐞𝐭𝐡𝐚𝐧𝐨𝐥 = 46 𝐦𝐨𝐥 and 𝐏𝐞𝐭𝐡𝐚𝐧𝐨𝐥 = 44 mmHg)
8.6.2 Boiling point elevation
Boiling point (t b ) is the temperature at which the vapor pressure of the liquid equalizes
the external pressure
The normal boiling point (t °b ) is the temperature at which the vapor pressure of the
liquid equalizes the normal external pressure (1 atm)
The vapor pressure of the solution became less than that of the pure liquid. So, the
vapor pressure of the solution, at the temperature at which the pure liquid boils,
will be less than that needed for the solution to boil
The temperature at which the vapor pressure of the solution equalizes the external
normal pressure is elevated by a certain value (ΔTb )
The value of ΔTb is proportional to the solution molality (m):
ΔTb ∝ m
ΔTb = K b m
K b is the molal boiling-point elevation constant; its value differs from liquid to
another
K ×n
ΔTb = m b solute
(kg)
solvent
°C msolute (kg)
Kb ( mol ) × kg °C kg 1000 g
Msolute ( ) Kb ( )× msolute (g) × ( )
kg mol mol 1 kg
ΔTb (ºC) = = g
msolvent (kg) Msolute ( ) × msolvent (g)
mol
Kb × msolute × 1000
ΔTb = Msolute × msolvent
The last equation is used to determine “ΔTb ” but with its restriction that the unit of
masses is “g”
8.6.3 Freezing point depression
Freezing point is the temperature at which the liquid substance changes its state to
solid
Normal freezing point (t °f ) is the temperature at which the liquid substance changes
its state to solid at the normal external pressure (1 atm)
But because the liquid is not pure but contains a solute that is nonvolatile, its molecules
cannot freeze at the same temperature when the liquid is pure
Temperature of the solution must be lowered by a certain value (ΔTf ) to freeze
The value of ΔTf is proportional to the solution molality (m):
ΔTf ∝ m
ΔTf = K f m
K f is the molal freezing-point depression constant; its value differs from liquid to
another.
K ×n
ΔTf = m f solute
(kg)
solvent
114
°C msolute (kg)
Kf ( mol ) × kg °C kg g
Msolute ( ) )× msolute (g) × 1000 ( )
Kf (
kg mol mol kg
ΔTf (ºC) = = g
msolvent (kg) Msolute ( ) × msolvent (g)
mol
Kf × msolute × 1000
ΔTf = Msolute × msolvent
The last equation is used to determine “ΔTb ” but with its restriction that the unit of
masses is “g”
EXAMPLE 8.12
A 7.85-g sample of an unknown compound is dissolved in 301 g of benzene. The freezing point
of the solution is 1.05 °C below that of pure benzene. Calculate the molar mass of this
°𝐂 𝐤𝐠
compound. (𝐊 𝐟 = 𝟓. 𝟏𝟐 𝐦𝐨𝐥 )
Solution
ΔTf = 1.05 °C
°C kg g
Kf × msolute (g) × 1000
mol kg
ΔTf = g
Msolute ( ) × msolvent (g)
mol
°C kg g
5.12 × 7.85 (g) × 1000 ( )
mol kg
1.05 °C = Msolute × 301 (g)
g
Msolute = 127 mol
Practice Exercise 8.12
Calculate the boiling and freezing points of a solution containing 478 g of ethylene glycol (Molar
°
mass = 62.01 g/mol) in 3202 g of water. (M ethylene glycol = 62.01 g/mol), (𝐓𝐟𝐫𝐞𝐞𝐳𝐢𝐧𝐠,𝐰𝐚𝐭𝐞𝐫 = 0 °C),
°
(𝐓𝐛𝐨𝐢𝐥𝐢𝐧𝐠,𝐰𝐚𝐭𝐞𝐫 = 100 °C), (Kf,water = 1.86 °C/m, (Kb,water = 0.52 °C/m)
8.6.4 Osmotic pressure
What is a semipermeable membrane?
One of the ancient technologies to cool drinking water. is to put it in a pottery pot
The walls of the pottery pots permit water inside the to pass through its walls
allowing water to be in contact with the colder atmosphere, but does not allow other
substances such as ions of other materials to pass through but only allows water
Cells’ wall of the living creatures depicted below, allow the passage of water from
outside to inside and vice versa but not any other materials
These walls are named “semipermeable membranes” because they allow the
passage of solvent molecules and blocks the passage of any solute molecules
Osmosis phenomenon
Osmosis is the selective passage of solvent molecules through a porous membrane
or a wall from a dilute solution to a more concentrated one
115
First look and inspect the following figure.
116
EXAMPLE 8.14
A I L of hemoglobin solution contains 35.0 g of hemoglobin. Calculate the molar mass of
hemoglobin if the osmotic pressure is 10.0 mmHg at 25 °C.
Solution
1 atm
π 10 mmHg ×
= 5.38 × 10–4 mol/L
760 mmHg
M = R×T = atm L
0.0821 × 298 K
mol K
nHb = M × V (L) = 5.38 × 10–4 mol/L × I L = 5.38 × 10–4 mol
m 35 g
MHb = n Hb = 5.38 × 10–4 mol = 6.51 × 104 g/mol
Hb
Practice Exercise 8.14
A 202-mL benzene solution containing 2.47 g of an organic polymer has an osmotic pressure of
8.63 mmHg at 21 °C. Calculate the molar mass of the polymer.
117
ANSWERS OF
PRAXTICE EXERCISES
118
1. CHEMISTRY: THE STUDY OF CHANGE
(Practice Exercise 1.1) 96.5 g
(Practice Exercise 1.2) 341.2 g
(Practice Exercise 1.3) A) 234.22 K and – 37.89 °F, B) 174.44 °C and 447.59 K, C) – 196 °C and
– 321.07 °F
(Practice Exercise 1.4) A) 98258.3 Pa and 0.99 bar, B) 466095 Pa and 3469 Torr, C) 135.0 mmHg
and 18000 Pa
(Practice Exercise 1.5) A) Two significant figures, B) Four significant figures, C) Three
significant figures, D) Two significant figures, E) Three significant figures
(Practice Exercise 1.6) A) 27 L, B) 4.4 g, C) 1.6 × 107 dm, D) 7.56 × 10−2 mL, E) 6.69 × 104 m,
(Practice Exercise 1.7) 1.07 kg= 2.36 lb
(Practice Exercise 1.8) 1.08 × 108 dm3 = 1.08 × 105 m3
kg g
(Practice Exercise 1.9) 534 m3 = 0.534 cm3
119
(Practice Exercise 4.3) A) SO2− + 2−
4 (aq) + 2H (aq) → H2 SO4 (aq), Because SO4 (aq) accepts
protons, it is a Brønsted base, B) HI(aq) → H + (aq) + I− (aq), BecauseHI(aq) donates protons,
it is a Brønsted acid
(Practice Exercise 4.4)
A) +3 -1
PF3
+7 -2
MnO− 4
(Practice Exercise 4.5) A) Hydrogen displacement, B) Combination reaction, C) Decomposition
reaction, D) Metal displacement
mol
(Practice Exercise 4.6) M = 0.45 L
(Practice Exercise 4.7) V = 494 mLv
(Practice Exercise 4.8) We take 34.2 mL from the stock solution, then we dilute it with water
until its volume reaches 200 mL
(Practice Exercise 4.9) Br% in the compound = 92.02%
(Practice Exercise 4.10) mKHB = 0.382 g
(Practice Exercise 4.11) volume of H2 SO4 = 52.4 mL
(Practice Exercise 4.12) volumeHI = 204 mL
5 GASES
(Practice Exercise 5.1) V = 9.29 L
(Practice Exercise 5.2) V = 30.54 L
(Practice Exercise 5.3) P2 = 4459.7 mmHg
(Practice Exercise 5.4) P2 = 1.785 atm
(Practice Exercise 5.5) P2 = 2.62 atm
(Practice Exercise 5.6) d = 13.12 g/Ld = 13.12 g/L
(Practice Exercise 5.7) M = 44.09 g/mol
(Practice Exercise 5.8) B2H6
(Practice Exercise 5.9) VNO2 = 9 L
(Practice Exercise 5.10) V = 37.16 L
(Practice Exercise 5.11) V = 740.150 L
(Practice Exercise 5.12) Pmeth = 1.286 atm, Peth = 0.066 atm, Pprop = 0.018 atm
g
(Practice Exercise 5.14) Muknown = 19.56 mol 𝑣
g
(Practice Exercise 5.15) This gas is carbon dioxide, because carbon dioxide molar mass is 44 mol,
fermentation of glucose produces carbon dioxide
(Practice Exercise 5.16) P = 164.2 atm, Because the real pressure is less than the theoretically
calculated pressure, the gas is not an ideal gas.
6 THERMOCHEMISTRY
(Practice Exercise 6.1) w = – 285.55 J
(Practice Exercise 6.2) q = − 34.80 kJ
(Practice Exercise 6.3) ΔE = − 63 J
(Practice Exercise 6.4) Heat evolved = − 6468.91 kJ
(Practice Exercise 6.5) ΔE = − 112.71 kJ
120
kJ
(Practice Exercise 6.6) q v = − 726.24 mol
(Practice Exercise 6.7) Tfinal = 21.2 °C
(Practice Exercise 6.8) Tfinal = 22.5 °C
(Practice Exercise 6.9) Heat per gram= − 41.83 J/g
(Practice Exercise 6.10) C(graphite) + 2S(rhombic) CS2(l) °
ΔHrxn = + 86.3 kJ
°
(Practice Exercise 6.11) C(graphite) + 2H2(g) → CH4(g) ∆Hf,CH4 (g) = – 74.84 kJ
8 SOLUTIONS
(Practice Exercise 8.1) According to the rule “like dissolves like” iodine (I2) is more soluble in
the nonpolar carbon disulfide
(Practice Exercise 8.2) NaNO3% = 10.44%
(Practice Exercise 8.3) X NaNO3 = 0.024
121
(Practice Exercise 8.4) molality = 9.29 molal
(Practice Exercise 8.5) molality = 10.76 molal
(Practice Exercise 8.6) molality = 9.29 molal
(Practice Exercise 8.7) Solute% = 0.83%
(Practice Exercise 8.8) A) At 100 ºC, B) At 10 ºC
mol
(Practice Exercise 8.9) c = 2.86 × 10–4 L atm
(Practice Exercise 8.10) Psolution = 37.81 mmHg, ΔP = 4.39 mmHg
(Practice Exercise 8.11) Psolution = 73.45 mmHg
(Practice Exercise 8.12) Tb,solution = 101.25 °C, Tf,solution = − 4.48 °C
(Practice Exercise 8.13) π = 20.88 atm
(Practice Exercise 8.14) Mpolymer = 2.6 × 104 g/mol
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