Lecture Note PDF

1.
Introduction to study of modern chemistry

Chemistry is the science that tries to find to understand the composition, properties, and
transformations of matter by studying the behavior of atoms and molecules. We study chemistry
to provide ourselves with a better understanding of the underlying workings of nature, to learn
how to make new materials with useful properties that satisfy particular needs.
Matter is anything that occupies space, has mass and classified by its state and its composition.
1.1. The atom in modern chemistry

A. Introduction to Atoms and Elements
According to Democritus, Nothing exists except atoms and empty space; everything else is
opinion. Chemical process is not just beakers and test tubes which are found in labs but it going
on everywhere all around us and inside us, all the stuff you see around you is made of atoms and
you are also made of atoms.
Examples:
Breathing O 2 binds to Fe in Hemoglobin in red blood cells and thousands of other

chemical processes going on in our cells and bodies
We get energy from food we eat: sugar + oxygen carbon dioxide + water + energy
We get energy for industry by combustion:

Butane + oxygen carbon dioxide + water +energy
Atomic Theory is the central theme of chemistry and most important idea in science. Chemistry
is central to science; it deals with matter (stuff of the world) and transformations of matter. It is
important and essential in physics, biology, geology, dentistry, medicine, nursing, engineering,
and philosophy .etc.
1. Daltons atomic theory
Daltons atomic theory of matter: (based on knowledge at that time):
General Chemistry L. Note for Pre-Engineering Students
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1. All matter is made of atoms. These indivisible and indestructible objects are the ultimate
chemical particles.
2. All the atoms of a given element are identical, in both weight and chemical properties.
However, atoms of different elements have different weights and different chemical
properties.
3. Compounds are formed by the combination of different atoms in the ratio of small whole
numbers.
4. A chemical reaction involves only the combination, separation, or rearrangement of atoms;
atoms are neither created nor destroyed in the course of ordinary chemical reactions.
Modern Chemistry 1790 to present day

Modern chemistry makes connection between experiment and theory
Experimental observation theory
Two modifications have been made to Daltons theory

1. Subatomic particles and (2) Isotopes were discovered.
2. Early experiments to characterize the atom
Based on the work of Dalton, Gay-Lussac, Avogadro, & others, chemistry was beginning to
make sense and the concept of the atom was clearly a good idea!
The electron
J.J. Thomson, English (1898-1903)found that when high voltage was applied to an evacuated
tube, a ray he called a cathode ray, since it emanated from the (-) electrode or cathode when
you apply a voltage across it was produced.
When the power was turned on, a "ray" could be seen striking the phosphor-coated end of the
tube and emitting a glowing spot of light. The rays were called cathode rays because they
originated at the negative electrode (cathode) and moved to the positive electrode (anode).
Cathode rays typically travel in a straight line, but in a magnetic field the path is bent, indicating
that the particles are charged, and in an electric field the path bends toward the positive plate.
The ray is identical no matter what metal is used as the cathode. It was concluded that cathode
rays consist of negatively charged particles found in all matter. The rays appear when these
particles collide with the few remaining gas molecules in the evacuated tube. Cathode ray
particles were later named electrons.
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He then measured the deflection of beams of e- to determine the charge-to-mass ratio

e/m = -1.76 x 108 C/g or -1.76 x 1011 C/Kg
The Nucleus
Figure bellow is representation of Rutherford's experiment. Tiny, dense, positively charged alpha
particles emitted from radium were aimed, like minute projectiles, at thin gold foil.
The data showed that very few particles were deflected at all, and that only 1 in 20,000 was
deflected by more than 900 ("coming backwards"). It seemed that these few particles were
being repelled by something small, dense, and positive within the gold atoms. From the data,
Rutherford calculated that an atom is mostly space occupied by electrons, but in the center of
that space is a tiny region, which he called the nucleus, that contains all the positive charge and
essentially all the mass of the atom. He proposed that positive particles lay within the nucleus
and called them protons.
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The modern view of atomic structure: an introduction element

All matter composed of only one type of atom is an element. There are 92 naturally occurring
elements, all others are manmade.
Atoms
Atom--the smallest particle of an element that retains the chemical properties of that element.
Nucleus-contains the protons and the neutrons; the electrons are located outside the nucleus.
Diameter of the nucleus is 10-13 cm. The electrons are located 10-8cm from the nucleus. A mass
of nuclear material the size of a pea would weigh 250 million tons! Very dense! Proton--positive
charge, responsible for the identity of the element, defines atomic number. Neutron--no charge,
same size & mass as a proton, responsible for isotopes, alters atomic mass number. Electron-negative charge, same size as a proton or neutron, but 1/2,000 the mass of a proton or neutron,
responsible for bonding, hence reactions and ionizations, easily added or removed. Atomic
number (Z) The number of p+ in an atom, all atoms of the same element have the same number
of p+. Mass number (A): the sum of the number of neutrons and p+ for an atom. A different
mass number does not mean a different element--just an isotope.
ISOTOPES
Isotopes--atoms having the same atomic number (# of p+) but a different number of neutrons
or mass number and have nearly identical chemical behavior but different physical behavior.
Most elements have at least two stable isotopes, there are very few with only one stable isotope
(Al, F, P)
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Elements and Compounds

Atoms are building blocks of nature/matter
Elements composed of one type of atom e.g. Na
Compounds - composed of two or more types of elements/atoms e.g. NaCl
1.2. Chemical Formulas, Chemical Equation and Reaction Yields
The Chemical formula for a compound is the symbols of the individual elements followed by
subscripts which indicate the number of atoms of that element. (If no subscript is given, it is
understood to be 1.) E.g., NaCl, H 2 O, C 12 H 22 O 11 .
Shortly chemical formula is the short hand notation of one or more elements and compounds.
E.g., the formulas for elements potassium, oxygen, nitrogen and the compound sodium sulphate
are K, O 2 , N 2 and NaSO 4 respectively.
The meaning of a chemical equation
A chemical equation is a chemists shorthand expression for describing a chemical change. As an
example, - consider what takes place when iron rusts. The equation for this change is:
Fe + O 2 Fe 2 O 3
In this expression, the symbols and formulas of the reacting substances, called the reactants, are
written on the left side of the arrow and the products of the reaction are written on the right side.
The arrow is read as gives, yields, or forms and the plus (+) sign is read as and. When
the plus (+) sign appears between the formulas for two reactants, it can be read as reacts with.
(The + sign does not imply mathematical addition.)
The equation, above, can be read as iron reacts with oxygen to yield (or form) iron (III) oxide.
Balancing a chemical equation
As it is written, the equation indicates in a qualitative way what substances are consumed in the
reaction and what new substances are formed. In order to have quantitative information about the
reaction, the equation must be balanced so that it conforms to the Law of Conservation of Matter.
That is, there must be the same number of atoms of each element on the right hand side of the
equation as there are on the left hand side.
Half-Reaction Method for Balancing Redox Reactions
The following steps are used in balancing a redox reaction by the half-reaction method:
Step1. Divide the skeleton reaction into two half-reactions
Step2. Balance the atoms and charges in each half-reaction
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Step3. If necessary, multiply one or both half-reactions by an integer to make the number
of e - gained in the reduction equal the number lost in the oxidation.
Step4. Add the balanced half-reactions, and include states of matter.
Step5. Check that the atoms and charges are balanced.
Example: Balance the redox reaction between dichromate ion and iodide ion to form chromium
(III) ion and solid iodine, which occurs in acidic solution
Cr 2 O72- (aq) + I- (aq) Cr3+(aq) + I 2(s) [acidic solution]
Types of chemical reactions
Most inorganic reactions can be classified into one of five general categories: direct union or
combination, decomposition, displacement, metathesis or double displacement, and combustion
reactions. Each of these will be discussed in more detail in the following sections.
1. Direct Union or Combination Reactions
Any reaction in which two or more substances combine to form a single product is a direct union
or combination reaction. The general form of a direct union reaction is
A + B AB
2Na + Cl2 2NaCl
2. Decomposition Reactions
Decomposition is the reverse of combination. That is, a single reactant is broken down into two
or more products either elements or compounds. A decomposition reaction will take place
because the compound is unstable or as a result of heating or electrical decomposition
(electrolysis). The general form for a decomposition reaction is:
AB A + B
2HgO 2Hg + O 2
3. Single Displacement Reactions (Sometimes called oxidation-reduction equations)

A displacement reaction involves an element reacting with a compound whereby the element
displaces a second element from the compound. The general form of this type reaction is:
A + BC AC + B
Zn + 2HCl ZnCl2 + H 2
4. Metathesis or Double Displacement Reactions

A metathesis is a double displacement reaction that usually occurs in water solution. The general
form of a metathesis reaction is:
AB + CD AD + CB
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In order to have any appreciable degree of completion of metathesis reactions, one or both of the
products must become unavailable for the reverse reaction. The principal conditions that favor
the completion of these reactions are:
(1) Formation of an insoluble compound - a precipitate
(2) Formation of a gas
(3) Formation of water
Metathesis reactions are generally classified as precipitation reactions or as neutralization
reactions.
a. Precipitation Reactions
In this type of reaction, two compounds which are water soluble react to form two new
compounds, one of which is a precipitate (i.e. insoluble in water). The precipitate is often
indicated by an arrow pointing downward, , written next to its formula.
AgNO 3 + NaCl AgCl + NaNO 3
b. Neutralization Reactions (sometimes called acid-base reactions)
A neutralization reaction occurs between an acidic compound and a basic compound to form a
chemical salt and water.
HCl + NaOH NaCl + H 2 O
5. Combustion Reactions
Combustion reactions generally apply to organic compounds, such as hydrocarbons, which are
used as fuels. In these cases, the compound is being burned in air (or oxygen) and producing
carbon dioxide and water as products. A general form for a combustion reaction is:
C 3 H 8 + 5O 2 3CO 2 + 4H 2 O
The meaning of a chemical formula
A chemical formula is a shorthand method of representing the elements in a compound. The
formula shows the formulas of the elements in the compound and the ratio of the elements to one
another. For example, the formula for sodium chloride: NaCl tells us that the compound is
composed of the elements sodium, Na, and chlorine, Cl, in a one-to-one ratio, That is, one atom
of sodium combines with one atom of chlorine.
When elements combine in different ratios, subscripts are added, following the element symbol,
to -indicate that the number of atoms of that element in the compound if it is greater than one.
The subscript refers only to the element it immediately follows. For example, the formula for
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magnesium bromide: MgBr 2 tells us that two bromine atoms combine with one magnesium
atom.
Types of Chemical Formulas
In a chemical formula, element symbols and numerical subscripts show the type and number of
each atom present in the smallest unit of the substance. There are several types of chemical
formulas for a compound:
1. The empirical formula shows the relative number of atoms of each element in the compound.
It is the simplest type of formula and is derived from the masses of the component elements.
For example, in hydrogen peroxide, there is 1 part by mass of hydrogen for every 16 parts by
mass of oxygen. Therefore, the empirical formula of hydrogen peroxide is HO: one H atom
for every O atom.
2. The molecular formula shows the actual number of atoms of each element in a molecule of the
compound. The molecular formula of hydrogen peroxide is H 2 O 2 ; there are two H atoms and
two O atoms in each molecule.
3. A structural formula shows the number of atoms and the bonds between them; that is, the
relative placement and connections of atoms in the molecule. The structural formula of
hydrogen peroxide is H-O-O-H; each H is bonded to an O, and the O's are bonded to each
other.
Example: During excessive physical activity, lactic acid (M = 90.08 g/mol) forms in muscle
tissue and is responsible for muscle soreness. Elemental analysis shows that this compound
contains 40.0 mass % C, 6.71 mass % H, and 53.3 mass %O.
(a) Determine the empirical formula of lactic acid.
(b) Determine the molecular formula.
Exercise: One of the most widespread environmental carcinogens (cancer-causing agents) is
benzo[a]pyrene (M = 252.30 g/mol). It is found in coal dust, in cigarette smoke, and even in
charcoal-grilled meat. Analysis of this hydrocarbon shows 95.21 mass % C and 4.79 mass % H.
What is the molecular formula of benzo[a]pyrene?
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Reaction yields
There are three types of reaction yields. These are namely actual yield (AY), theoretical yield
(TY) and percentage yield (%Y).
Actual yield is the amount of product you actually got while theoretical yield is the
maximum possible yield or the calculated product. Be sure that actual and theoretical
yields are both in the same units so that units cancel in the calculation.
Notice: Always theoretical yield is greater than or equal to actual yield.

Percent Yield: is the actual yield expressed as a percentage of the theoretical yield. It is used is
cases where a chemical transformation occurs.
To calculate the % yield, you need the following information:
1. The molar ratio of product to starting material.
2. Molecular weights of product and starting material.
3. Limiting reagent.
Percent yield is calculated as follows:
% yield =
Actual yield (g)
Theoretical yield (g)
x 100
Calculating percent yield actually involves a series of short calculations. Yield calculations can
be broken up into a series of six steps. These are:
1. Write a balanced equation for the reaction
2. Calculate the molecular weight of each reactant and product
3. Convert all amounts of reactants and products into moles
4. Figure out the limiting reagent
5. Calculate the theoretical yield
6. Calculate the percentage yield
Limiting reagent; the reactant run out first is the limiting reagent while the reactant
remains left as excess is excess reagent.
Exercise1: When 5.00 g of KClO 3 is heated it decomposes according to the equation:

2KClO 3 2KCl + 3O 2
a) Calculate the theoretical yield of oxygen.
b) Give the % yield if 1.78 g of O 2 is produced.
c) How much O 2 would be produced if the percentage yield was 78.5%?
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Exercise2: How many grams of solid aluminum sulfide can be prepared by the reaction of 10.0 g
of aluminum and 1 5.0 g of sulfur?
a. How much of the reactant is remains in excess?
b. Give the % yield if 22.3 g of Al2 S 3 is produced.
Chapter Two
2. Chemical bonding and molecular structure
2.1. Chemical bonding: the classical description
By classical, we mean models that do not take into account the quantum behavior of small
particles, notably the electron. These models generally assume that electrons and ions behave as
point charges which attract and repel according to the laws of electrostatics. Although this
completely ignores what has been learned about the nature of the electron since the development
of quantum theory. In the 1920s, these classical models have not only proven extremely useful,
but the major ones also serve as the basis for the chemists general classification of compounds
into covalent and ionic categories.
1. The Ionic Bond
A chemical compound in which the component atoms exist as ions is called an ionic
compound. Potassium chloride, KCl, is a common ionic compound. The electronic
configurations of the potassium and chloride ions obey the octet rule.
The structure of crystalline KCl is shown in fig. below. In the KCl structure, which is typical of
many ionic compounds, each positive ion is surrounded by negative ions, and each negative ion
is surrounded by positive ions. The crystal structure is stabilized by an interaction between ions
of opposite charge. Such a stabilizing interaction between opposite charges is called an
electrostatic attraction. An electrostatic attraction that holds ions together, as in crystalline
KCl, is called an ionic bond. Thus, the crystal structure of KCl is maintained by ionic bonds
between potassium ions and chloride ions. The ionic bond is the same in all directions; that is, a
positive ion has the same attraction for each of its neighboring negative ions, and a negative ion
has the same attraction for each of its neighboring positive ions.
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When an ionic compound such as KCl dissolves in water, it dissociates into free ions (each
surrounded by water). Each potassium ion moves around in solution more or less independently
of each chloride ion. The conduction of electricity by KCl solutions shows that the ions are
present. Thus, the ionic bond is broken when KCl dissolves in water.
To summarize, the ionic bond
1. is an electrostatic attraction between oppositely charged ions;
2. is the same in all directionsthat is, it has no preferred orientation in space; and
3. is broken when an ionic compound dissolves in water.
2. The Covalent Bond
Many compounds contain bonds that are very different from the ionic bond in KCl. these
compounds will not conduct electricity in solutions. This observation indicates that these
compounds are not ionic. According to this model, the chemical bond in a nonionic compound is
a covalent bond, which consists of an electron pair that is shared between bonded atoms. Lets
examine some of the ideas associated with the covalent bond.
The Polar Covalent Bond
In many covalent bonds the electrons are not shared equally between two bonded atoms.
Consider, for example, the covalent compound hydrogen chloride, HCl. (Although HCl dissolves
in water to form H 3 O+ and Cl- ions, in the gaseous state pure HCl is a covalent compound). The
electrons in the H-Cl covalent bond are unevenly distributed between the two atoms; they are
polarized, or pulled, toward the chlorine and away from the hydrogen. A bond in which
electrons are shared unevenly is called a polar bond. The H-Cl bond is an example of a polar
bond. The tendency of an atom to attract electrons to itself in a covalent bond is indicated by its
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electronegativity. When the ligand (Lewis base) donates the electron pair and the metal ion
(Lewis acid) accepts it to form one of the covalent bonds of the complex ion. Such a bond, in
which one atom in the bond contributes both electrons, is called a coordinate covalent bond,
although, once formed, it is identical to any covalent single bond.
2.2. Introduction to quantum mechanics
This sub portion introduces some of the basic principles of quantum mechanics. First, it reviews
the experimental results that overthrew the concepts of classical mechanics. These experiments
led to the conclusion that particles may not have an arbitrary energy and that the classical
concepts of 'particle' and 'wave' blend together. In quantum mechanics, all the properties of a
system are expressed in terms of a wave function that is obtained by solving the Schrodinger
equation. Quantum mechanics is the branch of physics that mathematically describes the wave
properties of submicroscopic particles. It is a collection of postulates based on a huge number of
experimental observations.
Classical physics (mechanics) (1) predicts a precise trajectory for particles, with precisely
specified locations and momenta at each instant, and (2) allows the translational, rotational, and
vibrational modes of motion to be excited to any energy simply by controlling the forces that are
applied. These conclusions agree with everyday experience. Everyday experience, however, does
not extend to individual atoms, and careful experiments of the type described below have shown
that classical mechanics fails when applied to the transfers of very small energies and to objects
of very small mass.
Classical mechanics (newton's mechanics) and maxwell's equations (electromagnetics theory)
can explain macroscopic phenomena such as motion of billiard balls or rockets while quantum
mechanics is used to explain microscopic phenomena such as photon-atom scattering and flow
of the electrons in a semiconductor. In newtonian mechanics, the laws are written in terms of
particle trajectories. It state descriptor of newtonian physics. A particle is an indivisible mass
point object that has a variety of properties that can be measured, which we call observables.
Quantum particles can act as both particles and waves in nature (wave-particle duality.
Quantization of energy is yet another property of "microscopic" particles.
The electromagnetic field is characterized by a wavelength, (lambda), the distance between the
neighbouring peaks of the wave, and its frequency, (nu), and the number of cycles per second
at which its displacement at a fixed point returns to its original value (Fig. 2). The frequency is
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measured in hertz, where 1Hz = 1 s-1. The wavelength and frequency of an electromagnetic wave
are related by
=
Fig.2: The wave length of a waveis the peak-to-peak distance.

The shorter the wavelength leads the higher the frequency. The characteristics of the wave are
also reported by giving the wave number, (nu tilde), of the radiation, where
1
=

The first clue in the development of quantum theory came with the discovery of the
=
deBroglie relation. In 1923, Louis de Broglie reasoned that if light exhibits particle aspects,
perhaps particles of matter show characteristics of waves. He postulated that a particle with mass
m and a velocity v has an associated wavelength. Light has both wave & particle properties. He
proposed that all moving objects have wave properties. Thus
For wave characteristics: E = h = hc/
For particles: E = mc2 (Einstein)
Therefore, mc = h / and for particles (mass) x (velocity) = h / .where wave length () for
particles is called the de Broglie wavelength.
Example: Determine the de Broglie wavelength of a person with a mass of 90 kg who is running
10 m/s?
The description and classification of the electromagnetic field according to its frequency and
wavelength were vied in the electromagnetic spectrum.
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Fig.2.1: The electromagnetic spectrum and the classification of the spectral regions.
In 1900 Max Planck found that he could account for the permitted energies of an electromagnetic
oscillator of frequency are integer multiples of hv. Light is a wave arriving as stream of
particles called "photons". Each photon is considered as quantum of energy. An increase in the
frequency the cause for increase in the energy similarly, an increase in the wavelength gives a
decrease in the energy of the photon.
E = hv =
, Where h (Planck's constant) = 6.63x1034Js.
Example: Determine the energies of photons with wavelengths of 650 nm, 700 nm?
Solution:
a. Frequencies 4.50x1014 s1, 6.50x1014 s1, respectively.
b. The total energy of a stream of particles (photons) of that energy will be:
E = nhv
Where n = 1, 2 ... (only discrete energies).
c. The wave number?

2.3. Quantum mechanics and atomic structure
In this sub portion we see how to use quantum mechanics to describe the electronic structure of
an atom, the arrangement of electrons around a nucleus. It provides universal description of the
electron distribution in atoms. The concepts we meet are of central importance for understanding
the structures and reactions of atoms and molecules, and hence have extensive chemical
applications. Bohrs theory established the concept of atomic energy levels but did not
thoroughly explain the wave-like behavior of the electron. Current ideas about atomic structure
depend on the principles of quantum mechanics, a theory that applies to subatomic particles such
as electrons.
Atomic structure elucidated by interaction of matter with light. Light properties: characterized by
wavelength,, and frequency,. Light is an electromagnetic radiation, a wave of oscillating
electric and magnetic influences causes the so called fields. Frequency and wavelength have
inversely proportional to each other. The structure of an atom is composed of subatomic particles
(proton, neutron, and electron). When it interacts with quanta will causes accumulation of energy
like potential, kinetic, translational etc.
c =
where c = the speed of light = 3.00x108 m/s; units = s1, = m
Examples: Calculate the frequency of light with a wavelength of 500 nm?

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Schrdinger applied: idea of an electron behaving as a wave to the problem of electrons in

atoms. Although we cannot precisely define an electrons orbit, we can obtain the probability of
finding an electron at a given point around the nucleus. Erwin Schrodinger defined this
probability in a mathematical expression called a wave function, denoted (psi). It is a function
of distance and two angles.
For 1 electron, corresponds to an orbital the region of space within which an

electron is found.
Does not describe the exact location of the electron.
2 are proportional to the probability of finding an electron at a given point.

P
Uncertainty Principle: Problem of defining nature of electrons in atoms solved by Werner

Heisenberg in 1927 cannot simultaneously define the position and momentum (p = mv) of an
electron. We can no longer think of an electron as having a precise orbit in an atom. To describe
such an orbit would require knowing its exact position and velocity. Heisenbergs uncertainty
principle is a relation that states that the product of the uncertainty in position (x) and the
uncertainty in momentum (mv x ) of a particle can be no larger than h/4.
(x)(m )
When m is large (for example, a baseball) the uncertainties are small, but for electrons, high
uncertainties disallow defining an exact orbit. At best we can describe the position and velocity
of an electron by a probability distribution, which is given by 2. The square of probability ( 2)
P
is proportional to the probability of finding an electron at a given point.
Orbital Quantum Numbers: An atomic orbital is defined by 3 quantum numbers: n, l, and ml .

Electrons are arranged in shells and subshells of orbitals.
n shell
l subshell
ml designates an orbital within a subshell
Generally, the wave function of a particle (atom) must be;
Single valued, Continuous, Continuous first derivative, Quadratically integrable
And
*d must be finite
, where is volume element (i. e. = , , )
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Examples: Give the name, magnetic quantum numbers, and number of orbitals for each sublevel
with the given quantum numbers:
(a) n = 3, l = 2 (b) n = 2, l = 0 (c) n = 5, l = 1 (d) n = 4, l = 3
Answer
n
Possible m l Values
(a)
-2, -1, 0, +1, + 2
(b)
(c)
(d)
sublevel name
No. of
Orbitals
3d
2s
-1,0,+1
5p
-3, -2, -1, 0, +1, +2, +3
4f
To name the sublevel (subshell), we combine the n value and l letter designation. We know l, so
we can find the possible ml values, whose total number equals the number of orbitals.
2.4. Quantum mechanics and molecular structure
Quantum mechanics allows the prediction of molecular structure such as: bond lengths, bond
angles, and dissociation energies. The concepts developed in the structure of atomic orbitals, can
be extended to a description of the electronic structures of molecules. There are two principal
quantum mechanical theories of molecular electronic structure. These are molecular orbital
theory (MO theory) and valence-bond theory is the concept of the shared electron pair. We see
how to write the wave function for such a pair, and how it may be extended to account for the
structures of a wide variety of molecules. The theory introduces the concepts of and bonds,
promotion, and hybridization that are used widely in chemistry.
The concept of atomic orbital
is extended to that of molecular orbital, which is a wave function that spreads over all the atoms
in a molecule.
There are two major approaches to the calculation of molecular structure, valence bond theory
(VB theory) and The Schrodinger equation for a hydrogen atom can be solved exactly; an exact
solution is not possible for any molecule because the simplest molecule consists of three particles
(two nuclei and one electron).
We therefore adopt the Born-Oppenheimer approximation in which it is supposed that the nuclei,
being so much heavier than an electron, move relatively slowly and may be treated as stationary
while the electrons move in their field. We can therefore think of the nuclei as being fixed at
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arbitrary locations, and then solve the Schrodinger equation for the wave function of the
electrons alone.
Valence bond theory: In VB theory, a bond is regarded as forming when an electron in an
atomic orbital on one atom pairs its spin with that of an electron in an atomic orbital on another
atom. The basic principle of VB theory is that a covalent bond forms when orbitals of two atoms
overlap and the overlap region, which is between the nuclei, is occupied by a pair of electrons.
("Orbital overlap" is another way of saying that the two wave functions are in phase, so the
amplitude increases between the nuclei).
Example: considering the simplest possible chemical bond in molecular hydrogen, H 2 .
= 1 (1 )1 (2 )
if electron 1 is on atom A and electron 2 is on atom B; in this chapter we use X (chi) to denote
atomic orbitals. For simplicity, we shall write this wavefunction as =A(l) B(2). When the
atoms are close, it is not possible to know whether it is electron 1 that is on A or electron 2. An
equally valid description is therefore = A (2) B (l), in which electron 2 is on A and electron 1 is
on B. When two outcomes are equally probable, quantum mechanics instructs us to describe the
true state of the system as a superposition of the wavefunctions for each possibility.
= A(1)B(2) A(2)B(1)
It turns out that the combination with lower energy is the one with a + sign, so the valence-bond
wavefunction of the H 2 molecule is
= A(1)B(2) + A(2)B(1)
This wave function is called a bond. A bond arises from the spin pairing of electrons in two p
orbitals that approach side-by-side.
Example1: Use partial orbital diagrams to describe how mixing of the atomic orbitals of the
central atom(s) leads to the hybrid orbitals in each of the following:
(a) Methanol, CH 3 OH
(b) Sulfur tetrafluoride, SF4
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b
Examples: Describe the types of bonds and orbitals in acetone, (CH 3 HCO.
From the Lewis structure, we determine the number and arrangement of electron groups around
each central atom, along with the molecular shape. From that, we postulate the type of hybrid
orbitals involved. Then, we write the partial orbital diagram for each central atom before and
after the orbitals are hybridized.
(a).For CH 3 OH. The electron-group arrangement is tetrahedral around both C and O atoms.
Therefore, each central atom is Sp3 hybridized. The C atom has four half filled Sp3 orbitals:
Answer: the shape around each central atom to postulate the type of the hybrid orbitals, paying
attention to the multiple bonding of the C and O bond.
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Molecular orbital theory:

In VB theory, a molecule is pictured as a group of atoms bound together through localized
overlap of valence-shell atomic orbitals. In MO theory, a molecule is pictured as a collection of
nuclei with the electron orbitals delocalized over the entire molecule. The MO model is a
quantum-mechanical treatment for molecules. Just as an atom has atomic orbitals (AOs) with a
given energy and shape that are occupied by the atom's electrons, a molecule has molecular
orbitals (MOs) with a given energy and shape that are occupied by the molecules electrons.
Despite the great usefulness of MO theory, it too has a drawback: MOs are more difficult to
visualize than the easily depicted shapes of VSEPR theory or the hybrid orbitals of VB theory.
The Central Themes of MO Theory
Several key ideas of MO theory appear in its description of the hydrogen molecule and other
simple species. These ideas include the formation of MOs, their energy and shape, and how they
fill with electrons.
Formation of molecular orbitals: because electron motion is so complex, we use
approximations to solve the Schrodinger equation for an atom with more than one electron.
Similar complications arise even with H 2 , the simplest molecule, so we use approximations to
solve for the properties of MOs. The most common approximation mathematically combines
(adds or subtracts) the atomic orbitals (atomic wave functions) of nearby atoms to form MOs
(molecular wave functions).
When two H nuclei lie near each other, as in H 2 , their AOs will overlap. The two ways of
combining the AOs are as follows:
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a. Adding the wave functions together: This combination forms a bonding MO, which has a
region of high electron density between the nuclei. Additive overlap is analogous to light
waves reinforcing each other, making the resulting amplitude higher and the light brighter.
For electron waves, the overlap increases the probability that the electrons are between the
nuclei see fig. a below.
Figure. An analogy between light waves and atomic wave functions, when light waves undergo
interference, their amplitudes either add together or subtract.
(a), when the amplitudes of atomic wave functions (dashed lines) are added, a bonding molecular
orbital (MO) results, and electron density (red line) increases between the nuclei.
(b) Conversely, when the amplitudes of the wave functions are subtracted, an antibonding MO
results, which has a node (region of zero electron density) between the nuclei.
b. Subtracting the wave functions from each other. This combination forms an antibonding MO,
which has a region of zero electron density (a node) between the nuclei (Figure above b).
Subtractive overlap is analogous to light waves canceling each other, so that the light
disappears. With electron waves, the probability that the electrons lie between the nuclei
decreases to zero.
The two possible combinations for hydrogen atoms H A and H B are
AO of H A + AO of H B = bonding MO of H 2 (more e - density between nuclei)
AO of H A - AO of H B = antibonding MO of H 2 (less e- density between nuclei)
Notice that the number of AOs combined always equals the number of MOs formed: two H
atomic orbitals combine to form two H 2 molecular orbitals.
Energy and Shape of H 2 Molecular Orbitals The bonding MO is lower in energy and the
antibonding MO higher in energy than the AOs that combined to form them. Let's examine
Figure below to see why this is so.
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Fig. Contours and energies of the bonding and anti bonding molecular orbitals (MOs) in H 2
When two H1s atomic orbitals (AOs) combine, they form two H 2 MOs. The bonding MO
( 1s) forms from addition of the AOs and is lower in energy because most of its electron
R
density lies between the nuclei (shown as dots). The antibonding MO ( 1s*) forms from
R
subtraction of the AOs and is higher in energy because there is a node between the nuclei
and most of the electron density lies outside the internuclear region.
The bonding MO in H 2 is spread mostly between the nuclei, with the nuclei attracted to the
intervening electrons. An electron in this MO can delocalize its charge over a much larger
volume than is possible in an individual AO in either H. Because the electron-electron repulsions
are reduced, the bonding MO is lower in energy than the isolated AOs. Therefore, when
electrons occupy this orbital, the molecule is more stable than the separate atoms. In contrast, the
anti bonding MO has a node between the nuclei and most of its electron density outside the
internuclear region. The electrons do not shield one nucleus from the other, which increases the
nucleus-nucleus repulsion and makes the antibonding MO higher in energy than the isolated
AOs. Therefore, when the antibonding orbital is occupied, the molecule is less stable than when
this orbital is empty.
Both the bonding and antibonding MOs of H 2 are sigma () MOs because they are cylindrically
symmetrical about an imaginary line that runs through the two nuclei. The bonding MO is
denoted by 1s that is, a MO formed by combination of 1s AOs. Antibonding orbitals are
R
denoted with a superscript star, so the orbital derived from the 1s AOs is 1s* (spoken "sigma,
R
one ess, star").
To interact effectively and form MOs, atomic orbitals must have similar energy and orientation.
These orbitals on two H atoms have identical energy and orientation, so they interact strongly.
Filling Molecular Orbitals with electrons is just the same as they fill AOs:
MOs are filled in order of increasing energy (aufbau principle).
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An MO has a maximum capacity of two electrons with opposite spins (exclusion prin.).
MOs of equal energy are half-filled, with spins parallel, before any of them is
completely filled (Hund's rule).
2.5. Bonding in organic molecules
It begins with an introduction to the important classes of organic molecules followed by a
description of chemical bonding in those molecules. Most organic molecules have much more
complex structures than most inorganic molecules.
1. Electron configuration, electro negativity, and covalent bonding: Carbon's ground-state
electron configuration of [He] 2S22p2 -four electrons more than He. Its electro negativity are
midway between the most metallic and nonmetallic elements of Period 2. Therefore, carbon
shares electrons to attain a filled outer (valence) level, bonding covalently in all its elemental
forms and compounds.
2. Bond properties, catenation, and molecular shape: The number and strength of carbons
bonds lead to its outstanding ability to catenate (form chains of atoms), which allows it to
form a multitude of chemically and thermally stable chain, ring, and branched compounds.
Through the process of orbital hybridization carbon forms four bonds in virtually all its
compounds, and they point in as many as four different directions.
3. Molecular stability. Although silicon and several other elements also catenate, none can
compete with carbon.
The Chemical Diversity of Organic Molecules
1. Bonding to heteroatoms. Many organic compounds contain heteroatoms, atoms other than C
or H. The most common heteroatoms are N and O, but S, P, and the halogens often occur as well.
2. Electron density and reactivity. Most reactions start-that is, a new bond begins to form-when
a region of high electron density on one molecule meets a region of low electron density on
another.
For example, consider four bonds commonly found in organic molecules:
The C-C bond: When C is singly bonded to another C, as occurs in portions of nearly
every organic molecule, the elecronegativity (EN) values are equal and the bond is
nonpolar. Therefore, in general, C-C bonds are unreactive.
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The C-H bond: This bond, which also occurs in nearly every organic molecule, is very
nearly nonpolar because it is short (109 pm) and the EN values of H (2.1) and C (2.5) are
close. Thus, C-H bonds are largely unreactive as well.
The C-O bond: This bond, which occurs in many types of organic molecules, is highly
polar (EN = 1.0), with the O end of the bond electron rich and the C end electron poor.
As a result of this imbalance in electron density, the C-O bond is reactive and, given
appropriate conditions, a reaction will occur there.
Bonds to other heteroatoms: Even when a carbon-heteroatom bond has a small EN,
such as that for C-Br (EN = 0.3), or none at all, as for C S (EN = 0), heteroatoms
like these are large, arid so their bonds to carbon are long, weak, and thus reactive.
3. Nature of functional groups. One of the most important ideas in organic chemistry is that of
the functional group, a specific combination of bonded atoms that reacts in a characteristic
way, no matter what molecule it occurs in. In nearly every case, the reaction of an organic
compound takes place at the functional group. Functional groups vary from carbon-carbon
multiple bonds to several combinations of carbon-heteroatom bonds, and each has its own
pattern of reactivity. A particular bond may be part of one or more functional groups. For
example, the C-O bond occurs in four functional groups.
2.6. Bonding in transition metals compounds and coordination complexes

The transition elements (transition metals) make up the d block (B groups) and f block (inner
transition elements). In this chapter, we cover the d-block elements only. We first discuss some
properties of the elements and then focus on the most distinctive feature of their chemistry, the
formation of coordination compounds-substances that contain complex ions.
The electron configuration of the transition metal atom that correlates with physical properties
of the element: such as density and magnetic behavior, whereas it is the electron configuration of
the ion that determines the properties of the compounds.
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Sample Problem:
1. Write the Electron Configurations of Transition Metal Atoms and Ions?
a) Fe and Ni
b) Cd2+ and V3+
2. Discus the physical and chemical properties of transition metals?
Coordination compounds
The most distinctive aspect of transition metal chemistry is the formation of coordination
compounds (also called complexes). These are substances that contain at least one complex ion,
a species consisting of a central metal cation (either a transition metal or a main-group metal)
that is bonded to molecules and/or anions called ligands.
The coordination compound is [Co(NH 3 ) 6 ]Cl3 , the complex ion (always enclosed in square
brackets) is [Co(NH 3 ) 6 ]3+ , the six NH 3 molecules bonded to the central Co3+ are ligands, and
the three Cl- ions are counter ions. A coordination compound behaves like an electrolyte in
water.
A complex ion is described by the metal ion and the number and types of ligands attached to it.
Its structure has three key characteristics-coordination number, geometry, and number of donor
atoms per ligand:
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Coordination number: The coordination numbers is the number of ligand atoms bonded
directly to the central metal ion.
Geometry: The geometry (shape) of a complex ion depends on the coordination number
and nature of the metal ion.
Example: A complex ion whose metal ion has a coordination number of 2 is linear. The
coordination number 4 gives rise to either of two geometries-square planar or tetrahedral.
Most d8 metal ions form square planar complex ions. The d10 ions are among those that
form tetrahedral complex ions. A coordination number of 6 results in an octahedral
geometry, as shown by [Co (NH 3 ) 6 ]3+
Donor atoms per ligand. The ligands of complex ions are molecules or anions with one
or more donor atoms that each donates a lone pair of electrons to the metal ion to form a
covalent bond.
Complex Ion and Ligands

Definitions
Complex ion - a metal ion with Lewis bases attached to it through coordinate covalent bonds.
A Complex (Coordination compound) is a compound consisting either of complex ions with
other ions of opposite charge or a neutral complex species.
Ligand - is the Lewis bases attached to the metal ion in a complex. Lewis bases are electron pair
donors. They can be ions or neutral molecules. Anions are the most common ionic Lewis bases.
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Cations only very rarely form ligands with metal ions because the electron pair is usually held in
place by the positive charge.
Coordination number- the total number of bonds metal forms with ligands. The most common
coordination number is 6, although 4 are somewhat common also. Complex ions with
coordination number of 2 through 8 are known.
Monodentate is ligand that bonds through one of its atoms to the metal ion.
Example H 2 O, NH 3 , CO, CN-)
Bidentate is ligand that bond through two of its atoms with the metal ion.
Example C 2 O 4 2- , ethylenediamine (C 2 H 8 N 2 ) represented as "en")
Polydentate is ligand that bonds through two or more of its atoms to the metal ion.
Example EDTA)
Chelate - a complex formed from polydentate ligands
Nomenclature of Complex ions
1. Name the cation first and then the anion.
2. Nonionic compounds are given a one word name.
3. Name ligands:
A. ligands are named first and central atom last
B. ligands are named in alphabetical order
C. Anionic ligands end in -o. For anions that end in -ide(e.g. chloride, hydroxide), ate (e.g. sulfate, nitrate), and - ite (e.g. nirite), change the endings as follows:
-ide -o; e.g., chloride chloro and hydroxide hydroxo
-ate -ato; e.g., sulfate sulfato and nitrate nitrato
-ite - ito; e.g., nitrite nitrito
D. For neutral ligands, the common name of the molecule is used (e.g. H 2 NCH 2 CH 2 NH 2
(ethylenediamine)). Important exceptions: water is called aqua, ammonia is called
ammine, carbon monoxide is called carbonyl, and the N 2 and O 2 molecules are
called dinitrogen and dioxygen.
E. the ligand name is preceded by a Latin or Greek prefix to indicate how many are
present di, tri, tetra, penta, hexa, if the ligand already contains a Greek prefix (e.g.
ethylene diamine) or if it is a polydentate ligand (i.e. it can attach at more than one
coordination site), the prefixes , by using bis, tris, tetrakis, pentakis
Page 26
4. In a neutral or cationic complex, the name of the central metal is followed by its oxidation
number in Roman numerals in parentheses.
5. In an anionic complex, the suffix .ate is added to the name of the central metal, followed by its
oxidation number in Roman numerals in parentheses.
Examples
[Cr(NH 3 ) 3 (H 2 O) 3 ]Cl3
-triamminetriaquachromium(III) chloride
[Pt(NH 3 ) 5 Cl]Br 3
-pentaamminechloroplatinum(IV) bromide
[Pt(H 2 NCH 2 CH 2 NH 2 ) 2 Cl2 ]Cl2
-dichlorobis(ethylenediamine)platinum(IV) chloride
K 3 [CoF6 ]
-potassium hexafluorocobaltate(III)
Bonding and Properties of Complexes

In this section, we consider two models that address, in different ways, several key features of
complexes: how metal-ligand bonds form, why certain geometries are preferred, and why these
complexes are brightly colored and often paramagnetic.
According to Valence bond (VB) theory, in the formation of a complex ion, the filled ligand
orbital overlaps the empty metal-ion orbital. The ligand (Lewis base) donates the electron pair,
and the metal ion (Lewis acid) accepts it to form one of the covalent bonds of the complex ion
(Lewis adduct). Such a bond, in which one atom in the bond contributes both electrons, is called
a coordinate covalent bond.
VB concept of hybridization proposes the mixing of particular combinations of s, p, and d

orbitals to give sets of hybrid orbitals, which have specific geometries.
Let's discuss the orbital combinations that lead to octahedral, square planar, and tetrahedral
geometries.
Octahedral Complexes: d2sp3 hybrid orbital.
Page 27
Square Planar Complexes: Metal ions with a d8 configuration usually form square planar
complexes and form four dsp2 hybrid orbitals. most of the time in strong ligand.
Tetrahedral Complexes: having sp3 hybrid orbital.
Crystal Field Theory: The VB model is easy to picture and rationalizes bonding and shape, but
it treats the orbitals as little more than empty "slots" for accepting electron pairs. Consequently,
it gives no insight into the colors of coordination compounds and sometimes predicts their
magnetic properties incorrectly. In contrast to the VB approach, crystal field theory provides
little insight about metal-ligand bonding but explains color and magnetism clearly.
Splitting of d Orbitals in an Octahedral Field of Ligands
The crystal field model explains that the properties of complexes result from the splitting of dorbital energies, which arises from electrostatic interactions between metal ion and ligands.
Page 28
An energy diagram of the orbitals shows that all five d orbitals are higher in energy in the
forming complex than in the free metal ion because of repulsions from the approaching ligands,
but the orbital energies split, with two d orbitals higher in energy than the other three. The two
higher energy orbitals are called e g orbitals, and the three lower energy ones are t 2g orbitals.
(These designations refer to features of the orbitals that need not concern us here.) The splitting
of orbital energies is called the crystal field effect, and the difference in energy between the e g
and t 2g sets of orbitals is the crystal field splitting energy (). Different ligands create crystal
fields of different strength and, thus, cause the d-orbital energies to split to different extents.
Strong-field ligands lead to a larger splitting energy (larger ); weak-field ligands lead to a
smaller splitting energy (smaller ). For instance, H 2 O is a weak-field ligand, and CN- is a
strong-field ligand.
I-< Cl- < F- < OH- < H 2 O < SCN- < NH 3 < en < NO 2 - < CN- < CO
Weak Field
Stronger Field
Smaller
Larger
Longer
Example:
Shorter
Rank the ions [Ti (H 2 O) 6 ]3+, [Ti (NH 3 ) 6 ]3+, and [Ti (CN) 6 ]3- in terms of the relative values of
and of the energy of visible light absorbed.
Solution:
The ligand field strength is in the order CN- > NH 3 > H 2 O, so the relative size of and energy of
light absorbed is
[Ti (CN) 6 ]3- > [Ti (NH 3 ) 6 ]3+ > [Ti (H 2 O) 6 ]3+
Page 29
The orbital occupancy is affected by the ligand in one of the two ways:
Weak-field ligands and high-spin complexes.
Strong-field ligands and low-spin complexes.
Crystal Field Splitting in Tetrahedral and Square Planar Complexes

Tetrahedral complexes:
Square planar complexes:
Square planar complexes with d8 metal ions, such as [PdCl] 4 2-, are diamagnetic, with four pairs
of d electrons filling the four lowest energy orbitals . Thus, as a general rule, square planar
complexes are low spin.
Page 30
3. Kinetic molecular description of the state of mater

3.1. The gaseous state
Gas molecules are less dense than other states of matter and moves at very high velocities and
have high kinetic energy (KE). For example, average velocity of H 2 molecules at 0oC is over
1600 m/sec. Mixture of gases are uniformly distributed within the container the same quantity of
a substance occupies a much greater volume as a gas than other two states. For example, 1 mole
of water V = 18 mL at 4oC, V = 22400 mL in the gaseous state. Generally gass:
(1) Molecules are relatively far apart
(2) Can be greatly compressed
(3) Volume occupied by a gas is most empty space
The kinetic-molecular theory
Kinetic-molecular theory (KMT) is based on the motion of particles, particularly gas
molecules a gas behaves exactly as outlined by KMT is known as an ideal gas
The principal assumptions of KMT are:
1. Gases consist of tiny particles
2. The distance between particles is large compared with the size of particles the volume
occupied by a gas consists mostly of empty space
3. Gas particles have no attraction for one another
4. Gas particles move straight lines in all directions colliding frequently with one another and
with the wall of container
5. No energy is lost by collision of a gas particle with another gas particle or with the wall of
container all collisions are perfectly elastic
6. The average kinetic energy for particles is the same for all gases at the same temperature and
its value is directly proportional to the Kelvin temperature
K = mv2
The lighter molecules will have a greater velocity than the heavier ones
ex. the velocity of H 2 is four times the velocity of O 2
Diffusion the ability of two or more gases to mix spontaneously until they form a uniform
mixture
Effusion a process by which gas molecules pass through a very small orifice from a container
at higher pressure to one at lower pressure
Grahams law of effusion the rate of effusion depends on the density of a gas the rates of
effusion of two gases at the same temperature and pressure is inversely proportional to the square
roots of their densities or molar masses
Rate of effusion of A
Rate of eff usion of B
molar mass B
molar mass A
Application of Grahams law: separation of two gasses

Measurement of pressure of gases; pressure is defined as force per unit area
Pressure results from the collisions of gas molecules with the walls of container the mixture of
the pressure exerted by a gas depends on the number of gas molecules, the temperature, the
volume in which the gas is confined.
Pressure units
1 atm = 760 torr = 760 mm Hg = 76 cm Hg = 101.325 kPa = 1013 mbar
1013 mbar = 29.9 in. Hg = 14.7 lb/in.2
Example: 12.1 740 mm Hg =? torr = ? Atm
740 mm Hg = 740 torr = 740/760 atm = 0.974 atm
Page 31
Dependence of pressure on number of molecules and temperature

When the temperature and pressure are kept constant, the pressure is directly proportional to the
number of moles or molecules of gas present
The pressure of a gas in a fixed volume also varied with the temperature
Temperature is increased
KE of the molecules increases more frequent and more energetic collisions occur pressure
increases
Boyles law
Boyles law the relationship of P and V at constant temperature (T), the volume (V) of a fixed
mass of a gas is inversely proportional to the pressure (P)
1
V or P 1 V 1 = P 2 V 2 , PV = constant
P
Ex. a gas occupies 200 mL at 400 torr pressure, what pressure will be when the volume is
changed to 75.0 mL?
(200 mL) (400 torr) = (75 mL) P, P = 1067 torr
Charles law
Charles law the effect of temperature (T) on the volume (V) of a gas at constant pressure the
volume of a fixed mass of any gas is directly proportional to the absolute temperature
absolute zero 0K = -273.15oC
V T or V 1 T 2 = V 2 T 1
Example: 3 L of H 2 at -20oC warmed to room temperature of 27oC, V =? If P = constant
V = 3.56 L
Gay-Lussacs law
Gay-Lussacs law relationship involving pressure and temperature at constant volume the
pressure of a fixed mass of a gas, at constant volume, is directly proportional to the Kelvin
temperature
P = kT or P 1 T 2 =T 1 P 2
Example: pressure of a container of He is 650 torr at 25oC, the sealed container is cooled to 0oC,
what will the pressure be?
P = 595 torr
Combined gas law
Common reference points of temperature and pressure were selected and called standard
condition or standard temperature and pressure (STP)
T = 273.15 K (0oC), P = 1 atm (760 torr or 760 mm Hg or 101.325 kPa)
T and P change at the same time
P1V1
P2V2
=
T1
T2
(i) T is constant Boyles law
(ii) P is constant Charles law
(iii) V is constant Guy-Lussacs law
Example. 20.0 L of NH 3 at 5oC and 730 torr, what is volume at 50oC and 800 torr?
V 2 = 21.2 L
Daltons law of partial pressure
The total pressure of a mixture of gases is the sum of the partial pressure exerted by each of the
gases in the mixture
P total = P A + P B + P C
Avogadros law
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1809 Gay-Lussacs law of combing volume when measured at the same temperature and
pressure, the ratio of the volumes of reacting gases are small whole number
ex. H 2 and O 2 combine to form H 2 O
Avogadros law equal volumes of different gases at the same temperature and pressure contain
the same number of molecules
H2
+
Cl2
2 HCl
1 mole
1 mole
2 mole
1 molecule
1 molecule
2 molecules
1 volume
1 volume
2 volumes
This law afforded a firm foundation for the kinetic-molecular theory different gases at the same
temperature have the same kinetic energy if two different gases at the same temperature, occupy
the same volumes, and exhibit equal pressure, must contain the same number of molecules
Density of gases
The density of a gas
mass
d=
(g)
Volume (L)
The volume of a gas depends on temperature and pressure increasing the temperature will
reduce the density.
At STP, the density of a gas
.
d STP = molar mass (
)

.
d STP = (79.90 g/mol) (

) = 3.17 g/L

Ideal gas equation
Four variables in calculations involving gases: volume (V), pressure (P), temperature (T) and the
number of molecules or moles (n) combining these variables into a single expression
Ideal gas equation PV = nRT
R: ideal gas constant 0.0821 L-atm/mol-K
ex. 12.15 what pressure will be exerted by 0.400 mol of a gas in 5.0-L container at 17oC?
(0.4 mol )(0.0821 Latm /mol K)(290 K)
P=
= 1.90 atm
(5.0 L)
3.2. Solid, liquid and gas phase transition

It is particularly instructive to assemble graphs and diagrams that contrast the properties of a
compound's phases. For example, the phase diagram that is most famous is a plot of pressure vs.
temperature in which the various states of matter are identified.
Presented below are three ways we can draw a phase diagram:
Certainly the simplest is a triangle with the 3 phases at the vertices and the names of the
phase changes along the sides of the triangle.
A second phase transition tracks the temperature change over time energy is added or removed
from the system. Note that there are five different constants for five different possible
calculations within specific temperature regions.
The total energy change is simply determined by adding up the individual energy changes over
the temperature range.
C solid - which is used in a H = mCT
H fus - which is a molar quantity that needs to be scaled to the amount of material to find the
heat change
C liquid - which is used in a H = mCT
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H vap - which is a molar quantity that needs to be scaled to the amount of material to find the
heat change
C gas - which is used in a H = mCT
Note bellow that in the heating of a solid until it becomes a vapor there are five distinct points at
which you can calculate an amount of heat change.
A third and most informative phase diagram: the Pressure-Temperature (PT) Phase Diagram
As described below, (a) the PT diagram is used to determine the phase of a substance at any
combination of pressures and temperatures. In addition, the lines that separate the phases define
equilibrium transitions pressures and temperatures. (b) PT Diagram for water: spend some time
staring at this diagram and looking at the numbers, especially around phase transitions. Your
familiarity with the quantitative aspects of waters phase changes will help you appreciate the
kind of information realized from this kind of graph.
a
b
Things to notice on any PT diagram:
(1) If you are given a P and a T, then you can read the actual phase (s,l,g) at that PT point.
Page 34
(2) In general, and sensibly,

As T gas forms
As T solid forms
As P solid forms
As P gas forms
(3) The solid lines on a PT diagram (a) represent equilibrium phase transitions (the six shown on
the triangle above.) So for example, at the line separating solid from liquid, both liquid and
solid exist simultaneously and define the melting or freezing point for the compound. For
example, on a water PT diagram (b), at 1 atm pressure you would expect to see crossing
points at 0oC and 100 oC.
(4) When you are on a line, you are at equilibrium. In other words, if you see both phases present
simultaneously, /\G=0. We will use this fact to do a calculation shortly.
(5) There are two special regions on a PT diagram.
i)The triple point where all 3 phases exist at equilibrium simultaneously, (For water this
occurs just below 0oC at 4.6 torr) Were you to create this environment you would see ice,
water, and steam all present at the same timekind of gives you chills just thinking about
the excitement of it all.
ii) Supercritical region an odd thing happens if you crank up the pressure and temperature.
You reach a place at the end of the gas liquid line where a new fluid, termed a
supercritical fluid, is formed. It has different properties than either the liquid or vapor of a
substance. (For example, this is the region where supercritical carbon dioxide solubilizes
caffeine in coffee--there was a commercial a few years ago for decaf coffee that referred to
the natural effervescence found in nature as a way to describe using supercritical CO 2
rather than a dry cleaning solvent to extract the caffeine from coffee beans.) What is
interesting to note about the supercritical region is above the critical temperature it is not
possible to turn vapor into a liquid by increasing the pressure. For water the critical
temperature is 374 oC at a pressure of 218 atm. For CO 2 it is 31oC at 73 atm.
Water is Weird and its PT Diagram (above b) Proves It.
The PT diagram proves it. The slope of the line at the solid/liquid phase diagram is like no other
common material--it is negative!!
The unique feature of the graph is the negative slope of the ice-liquid transition. (Every other
phase diagram shows a positive slope for the solid-liquid interface. Why is this negative slope for
H 2 O so interesting? It means that
Ice is less dense than water-it is why ice floats on water but in all other substances the solid
form sinks. It is also why when you put a glass of water in the freezer, the frozen ice
increases in size and can break the glass.
The PT diagram also suggests that for water, as the pressure goes up, ice melts. Think about
it this way: when you bite an ice cube it liquefies. When you bite any other solid, it stays a
solid!!
By the way, the reason for this peculiar behavior of water is the enormous H-bonding capacity of
H 2 O that more tightly packs it in liquid form/
3.3. Solution
Solutions are homogeneous mixtures consisting of a solute dissolved in a solvent through the
action of intermolecular forces. The solubility of a solute in a given amount of solvent is the
maximum amount that can dissolve at a specified temperature. (For gaseous solutes, the pressure
must be specified also.) In addition to the intermolecular forces that exist in pure substances, ionGeneral Chemistry L. Note for Pre-Engineering Students
Page 35
dipole, ion-induced dipole, and dipole-induced dipole forces occur in solution. If similar
intermolecular forces occur in solute and solvent, a solution will likely form solution, "like
dissolves like". When ionic compounds dissolve in water, the ions become surrounded by
hydration shells of H-bonded water molecules.
Solubility of organic molecules in various solvents depends on their polarity and the extent of
their polar and nonpolar portions. The solubility of nonpolar gases in water is low because of
weak intermolecular forces. Gases are miscible with one another and dissolve in solids by fitting
into spaces in the crystal structure. Solid-solid solutions, such as alloys and waxes, form when
the components are mixed while molten.
4. Equilibrium in chemical reaction
4.1. Thermodynamic process and Thermochemistry
Chemical Thermodynamics is the study of the energetics of a chemical reaction.
Thermodynamics deals with the absorption or release of energy (generally as heat) that
accompanies chemical reactions.
These dynamics generally give us an idea of whether a reaction will be spontaneous
Spontaneous describes a process that can occur without outside intervention (i.e. changing the
temperature, pressure or concentration)
Spontaneity does not imply that the process occurs quickly, but rather describes a capability to
proceed.
If a chemical reaction is found to be spontaneous in one direction, then under the same
conditions, the reverse reaction will be non-spontaneous
This does not mean that the reaction cannot occur, but that it will need some outside help.
Energy
Energy is the capacity to do work, or supply heat.
Energy = Work + Heat
Potential energy, PE, is stored energy; it results from position or composition.
Kinetic energy, KE, is the energy matter has as a result of motion.
KE = 1/2 mv2
Units for KE: 1 Joule = 1 kg.m2/s2 or 1 calorie = 4.184 J
Units of Energy the SI unit for energy is the Joule (J)
The joule is a small amount of energy so scientists generally refer to Kilojoules (kJ)
The calorie (cal) is another unit of energy.
It is defined as the amount of energy needed to raise the temperature of 1.00 g of water by one
degree Celsius, 1 cal = 4.184 J
KE, Temperature & State
All substances have kinetic energy no matter what physical state they are in.
Solids have the lowest kinetic energy, and gases have the greatest kinetic energy.
As you increase the temperature of a substance, its kinetic energy increases.
Forms of Energy
There are six forms of energy:
Heat, Radiant, Electrical, Mechanical, Chemical and Nuclear
We can convert among these types of energy
Thermal Energy
Thermal Energy is the kinetic energy of molecular motion (translational, rotational, and
vibrational).
We measure this energy by finding the temperature of an object
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Thermal energy is proportional to the temperature in degrees Kelvin Ethermal T(K)

Chemical Energy is the PE of a chemical compound where the chemical bonds act as
storage containers for the energy
The System and the Surroundings
The system is the specific part of the universe that is of interest to us (i.e. the reaction with
reactants & products)
The surroundings is the rest of the universe
When performing experiments, we measure changes to the surroundings then apply those
findings to the system.
Energy is transferred between the system and the surroundings
Energy that is transferred from the system to the surroundings has a negative sign
Energy that is transferred from the surroundings to the system has a positive sign
E = Efinal - EInitial
State Functions
A State Function is a function or property whose value depends only on the present state
(condition) of the system not the path used to arrive at that condition.
The change in a state function is zero when the system returns to its original condition.
For non-state functions, the change is not zero if the path returns to the original condition
Heres an example with a chemical reaction:
The two paths below give the same final state:
N 2 H 4 (g) + H 2 (g) 2NH 3 (g) + heat (188 kJ)
N 2 (g) + 3H 2 (g) 2NH 3 (g) + heat (92 kJ)
State properties include for the formation of NH3: temperature, total energy, pressure, density,
and [NH 3 ]
Non-state properties include for the formation of NH 3 : heat and reactants used
Work
Work (w) is the application of a force (F) through a distance (d)
This work produces an objects movement
If the system performs work on the surroundings, the sign of w is negative.
If the surroundings perform work on the system, the sign of w is positive.
Work = Force Distance
Units for W: Newton-meters (N-m) or Joules (J), 1J = 1N-m
A system that contains one or more gases performs a specific type of work called PV Work or
expansion work.
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Expansion Work
A system that contains a gas can perform work as the gas expands against an opposing pressure
(P) exerted by the surroundings.
This type of work is called Expansion Work or PV Work
w = - PV, V = V Final - V Initial , 1 L atm = 101 J
When a gas expands, w is negative because the system transfers energy to the surroundings
When a gas contracts, w is positive because the surroundings transfer energy to the system
Heat
Heat (q) is the energy that flows from a warmer object (higher temperature) to a cooler object
(lower temperature)
Heat is associated with the movement of particles
The faster the particles are moving, the more heat you generate (and vice versa)
If the system gives heat to the surroundings, the sign of q is negative.
If the surroundings give heat to the system, the sign of q is positive.
The First Law of Thermodynamics
In a reaction, energy is conserved. It is neither created nor destroyed.
It can be converted into a different type of energy though!
The energy change in a system equals the work done on the system + the heat added.
Total Energy of Reactants = Total Energy of Products
E = E final E initial = q + w
Energy and Enthalpy
Most chemical reactions are performed in containers that are open to the atmosphere.
The volume of the system is allowed to change but the pressure (atmospheric pressure) remains
constant.
If the work performed is limited to PV work, a state function called Enthalpy (H), it can be
defined.
H = E + PV
The change in enthalpy (H) is equal to the heat absorbed by the system under conditions of
constant pressure.
H = E + PV
Enthalpy Changes: Physical Change
There are two types of Enthalpy changes:
The Enthalpy of Physical Change.
The Enthalpy of Chemical Change
The Enthalpy of Physical Change is the amount of heat required to change the state of matter
Enthalpy Changes: Chemical Change
The Enthalpy of Chemical change deals with the energy requirements of chemical reactions.
The Heat of the Reaction (H rxn ) gives the amount of heat absorbed or released due to a
chemical reaction at constant pressure.
H rxn = H products H reactants
If a reaction has more than one step, the Hrxn is the sum of the H for each individual
reaction.
(1) Reactants Elements Heat Absorbed = H 1
(2) Elements Products Heat Absorbed = H 2
(Overall) Reactants Products Heat Absorbed = H rxn
Enthalpy Changes: Chemical Change
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In an Exothermic reaction, the reaction releases energy in the form of heat to the surroundings
(you feel the reaction get hot!)
The energy of the reactants is greater than that of the products.
C(s) + O 2 (g) CO 2 + Energy
In an Endothermic reaction, the reaction absorbs energy in the form of heat from the
surroundings (you feel the reaction get cold!)
The energy of the products is greater than that of the reactants.
2H 2 O (l) + Energy 2 H 2 (g) + O 2 (g)
Hesss Law: The overall enthalpy change for a reaction is equal to the sum of the enthalpy
changes for the individual steps in the reaction.
3H 2 (g) + N 2 (g) 2NH 3 (g) H = 92.2 kJ
Reactants and products in individual steps can be added and subtracted to determine the overall
equation.
(a) 2 H 2 (g) + N 2 (g) N 2 H 4 (g)
H1 = ?
(b) N 2 H 4 (g) + H 2 (g) 2 NH3 (g)
H2 = 187.6 kJ
(c) 3 H 2 (g) + N 2 (g) 2 NH 3 (g)
H3 = 92.2 kJ
H 1 = H 3 H 2 = (92.2 kJ) (187.6 kJ) = +95.4 kJ
Manipulating Chemical Enthalpy Changes
Reversing a reaction changes the sign of H for a reaction:
C 3 H 8 (g) + 5O 2 (g) 3CO 2 (g) + 4H 2 O(l)
H = 2219 kJ
H = +2219 kJ
3CO 2 (g) + 4H 2 O(l) C 3 H 8 (g) + 5O 2 (g)
Multiplying a reaction increases H by the same factor because H is also stoichiometrically
related to the coefficients of the balanced chemical equation:
3(C 3 H 8 (g) + 5O 2 (g) 3CO 2 (g) + 4H 2 O(l)
H = 2219 kJ)
3 C 3 H 8 (g) + 15O 2 (g) 3CO 2 (g) + 12H 2 O(l)
H = 6657 kJ
Standard Heats of Formation
Where do all of these H values come from that we have been using? Has someone
determined these values for all of these reactions?
Standard Heats of Formation (H f ): The enthalpy change for the formation of 1 mole of
substance in its standard state from its constituent elements in their standard states.
C(s) + 2H 2 (g) CH 4 (g) H f = -74.5 kJ
The standard heat of formation for any element in its standard state is defined as being ZERO.
H f = 0 for an element in its standard state
The standard enthalpy change for any chemical reaction is found by subtracting the sum of the
heats of formation of all reactants from the sum of the heats of formation of all products
H = Hf (Products) Hf (Reactants)
For a balanced equation, each heat of formation must be multiplied by the stoichiometric
coefficient.
aA + bB cC + dD
H = [cH f (C) + dH f (D)] [aH f (A) + bH f (B)]
Bond Dissociation Energy
There are over 18 million chemical compounds known at this time. Who do you think is making
all of the H f determinations for those compounds?
It is possible to get an approximate H f for a compound based on the bonds present.
The Bond Dissociation Energy can be used to determine an approximate value for Hf .
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H f = D (Bonds Broken) D (Bonds Formed)

H f = D (Reactant Bonds) D (Product Bonds)
Calorimetry and Heat Capacity
The Bond energies and Heats of Formation give us an approximate idea of H f .
How do we experimentally measure the amount of heat transferred during a reaction?
Calorimetry is the science of measuring heat changes (q) for chemical reactions. There are two
types of calorimeters:
Bomb Calorimetry: A bomb calorimeter measures the heat change at constant volume such that
q = E.
Constant Pressure Calorimetry: A constant pressure calorimeter measures the heat change at
constant pressure such that q = H.
Heat capacity (C) is an extensive property that gives the amount of heat required to raise the
temperature of an object or substance a given amount.
The greater the Heat Capacity, the greater the amount of heat needed to increase the
temperature
C=
Specific Heat (SH): The amount of heat required to raise the temperature of 1.00 g of substance
by 1.00C.
q = SH m T
Molar Heat Capacity (CM): The amount of heat required to raise the temperature of 1.00
mole of substance by 1.00C.
q = CM n T
Introduction to Entropy
We have stated that chemical and physical processes occur spontaneously only if they go
downhill energetically (give off energy) so that the final state is more stable and lower in
energy than the initial state.
However, we know that reactions that require energy (endothermic reactions) will also occur.
This is possible because energy is more than just heat. There are other forms of energy present
in reactions that allow it to be spontaneous despite absorbing heat.
Another factor that affects spontaneity of a reaction is the molecular disorder of the reaction.
The amount of molecular disorder (or randomness) in a system is called the systems Entropy
Entropy has units of J/K (Joules per Kelvin).
S = S final S initial
Positive value of S indicates increased disorder.
Negative value of S indicates decreased disorder.
Second Law of Thermodynamics:
Reactions proceed in the direction that increases the entropy of the system plus surroundings.
Entropy and Enthalpy
To decide whether a process is spontaneous, both enthalpy and entropy changes must be
considered:
Spontaneous process: Decrease in enthalpy (H) and Increase in entropy (+S).
Nonspontaneous process: Increase in enthalpy (+H) and Decrease in entropy (S).
Introduction to Gibbs free energy
Gibbs Free Energy Change (G) weighs the relative contributions of enthalpy and entropy to
the overall spontaneity of a process.
G = H TS, G < 0 Spontaneous, G = 0 Equilibrium and G >0 Non-spontaneous
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G = H TS
Gibbs free energy at Equilibrium
Equilibrium (G = 0): Estimate the temperature at which the following reaction will be at
equilibrium. Is the reaction spontaneous at room temperature?
N 2 (g) + 3 H 2 (g) 2 NH 3 (g)
H = 92.0 kJ S = 199 J/K
4.2. Spontaneous process and thermodynamic equilibrium
Spontaneous processes
Spontaneous process: takes place naturally, without continuous outside intervention
e.g. a drop of food coloring will spread in a glass of water or once ignited H 2 gas burns in O 2
gas.
nonspontaneous process: only takes place as a result of continuous intervention
e.g., electricity is required to convert water to H 2 gas and O 2 gas
Keep in mind that spontaneous processes may be fast or slow.
a. An explosion is fast and spontaneous.
b. The process of rusting is slow and spontaneous.
Consider the following spontaneous processes at room temperature:
A drop of food coloring will spread in a glass of water.
Methane (CH 4 ) burns in O 2 gas.
Ice melts in your hand.
Ammonium chloride dissolves in a test tube with water, making the test tube colder.
Example: What do these processes or reactions have in common? Are they all exothermic?
Are they all endothermic?
4.3. Chemical equilibrium
The concept of equilibrium and the equilibrium constant
Many chemical reactions do not go to completion but instead attain a state of chemical
equilibrium.
Chemical equilibrium: A state in which the rates of the forward and reverse reactions are equal
and the concentrations of the reactants and products remain constant.
Equilibrium is a dynamic process. The conversions of reactants to products and products to
reactants are still going on, although there is no net change in the number of reactant and product
molecules.
For the reaction: N 2 O 4 (g) 2NO 2 (g)
The Equilibrium Constant

For a reaction: aA + bB cC + dD
[] []
Equilibrium constant: K c = [] []
The equilibrium constant, K c , is the ratio of the equilibrium concentrations of products over the
equilibrium concentrations of reactants each raised to the power of their stoichiometric
coefficients.
Example. Write the equilibrium constant, Kc , for N 2 O 4 (g) 2NO 2 (g)
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Law of mass action - The value of the equilibrium constant expression, K c, is constant for a
given reaction at equilibrium and at a constant temperature.
The equilibrium concentrations of reactants and products may vary, but the value for K c
remains the same.
Other Characteristics of K c
1) Equilibrium can be approached from either direction.
2) Kc does not depend on the initial concentrations of reactants and products.
3) Kc does depend on temperature.
Magnitude of K c
If the K c value is large (K c >> 1), the equilibrium lies to the right and the reaction mixture
contains mostly products
If the K c value is small (K c <<1), the equilibrium lies to the left and the reaction mixture
contains mostly reactants.
If the K c value is close to 1 (0.10 < K c < 10), the mixture contains appreciable amounts of
both reactants and products.
Writing equilibrium constant expressions
Calculating Equilibrium Constants, K c
K c values are listed without units dont include units when calculating K c .
If equilibrium concentrations are known, simply substitute the concentrations into the
equilibrium constant expression:
Example- For the reaction, CO + 3H 2 CH 4 + H 2 O, calculate Kc from the following equilibrium
concentrations: [CO] = 0.0613 M; [H 2 ] = 0.1839 M; [CH 4 ] = 0.0387 M; [H 2 O] = 0.0387 M.
Homogeneous equilibria: reactants and products exist in a single phase.
For the gas phase reaction: N 2 O 4 (g) 2NO 2 (g)
The equilibrium constant with the concentrations of reactants and products expressed in terms of
molarity, Kc, is:
[NO 2 ]2
Kc = [N
2O4]
Gas Phase Expressions can also be expressed by Kp

The Kp expression is written using equilibrium partial pressures of reactants & products.
For the reaction given above, the Kp expression is:
[P
Kp = [P NO 2
]2
N2O 4 ]
Kp is related to Kc
Since pressure and molarity are related by the Ideal Gas Law, the following equation relates Kp
and Kc:
Kp = Kc(RT)n
Where R = 0.0821 L.atm/ K mol, T = temperature in Kelvin
n = moles of gaseous products, moles of gaseous reactants
Note that Kc = Kp when the number of gas molecules are the same on both sides.
Example- Does Kc = Kp for (a) H 2 (g) + F2 (g) 2HF(g)? (b) 2SO 2 (g) + O 2 (g) 2SO 3 (g)?
Example- For the reaction, 2SO 2 (g) + O 2 (g) 2SO 3 (g) (a) write the equilibrium
constant expression, Kp. (b) What is the value for Kp if Kc = 2.8x102 at 1000 K?
Heterogeneous Equilibria and Solvents in Homogeneous Equilibria
Heterogeneous equilibria: reactants and products are present in more than one phase.
Pure solids and liquids: concentrations of pure solids and liquids are fixed by their density and
molar mass (both constants) and do not vary with the amount.
Page 42
[] =M =
Density
MolarMass
mol
L
ml
10 3 mL
1L
mol
g
Thus, the concentrations of solids and liquids are incorporated in the K c value; they are not
part of the variable K c expression:
Example: Write the K c expression for CaCO 3 (s) CaO(s) + CO 2 (g)
Omit concentration terms for solids and liquids from K c and K p expressions; only include
terms for gases (g) and aqueous substances (aq).
Example-Write the Kc expression for the following reaction:
3Cu(s) + 2NO 3 -(aq) + 8H+(aq) 3Cu2+(aq) + 2NO(g) + 4H 2 O(l)
The relationship between chemical kinetics and chemical equilibrium
For the reaction N 2 O 4 (g) 2NO 2 (g)
Rate of forward reaction = Rate of reverse reaction
k f[N 2 O 4 ] = kr[NO 2 ]2
[NO 2 ]2
Rearrange: [N
2 O 4]
= K f = Kc
r
Thus, the equilibrium constant is simply the ratio of the forward and reverse rate constants which
are both constant values at a given temperature.
What does the equilibrium constant tell us?
Predicting the Direction of Reaction
The reaction quotient, Q, is the resulting value when we substitute reactant and product
concentrations into the equilibrium expression.
1. If Q > K, the reaction will go to the left.
The ratio of products over reactants is too large & the reaction will move toward equilibrium by
forming more reactants.
2. If Q < K, the reaction will go to the right.
The ratio of products over reactants is too small & the reaction will move toward equilibrium
by forming more products.
3. If Q = K, the reaction mixture is already at equilibrium, so no shift occurs.
Example. For the reaction, B 2A, K c = 2. Suppose 3.0 moles of A and 3.0 moles of B are
introduced into a 2.00 L flask. (a) In which direction will the reaction proceed to attain
equilibrium?
(b) Will the concentration of B increase, decrease or remain the same as the system moves
towards equilibrium?
Factors that affect chemical equilibrium
Le Chatelier's Principle: If a system at equilibrium is disturbed by an external stress, the system
adjusts to partially offset the stress as the system attains a new equilibrium position.
Changes in Concentration
adding a reactant or product, the equilibria shifts away from the increase in order to consume
part of the added substance.
removing a reactant or product, the equilibria shifts toward the decrease to replace part of the
removed species.
E.g. for H 2 + I 2 2HI, does the equilibria shift left or right if we: a) add H 2 ? b) Remove I 2 ?
Changes in Volume and Pressure
Because the pressure of gases is related directly to the concentration by P = n/V, changing the
pressure by increasing/decreasing the volume of a container will disturb an equilibrium system.
If P increases (V decreases), the system shifts to the side with a smaller number of gas
molecules (this effectively reestablishes equilibrium by decreasing the pressure).
Page 43
If P decreases (V increases), the system shifts to the side with a greater number of gas
molecules.
Example: For N 2 (g) + 3H 2 (g) 2NH 3 (g), does the equilibrium shift left or right if the pressure
is increased?
Changes in Temperature
Heat can be considered a reactant in an endothermic rxn and a product in an exothermic rxn.
Endothermic (H > 0) R + Heat Products
Exothermic (H < 0) R Products + Heat
Recall that both Kc and the position of the equilibrium system will vary with temperature:
Kc is larger when the reaction shifts right. This occurs if T is increased for an Endothermic
Reaction or T is decreased for an exothermic reaction.
Kc is smaller when the reaction shifts left. This occurs if T is decreased for an Endothermic
Reaction or T is increased for an exothermic reaction.
Example: If the temperature is decreased for the reaction: 2CO 2 2CO + O 2 , H = 566 kJ.
a) Will the equilibrium shift left or right? b) Does Kc become larger or smaller?
Effect of a Catalyst
Catalysts lower Ea for the reaction, so a catalyst decreases the amount of time taken to reach
equilibrium for both the forward and reverse reactions.
the catalyst does not affect the equilibrium concentrations of reactants and products in the
equilibrium mixture; thus, the Kc value does not change.
Choosing Optimum Conditions
Le Chatelier.s principle can be used to select optimum conditions to form a substance.
Example: To form more NH 3 , predict the optimum conditions for temperature and pressure.
N 2 (g) + 3H 2 (g) 2NH 3 (g) H = -91.8 kJ
4.4. Acid base equilibrium
Acid-base reactions
We are going to be working with acid-base equilibria in aqueous solution, and we will use the
Brnsted-Lowry definitions that an acid is a source of H+ and a base is an acceptor of H+.
Acid ionization constant Ka
A convenient way to write the reaction of an acid HA in water is
HA (aq) +H 2 O (l) H 3 O+ (aq) + A- (aq)
Here water is acting as a base, accepting the H+; the result, H3O+, called the conjugate acid of
H 2 O, since H 3 O+ can donate H+ to reform H 2 O. In a similar way, A- is called the conjugate base
of the acid HA, since A- can accept H+ to reform HA. The equilibrium constant is known as the
acid ionization constant K a ,
HA (aq) +H 2 O (l) H 3 O+ (aq) + A- (aq)
ka =
[H + ][A ]
[HA ]
with the understanding that [] stands for the numerical valuewithout unitsof the
concentration in mol/L. As usual, Ka is unit-less. An example acid ionization is
CH3COOH(aq)
H+(aq) + CH3COO- (aq)
[H 3 O + ][ CH 3 COO ]
[CH 3 COOH ]
If Ka is much greater than 1, the acid is mostly dissociated and so is said to be a strong acid. If
Ka is much less than 1, the acid is dissociated only to a small extent and so is said to be a weak
acid.
Base ionization constant Kb
Page 44
Similarly, we can write the reaction of a base B in water as

H 2 O(l) + B(aq) HB+ (aq) + OH-(aq).
Here water is acting as an acid, donating the H+; the result, OH-, is called the conjugate base of
H2O, since OH- can accept H+ to reform H 2 O. Analogously, HB+ is called the conjugate acid of
the base B, since HB+ can donate H+ to reform B. The equilibrium constant is known as the base
ionization constant K b ,
kb =
[OH ][ HB + ]
[NH 3 ]
Here is an example base ionization

NH 3 + H 2 O NH 4 + + OH- ,
kb =
[OH ][ NH 4+ ]
[B]
If Kb is much greater than 1, the base reacts nearly completely with water and so is said to be a
strong base. If K b is much less than 1, the base reacts hardly at all with water and so is said to be
a weak base.
Water autoionization constant K w
In this analysis of acid and base ionization we see that water in one case plays the role of a base
and the other plays the role of an acid. Indeed, the role that water plays in an aqueous
equilibrium can be used as another definition of acid or base. A consequence of this dual role of
water is that its equilibrium with H 3 O+ and OH- is the reference standard against which aqueous
acidity and basicity are defined.
Here is how this works. A general base ionization reaction is
H 2 O(l) + B(aq) HB+ (aq) + OH- (aq), K b , and the ionization reaction of its conjugate acid is
HB+ (aq) + H 2 O(l) H 3 O+ (aq) + B(aq), K a . The sum of these two reactions is
2H 2 O(l) H 3 O+ (aq) + OH- (aq), K w.
This equation is called the autoionization of water and its equilibrium constant is known as the
water autoionization constant K w. At 25C it is equal to
Kw = [H 3 O+][OH] = [H 3 O+]2 = [OH]2= 1.008 1014 at 25C = Ka K b
Now, we have seen that the equilibrium constant of a sum of two reactions is the product of the
equilibrium constants of the summed reactions. Therefore, we know that water autoionization
constant can be expressed as
pH
Because K w is so small, water is ionized only very slightly. We can compute the concentration of
H 3 O+ and OH- by solving the autoionization equilibrium.
[OH]
[H 3 O+]
Initial
0
0
Equilibrium
x
x
Initial and equilibrium activities for the autoionization of liquid water
The equilibrium expression is then
Kw = 1x10-14 = x2, and so the concentration of H 3 O+ and OH- are each 1x10-7 M at 25C.
Now, as we will see in a moment, strong acids can have H 3 O+ concentrations of 1 M or more.
This means that H 3 O+ varies over many powers of 10 (orders of magnitude), and so it is
convenient to measure [H 3 O+] on a logarithmic scale. Also, for weak acids and bases, which is
what we will be interested in primarily, concentrations of H 3 O+ and OH- are generally much less
than 1 M, which means their logarithms are negative, and so it is more convenient to work with
the negative logarithms so that we have a positive quantity.
For this reason, the notation pAnything is defined as
pAnything = -log 10 (Anything) and in particular pH and pOH are defined as
Page 45
pH = -log10 (H 3 O+] , pOH = -log10(OH-),

Where in each case the second equality is written with understanding that [] stands for the
numerical value without units of the concentration in mol/L
Since acids produce additional H 3 O+, their pH is always less than 7. Similarly, since bases
produce additional OH-, their pOH is always less than 7. We can relate pH and pOH, by
calculating pKw.
pKw = -log10 (K w ) = -log10 ([H 3 O+][OH-]) = -{log10 ([H 3 O+]) + log10 ([OH-]}
= - log10 ([H 3 O+]) - log10 ([OH-] = pH + pOH
This means that at 25C
pH = 14 pOH, so that bases have pH greater than 7, at 25C.
It is important always to be mindful of the temperature being used. The reason is that equilibrium
constants in general and the value of K w in particular, are different at different temperatures. This
means that the pH of pure water will be different at different temperatures. For this reason,
saying a solution has pH = 7 do not, by itself, mean the solution is "neutral" (have equal
concentrations of H 3 O+ and OH-. More generally, the acidic or basic character of a solution is
due to the relative concentrations of H 3 O+ and OH-, rather than a particular numerical value of
pH.
Common ion effect
Common ion effect: The shift in equilibrium caused by the addition of a substance having an
ion in common with the equilibrium mixture. Addition of the common ion causes the equilibrium
to shift left; this suppresses the ionization of a weak acid or a weak base.
The source of the common ion is typically provided by adding a strong acid, a strong base or a
soluble salt to the equilibrium reaction mixture.
E.g. Given this reaction: HC 2 H 3 O 2 H+ + C 2 H 3 O 2
-. What happens to the pH of the acetic acid solution if we add (a) HCl? (b) NaC 2 H 3 O 2 ?
Common Ion Problems:
1) Include the initial concentration of the common ion in the ICE table.
2) Use the approximation method to solve the equilibrium constant expression.
Buffer solutions
Buffer: A solution that resists changes in pH when a small amount of acid or base is added.
The best buffer systems consist of either
a) a weak acid and a salt containing its conjugate base (e.g. HC 2 H 3 O 2 and NaC 2 H 3 O 2 );
b) a weak base and a salt containing its conjugate acid (e.g. NH 3 and NH 4 Cl).
For these buffer systems:
1) The acid component of the buffer can neutralize added base and the base component of
the buffer can neutralize added acid.
2) Since they are a conjugate acid-base pair, the acid and base in the buffer dont react
with one another.
Buffer capacity is the amount of acid or base the buffer can neutralize before there is a
significant change in pH. The buffer capacity is a measure of the effectiveness of a buffer.
Buffer capacity is greater when larger amounts of HA and A- are present.
pH will stay relatively constant as long as [HA] and [A-] are greater than the amount of acid
or base added.
Buffers work best when [HA] and [A-] are approximately equal. For buffers to be effective,
the ratio of Base: Acid should be between 1:10 to 10:1.
Consider the following weak acid buffer reaction: HA(aq) H+(aq) + A-(aq)
Page 46
HA (aq) H 3 O+ (aq) + A-(aq)
ka =
[ + ][ ]
Taking - log both sides: - log [H+] = -log Ka - log
[]
[HA ]
pH = pKa + log
[HA ]
[A ]
[A ]
, [H +] = Ka
[]
[ ]
, Henderson-Hasselbalch equation
In solving common ion and buffer problems, assume [HA] eq and [A-] eq are equal to their initial
concentrations. (That is, the approximation method is valid for these problems.)
A special situation occurs when [HA] = [A-]:
By substitution, the Ka expression becomes: [H+] = Ka .
Thus, pH = pKa .
We can use the Henderson-Hasselbalch relationship to prepare a buffer solution with a certain
pH - select an acid with a pKa close to the pH you want (pKa 1), and adjust the [base]/[acid]
ratio to obtain the desired pH.
Acid-base titrations
Acid-base titration curve: plot of pH vs. volume added during a titration; 4 important regions.
Equivalence point: the point at which the acid and base are present in equal stoichiometric
amounts.
Calculations for finding pH during Strong Acid Strong Base Titration
Net-ionic neutralization reaction for SA/SB titration: H+ + OH- H 2 O
1) Initial pH: depends on the concentration of the strong acid.
A strong acid is 100 % ionized: HA(aq) H+(aq) + A-(aq)
The reaction is complete; thus, [H+] = [HA].
2) pH after initial but before equivalence point: depends on the amount of excess acid remaining
after neutralization.
moles acid initial moles base added
[H+] =
volume of solution
Where moles acid = Lacid x M acid and moles base = Lbase x M base
Volume of solution = volume (acid + base)
3) pH at equivalence point: pH = 7 only for SA/SB (or SB/SA) titrations because a neutral salt
water solution is present.
the acid has been completely neutralized by the base, leaving a neutral salt solution. Recall
that the cation of a strong base (e.g. Na+) and the anion of a strong acid (e.g. Cl-) are neutral
ions, so they do not react with water.
4) pH after equivalence pt: depends on the amount of excess base remaining after the
neutralization reaction.
moles base added moles base initial
[OH-] =
volume of solution
pOH = - log [OH-]; pH = 14.00 pOH
4.5. Solubility and precipitation equilibria

Solubility equilibria
Important biological examples:
Tooth decay - tooth enamel dissolves in acidic solutions
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Formation of kidney stones - salts precipitate in kidney

Many salts are only slightly soluble in water and form solid precipitates in aqueous solutions.
This insoluble salts dissolve to a small extent and forms a saturated solution
The undissolved solid and the dissociated ions in solution establish an equilibrium system.
An example of this is the dissolution of AgBr: AgBr(s) Ag+(aq) + Br-(aq)
Ksp = [Ag+][Br-]
Ksp is called the solubility product constant; it is the equilibrium constant for insoluble salts.
It is a measure of how soluble a salt is in water - the smaller the Ksp, the less soluble the salt.
Example: Which salt is less soluble?
(B) PbS, Ksp = 3.4x10-28
(A) CdS, K sp = 8.0x10-28
-21
(C) CoS, K sp = 4.0x10
(D) FeS, Ksp = 6.0x10-19
Relationship between K sp & salt solubility:
Solubility - the maximum amount of salt that will dissolve in a given quantity of solvent; units
can be or g/L or mol/L. (For molar solubility, the units are mol/L.)
Molar Solubility = concentration of the dissolved salt; ion concentrations are related to the
solubility of the salt by their coefficients.
For MgS , MgS(s) Mg2+(aq) + S2-(aq)
Solubility of MgS = [MgS] - This is the concentration of the salt that dissolved in solution.
From the balanced equation, for each mole of MgS that dissolves one mole of magnesium ions
and one mole of sulfide ions form, Thus,
[MgS] = [Mg2+] = [S2-]
Example: (a) Calculate K sp for Ag 2 S if [Ag+] = 5.8 x 10-17 M. (b) What is the solubility of
Ag 2 S?
Predicting Precipitation Reactions- Does a precipitate form?
We can modify the solubility of salts to dissolve minerals and ores, to precipitate ions from
solution, and to separate and purify ions. From calculating the reaction quotient, we can
determine if dissolution or precipitation will occur. For solubility problems, Q is called the ion
product.
3 Possibilities
1) If Q < K sp , an unsaturated solution is present precipitation does not occur. The ion
concentrations are not high enough to form a solid.
2) If Q = K sp , the system is at equilibrium so dissolution and precipitation occur at equal rates; a
saturated solution exists in which the ion [ ].s are just high enough for precipitation to occur.
3) If Q > K sp, precipitation occurs as the reaction shifts left. There are excess ions in solution that
will precipitate out to form a solid.
Types of problems
Calculate Q based on the [ ]s of the ions in the salt and compare to Ksp to determine whether
or not the salt will precipitate.
Predict whether or not a precipitate will form when two solutions are mixed.
4.6. Electrochemistry
Terms to know:
Electrochemistrythe study of the interchange of chemical and electrical energy
Oil rig oxidation is loss, reduction is gain (of electrons)
Oxidation the loss of electrons, increase in charge
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Reduction the gain of electrons, reduction of charge

Oxidation number the assigned charge on an atom
Oxidizing agent (oa) the species that is reduced and thus causes oxidation
Reducing agent (ra) the species that is oxidized and thus causes reduction
Electrochemistry involves two main types of processes:
a. galvanic (voltaic) cells which are spontaneous chemical reactions (battery)
b. electrolytic cells which are non-spontaneous and require external e source (DC
power source)
c. Both of these fit into the category entitled Electrochemical cells
Galvanic Cells
Parts of the voltaic or galvanic cell:
Anode--the electrode where oxidation occurs. After a period of time, the anode may
appear to become smaller as it falls into solution.
Cathode-- the anode where reduction occurs. After a period of time it may appear larger,
due to ions from solution plating onto it.
Inert electrodesused when a gas is involved OR ion to ion involved such as Fe3+ being
reduced to Fe2+ rather than Fe0. Made of P t or graphite
Salt bridge -- a device used to maintain electrical neutrality in a galvanic cell. This may
be filled with agar which contains a neutral salt or it may be replaced with a porous cup.
Electron flow -- always from anode to cathode. (Through the wire)
Standard cell notation (line notation) - anode/solution// cathode solution/ cathode Ex.
Zn/Zn2+M) // Cu2+ (1.0 M) / Cu
Voltmeter - measures the cell potential (emf) . Usually is measured in volts.
Balance this redox reaction:
MnO4- + Fe2+ Mn2+ + Fe3+ [acidic]
If we place MnO 4 - and Fe2+ in the same container, the electrons are transferred directly when the
reactants collide. No useful work is obtained from the chemical energy involved which is instead
released as heat!
We can harness this energy if we separate the oxidizing agent from the reducing agent, thus
requiring the e- transfer to occur through a wire! We can harness the energy that way to run a
motor, light a bulb, etc.
Salt bridgeits job is to balance the charge using an electrolyte [usually in a U-shaped tube
filled with agar that has the salt dissolved into it before it gels]. It connects the two
compartments, ions flow from it, and it keeps each cell neutral. Use KNO 3 as the salt when
constructing your own diagram so that no precipitation occurs!
Cell potentialEcell, Emf, or cellit is a measure of the electromotive force or the pull
of the electrons as they travel from the anode to the cathode [more on that later]
volt (V)the unit of electrical potential; equal to 1 joule of work per coulomb of charge
transferred
voltmetermeasures electrical potential; some energy is lost as heat [resistance] which
keeps the voltmeter reading a tad lower than the actual or calculated voltage. Digital
voltmeters have less resistance. If you want to get picky and eliminate the error introduced by
resistance, you attach a variable-external-power source called a potentiometer. Adjust it so
that zero current flowsthe accurate voltage is then equal in magnitude but opposite in sign
to the reading on the potentiometer.
Standard Reduction Potentials
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Each half-reaction has a cell potential

Each potential is measured against a standard which is the standard hydrogen electrode
[consists of a piece of inert Platinum that is bathed by hydrogen gas at 1 atm].
The hydrogen electrode is assigned a value of zero volts.
Standard conditions1 atm for gases, 1.0M for solutions and 25C for all (298 K)
Naught, -we use the naught to symbolize standard conditions [Experiencing a thermo
flashback?] That means
Ecell, Emf, or cell become Ecello, Emfo , or cello when measurements are taken at standard
conditions. Youll soon learn how these change when the conditions are nonstandard!
(c)
The diagram above (c) illustrates what really happens when a Galvanic cell is constructed from
zinc sulfate and copper (II) sulfate using the respective metals as electrodes.
Notice that 1.0 M solutions of each salt are used
Notice an overall voltage of 1.10 V for the process
Reading the reduction potential chart
Elements that have the most positive reduction potentials are easily reduced (in general, nonmetals)
Elements that have the least positive reduction potentials are easily oxidized (in general,
metals)
The table can also be used to tell the strength of various oxidizing and reducing agents.
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Can also be used as an activity series. Metals having less positive reduction potentials
are more active and will replace metals with more positive potentials.
How can we determine which substance is being reduced and which is being oxidized??
The more positive reduction potential gets to indeed be reduced IF you are trying to set up a cell
that can act as a battery, table above.
Calculating Standard Cell Potential Symbolized by Ecell or Emf ORcell [Ill mix and
match!]
1. Decide which element is oxidized or reduced using the table of reduction potentials.
Remember: The more positive reduction potential gets to be reduced.
2. Write both equations AS IS from the chart with their voltages.
3. Reverse the equation that will be oxidized and change the sign of the voltage [this is now
Eoxidation]
4. Balance the two half reactions do not multiply voltage values
5. Add the two half reactions and the voltages together.
6. Ecell = Eoxidation + Ereduction means standard conditions: 1atm, 1M, 25C
Devices that come in handy when constructing spontaneous cell--one that can act as a battery:
Oxidation occurs at the anode (may show mass decrease)
Reduction occurs at the cathode (may show mass increase)
The electrons in a voltaic or galvanic cell always flow from the Anode to the cathode the cathode
is + in galvanic (voltaic) cells
Salt Bridge bridge between cells whose purpose is to provide ions to balance the charge.
Usually made of a salt filled agar (KNO 3 ) or a porous cup
In an electrolytic cell, there is a positive anode.
Line notation
Standard cell notation (line notation) Ion sandwich in alphabetical order
Anode metal/anode ion//cathode ion//Cathode metal
For Reaction: M + N+ N + M+
Anode || Cathode (alphabetical order!)
M(electrode)|M+ (solution)|| N+ (solution)|N(electrode)| - indicates phase boundary
EX: Zn / Zn2+ (1.0 M)// Cu2+ (1.0 M) / Cu
Cell potential, electrical work & free energy
Combining the thermodynamics and the electrochemistry, not to mention a bit of physics:
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The work that can be accomplished when electrons are transferred through a wire depends on
the push or emf which is defined in terms of a potential difference [in volts] between two
points in the circuit.
work (J)
emf (V )=
charge (C)
Thus one joule of work is produced [or required] when one coulomb of charge is
transferred between two points in the circuit that differ by a potential of one volt
IF work flows OUT it is assigned a MINUS sign
When a cell produces a current, the cell potential is positive and the current can be
used to do work therefore and work have opposite signs!
work (J)
W
emf (V )= = - W = Vq
charge (C)
faraday(F)the charge on one MOLE of electrons = 96,485 coulombs

q = # moles of electrons F
For a process carried out at constant temperature and pressure, wmax [neglecting the very
small amount of energy that is lost as friction or heat] is equal to G, therefore.
Go = nFEo
Where, G = Gibbs free energy, n = number of moles of electrons, F = Faraday constant
9.6485309 104 J/V mol
So it follows that:
Eo implies nonspontaneous.
+Eo implies spontaneous (would be a good battery!)
Strongest Oxidizers are weakest reducers.
As Eo reducing strength .
As Eo oxidizing strength .
Dependence of cell potential on concentration
Voltaic cells at non standard conditions: LeChatliers principle can be applied. An increase in
the concentration of a reactant will favor the forward reaction and the cell potential will increase.
The converse is also true!
For a more quantitative approach..When cell is not at standard conditions, use Nernst
Equation:
E = E lnQ
Where, R = Gas constant 8.315 J/K mol, F = Faraday constant, Q = reaction quotient [products]
coefficient/[reactants] coefficient, E = Energy produced by reaction, T = Temperature in Kelvins,
n = # of electrons exchanged in BALANCED redox equation
Rearranged, another useful form
0.0592
Nernst equation: E = Eo logQ = at 25C (298K)
As E declines with reactants converting to products, E eventually reaches zero. Zero potential
means reaction is at equilibrium [dead battery]. Also, Q = K and G = 0 as well.
Concentration cells
We can construct a cell where both compartments contain the same components but at different
concentrations. Notice the difference in the concentrations pictured bellow.
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Because the right compartment contains 1.0 M Ag+ and the left compartment contains 0.10 M
Ag+, there will be a driving force to transfer electrons from left to right. Silver will be deposited
on the right electrode, thus lowering the concentration of Ag+ in the right compartment. In the
left compartment the silver electrode dissolves [producing Ag+ ions] to raise the concentration of
Ag+ in solution.
Applications of Galvanic Cells
Batteries: cells connected in series; potentials add together to give a total voltage.
Examples:
Lead-storage batteries (car)--Pb anode, PbO 2 cathode, H 2 SO 4 electrolyte
Dry cell batteries
Acid versions: Zn anode, C cathode; MnO 2 and NH 4 Cl paste
Alkaline versions: some type of basic paste, ex. KOH
Nickel-cadmium anode and cathode can be recharged
Fuel cells
Reactants continuously supplied (spacecraft hydrogen and oxygen)
Electrolysis and Electrolytic Cells
Electrolysis- the use of electricity to bring about chemical change, Literal translation split with
electricity
Electrolytic cells [NON spontaneous cells]:
Used to separate ores or plate out metals.
Important differences between a voltaic/galvanic cell and an electrolytic cell:
1) Voltaic cells are spontaneous and electrolytic cells are forced to occur by using an electron
pump or battery or any DC source.
2) A voltaic cell is separated into two half cells to generate electricity; an electrolytic cell
occurs in a single container.
3) A voltaic [or galvanic] cell is a battery; an electrolytic cell NEEDS a battery
4) AN OX and RED CAT still apply BUT the polarity of the electrodes is reversed. The
cathode is Negative and the anode is Positive (remember E.P.A electrolytic positive
anode). Electrons still flow FATCAT.
5) Usually use inert electrodes
Predicting the Products of Electrolysis:
If there is no water present and you have a pure molten ionic compound, then:
the cation will be reduced (gain electrons/go down in charge)
the anion will be oxidized (lose electrons/go up in charge)
If water is present and you have an aqueous solution of the ionic compound, then:
Youll need to figure out if the ions are reacting or the water is reacting.
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you can always look at a reduction potential table to figure it out but, as a rule of thumb:
no group IA or IIA metal will be reduced in an aqueous solution
Water will be reduced instead.
no polyatomic will be oxidized in an aqueous solution
Water will be oxidized instead.
*Since water has the more positive potential, we would expect to see oxygen gas produced at the
anode because it is easier to oxidize than water or chloride ion. Actually, chloride ion is the first
to be oxidized.
The voltage required in excess of the expected value (called the overvoltage) is much greater for
the production of oxygen than chlorine, which explains why chlorine is produced first. Causes of
overvoltage are very complex. Basically, it is caused by difficulties in transferring electrons from
the species in the solution to the atoms on the electrode across the electrode-solution interface.
Therefore, E values must be used cautiously in predicting the actual order of oxidation or
reduction of species in an electrolytic cell.
Half Reactions for the electrolysis of water
If Oxidized: 2H 2 O O 2 + 4H+ + 4e
If Reduced: 2H 2 O + 2e H 2 + 2OHApplications of electrolytic cells:
production of pure forms of elements from mined ores
Aluminum from Hall-Heroult process
Separation of sodium and chlorine (Down's cell)
Purify copper for wiring
electroplatingapplying a thin layer of an expensive metal to a less expensive one
Jewelry --- 14 K gold plated
Bumpers on cars --- Chromium plated
Charging a battery --- i.e. your car battery when the alternator functions
Corrosionprocess of returning metals to their natural state, the ores.
Involves oxidation of the metal which causes it to lose its structural integrity and
attractiveness.
The main component of steel is iron.
20% of the iron and steel produced annually is used to replace rusted metal!
Most metals develop a thin oxide coating to protect them, patinas, tarnish, rust, etc.
Corrosion of iron
An electrochemical process!
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Steel has a nonuniform surface since steel is not completely homogeneous. Physical strains
leave stress points in the metal as well causing iron to be more easily oxidized (anodic
regions) than it is at others (cathodic regions)
In the anodic region: Fe Fe2+ + 2e ; the electrons released flow through the steel to a
cathodic region where they react with oxygen
In the cathodic region: O 2 + 2H 2 O + 4e 4OH The iron (II) ions travel to the cathodic regions through the moisture on the surface of the
steel (just like ions travel through a salt bridge). Another reaction occurs in the cathodic
region:
4Fe2+(aq) + O 2 (g) + (4 + 2n) H 2 O (l) 2Fe 2 O 3 n H 2 O (s) + 8H+ (aq)
This means rust often forms at sites that are remote from those where the iron dissolved to
form pits in the steel
hydration of iron affects the color of the rust; black to yellow to the familiar reddish brown
Prevention: paint, coat with zinc [galvanizing], cathodic protectioninsert an active metal
like Mg connected by a wire to the tank or pipeline to be protected. Mg is a better reducing
agent than iron [so is more readily oxidized] the Mg anode dissolves and must be replaced,
BUT protects the steel in the meantime!
4. Equilibrium in chemical reaction
4.1. Thermodynamic process and Thermochemistry
Chemical Thermodynamics is the study of the energetics of a chemical reaction.
Thermodynamics deals with the absorption or release of energy (generally as heat) that
accompanies chemical reactions.
These dynamics generally give us an idea of whether a reaction will be spontaneous
Spontaneous describes a process that can occur without outside intervention (i.e.
changing the temperature, pressure or concentration)
Spontaneity does not imply that the process occurs quickly, but rather describes a
capability to proceed.
If a chemical reaction is found to be spontaneous in one direction, then under the same
conditions, the reverse reaction will be non-spontaneous
This does not mean that the reaction cannot occur, but that it will need some outside help.
The System and the Surroundings
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The system is the specific part of the universe that is of interest to us (i.e. the reaction with
reactants & products) and the surroundings is the rest of the universe
When performing experiments, we measure changes to the surroundings then apply those
findings to the system.
Energy is transferred between the system and the surroundings
Energy that is transferred from the system to the surroundings has a negative sign
Energy that is transferred from the surroundings to the system has a positive sign
E = E final - E Initial
State Functions
A State Function is a function or property whose value depends only on the present state
(condition) of the system not the path used to arrive at that condition.
The change in a state function is zero when the system returns to its original condition.
For non-state functions, the change is not zero if the path returns to the original condition
Heres an example with a chemical reaction:
The two paths below give the same final state:
o N 2 H 4 (g) + H 2 (g) 2NH 3 (g) + heat (188 kJ)
o N 2 (g) + 3H 2 (g) 2NH 3 (g) + heat (92 kJ)
State properties include for the formation of NH 3 : temperature, total energy, pressure,
density, and [NH 3 ]
Non-state properties include for the formation of NH 3 : heat and reactants used
Energy
Energy is the capacity to do work, or supply heat.
Energy = Work + Heat
Potential energy, PE, is stored energy; it results from position or composition.
Kinetic energy, KE, is the energy matter has as a result of motion.
KE = 1/2 mv2
Units for KE: 1 Joule = 1 kg.m2/s2 or 1 calorie = 4.184 J
Units of Energy the SI unit for energy is the Joule (J)
The J is a small amount of energy so scientists generally refer to Kilojoules (kJ)
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The calorie (cal) is another unit of energy, It is defined as the amount of energy
needed to raise the temperature of 1.00 g of water by one degree Celsius,
KE, Temperature & State
All substances have kinetic energy no matter what physical state they are in.
Solids have the lowest kinetic energy, and gases have the greatest kinetic energy.
As you increase the temperature of a substance, its kinetic energy increases.
Forms of Energy
There are six forms of energy: Heat, Radiant, Electrical, Mechanical, Chemical and Nuclear. We
can convert among these types of energy
Thermal Energy
Thermal Energy is the kinetic energy of molecular motion (translational, rotation, and vibration).
We measure this energy by finding the temperature of an object
Thermal energy is proportional to the temperature in degrees Kelvin
E thermal T(K)
Chemical Energy is the PE of a chemical compound where the chemical bonds act as
storage containers for the energy
Work
Work (w) is the application of a force (F) through a distance (d)
This work produces an objects movement
If the system performs work on the surroundings, the sign of w is negative.
If the surroundings perform work on the system, the sign of w is positive.
Work = Force Distance
Units for W: Newton-meters (N-m) or Joules (J), 1J = 1N-m
Expansion Work
A system that contains one or more gases performs a specific type of work called PV Work or
expansion work. It perform work as the gas expands against an opposing pressure (P) exerted by
the surroundings.
w = - PV, V = V Final - V Initial , 1L atm = 101 J
When a gas expands, w is negative because the system transfers energy to the surroundings
When a gas contracts, w is positive because the surroundings transfer energy to the system
Heat
Heat (q) is the energy that flows from a warmer object (higher temperature) to a cooler object
(lower temperature)
Heat is associated with the movement of particles
The faster the particles are moving, the more heat you generate (and vice versa)
If the system gives heat to the surroundings, the sign of q is negative.
If the surroundings give heat to the system, the sign of q is positive.
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Zero Law of Thermodynamics

If substance A is in thermal equilibrium with substance B and if substance B is in
thermal Equilibrium with C always substance A is in thermal equilibrium with C.
A
B
C
The First Law of Thermodynamics
It states that the internal energy (E) of a system, the sum of the kinetic and potential energy of all
its particles, changes when heat (q) and/or work (w) are added or removed, In a reaction, energy
is conserved. It is neither created nor destroyed.
Heat and/or work gained by the system is lost by the surroundings, and vice versa:
(q + w) sys = - (q + w) surr
It can be converted into a different type of energy though!
The energy change in a system equals the work done on the system + the heat added.
Total Energy of Reactants = Total Energy of Products
E = E final E initial = q + w
Energy and Enthalpy
Most chemical reactions are performed in containers that are open to the atmosphere.
The volume of the system is allowed to change but the pressure (atmospheric pressure)
remains constant.
If the work performed is limited to PV work, a state function called Enthalpy (H), it can
be defined.
H = E + PV
The change in enthalpy (H) is equal to the heat absorbed by the system under conditions
of constant pressure.
H = E + PV
There are two types of enthalpy changes:
1. The Enthalpy of Physical Change is the amount of heat required to change the state of matter
2. The Enthalpy of chemical change deals with the energy requirements of chemical reactions.
The Heat of the Reaction (H rxn ) gives the amount of heat absorbed or released due to a
chemical reaction at constant pressure.
H rxn = H products H reactants
In an Exothermic reaction, the reaction releases energy in the form of heat to the
surroundings (you feel the reaction get hot!)
o The energy of the reactants is greater than that of the products.
Eg. C(s) + O 2 (g) CO 2 + Energy
In an Endothermic reaction, the reaction absorbs energy in the form of heat from the
surroundings (you feel the reaction get cold!)
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o The energy of the products is greater than that of the reactants.

Eg. 2H 2 O (l) + Energy 2H 2 (g) + O 2 (g)
Hesss Law: The overall enthalpy change for a reaction is equal to the sum of the enthalpy
changes for the individual steps in the reaction.
Eg, 3H 2 (g) + N 2 (g) 2NH 3 (g) H = 92.2 kJ
Reactants and products in individual steps can be added and subtracted to determine the overall
equation.
(a) 2 H 2 (g) + N 2 (g) N 2 H 4 (g)
H1 = ?
(b) N 2 H 4 (g) + H 2 (g) 2 NH3 (g)
H2 = 187.6 kJ
(c) 3 H 2 (g) + N 2 (g) 2 NH 3 (g)
H3 = 92.2 kJ
H 1 = H 3 H 2 = (92.2 kJ) (187.6 kJ) = +95.4 kJ
Manipulating Chemical Enthalpy Changes
1. Reversing a reaction changes the sign of H for a reaction:
H = 2219 kJ
Eg. C 3 H 8 (g) + 5O 2 (g) 3CO 2 (g) + 4H 2 O(l)
3CO 2 (g) + 4H 2 O(l) C 3 H 8 (g) + 5O 2 (g)
H = +2219 kJ
2. Multiplying a reaction increases H by the same factor because H is also
stoichiometrically related to the coefficients of the balanced chemical equation:
Eg. 3(C 3 H 8 (g) + 5O 2 (g) 3CO 2 (g) + 4H 2 O(l)
H = 2219 kJ)
3C 3 H 8 (g) + 15O 2 (g) 3CO 2 (g) + 12H 2 O(l)
H = 6657 kJ
Standard Heats of Formation
Standard Heats of Formation (H f ): The enthalpy change for the formation of 1 mole of
substance in its standard state from its constituent elements in their standard states.
C(s) + 2H 2 (g) CH 4 (g) H f = -74.5 kJ
H f for any element in its standard state is defined as being zero.
H f = 0 for an element in its standard state
The standard enthalpy change for any chemical reaction is found by subtracting the sum of the
heats of formation of all reactants from the sum of the heats of formation of all products
H = H f (Products) H f (Reactants)
For a balanced equation, each heat of formation must be multiplied by the stoichiometric
coefficient.
aA + bB cC + dD
H = [cH f (C) + dH f (D)] [aH f (A) + bH f (B)]
Bond Dissociation Energy
There are over 18 million chemical compounds known at this time. Who do you think is making
all of the H f determinations for those compounds?
It is possible to get an approximate H f for a compound based on the bonds present.
The Bond Dissociation Energy can be used to determine an approximate value for
H f.
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H f = Reactant Bonds (Bonds Broken) Product Bonds (Bonds Formed)

Introduction to Entropy
We have stated that chemical and physical processes occur spontaneously only if they go
downhill energetically (give off energy) so that the final state is more stable and lower in
energy than the initial state.
However, we know that reactions that require energy (endothermic reactions) will also occur;
this is possible because energy is more than just heat. There are other forms of energy present
in reactions that allow it to be spontaneous despite absorbing heat.
Another factor that affects spontaneity of a reaction is the molecular disorder of the reaction.
The amount of molecular disorder in a system is called the systems entropy; it has units
of J/K (Joules per Kelvin).
S = S final S initial
Positive value of S indicates increased disorder and Negative value of S indicates
decreased disorder.
Limitations of the 1st law of thermodynamics, it tells nothing about the direction of a
spontaneous change
Second Law of Thermodynamics:
Reactions proceed in the direction that increases the entropy of the system plus surroundings.
A quantitative statement of the second law is that, for any real spontaneous process,
S = S sys + S surr > 0
Entropy and Enthalpy
To decide whether a process is spontaneous, sometimes both enthalpy and entropy changes must
be considered:
Spontaneous process: Decrease in enthalpy (H) and Increase in entropy (+S).
Non-spontaneous process: Increase in enthalpy (+H) and Decrease in entropy (S).
Third law of thermodynamics
Both entropy and enthalpy are state functions, but the nature of their values differs in a
fundamental way. Recall that we cannot determine absolute enthalpies because we have no easily
measurable starting point, no baseline value for the enthalpy of a substance. Therefore, we
measure only enthalpy changes.
Third law of thermodynamics, states that a perfect crystal has zero entropy at a temperature of
absolute zero: Ssys = 0 at 0 K. "Perfect" means that all the particles are aligned flawlessly in the
crystal structure, with no defects of any kind. At absolute zero, all particles in the crystal have
the minimum energy, and there is only one way it can be dispersed
Introduction to Gibbs free energy
Gibbs free energy change (G) weighs the relative contributions of enthalpy and entropy to
the overall spontaneity of a process.
G = H TS,
When G < 0 Spontaneous, G = 0 Equilibrium and G >0 Non-spontaneous
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Gibbs free energy at Equilibrium

Equilibrium (G = 0): Estimate the temperature at which the following reaction will be at
equilibrium. Is the reaction spontaneous at room temperature?
N 2 (g) + 3 H 2 (g) 2 NH 3 (g)
H = 92.0 kJ S = 199 J/K
4.2. Spontaneous process and thermodynamic equilibrium
Spontaneous processes
Spontaneous process: takes place naturally, without continuous outside intervention
E.g. a drop of food coloring will spread in a glass of water or once ignited H 2 gas
burns in O 2 gas.
Nonspontaneous process: only takes place as a result of continuous intervention
E.g., electricity is required to convert water to H 2 gas and O 2 gas
Keep in mind that spontaneous processes may be fast or slow.
a. An explosion is fast and spontaneous.
b. The process of rusting is slow and spontaneous.
Consider the following spontaneous processes at room temperature:
A drop of food coloring will spread in a glass of water.
Methane (CH 4 ) burns in O 2 gas.
Ice melts in your hand.
Ammonium chloride dissolves in a test tube with water, making the test tube colder.
Example: What do these processes or reactions have in common? Are they all exothermic?
Are they all endothermic?
4.3. Chemical equilibrium
The concept of equilibrium and the equilibrium constant
Many chemical reactions do not go to completion but instead attain a state of chemical
equilibrium.
Chemical equilibrium: A state in which the rates of the forward and reverse reactions are equal
and the concentrations of the reactants and products remain constant. It is a dynamic process.
The conversions of reactants to products and products to reactants are still going on, although
there is no net change in the number of reactant and product molecules.
E.g. For the reaction: N 2 O 4 (g) 2NO 2 (g)
1. The Equilibrium Constant

For a reaction: aA + bB cC + dD
[] []
Equilibrium constant: Kc = [] []
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The equilibrium constant, K c , is the ratio of the equilibrium concentrations of products over the
equilibrium concentrations of reactants each raised to the power of their stoichiometric
coefficients.
E.g. Write the equilibrium constant, K c, for N 2 O 4 (g) 2NO 2 (g)
Law of mass action - The value of the equilibrium constant expression, K c, is constant for a
given reaction at equilibrium and at a constant temperature. The equilibrium concentrations of
reactants and products may vary, but the value for K c remains the same.
Other Characteristics of K c
1) Equilibrium can be approached from either direction.
2) K c does not depend on the initial concentrations of reactants and products.
3) K c does depend on temperature.
Magnitude of K c
If K c >> 1, the equilibrium lies to the right and the reaction mixture contains mostly products
If K c <<1, the equilibrium lies to the left and the reaction mixture contains mostly reactants.
If 0.10 < Kc < 10, the mixture contains appreciable amounts of both reactants and products.
Writing equilibrium constant expressions
Calculating Equilibrium Constants, K c
K c values are listed without units
If equilibrium concentrations are known, simply substitute the concentrations into the
equilibrium constant expression:
Example- For the reaction, CO + 3H 2 CH 4 + H 2 O,
Calculate Kc from the following equilibrium concentrations: [CO] = 0.0613 M; [H 2 ] = 0.1839
M; [CH 4 ] = 0.0387 M; [H 2 O] = 0.0387 M.
Heterogeneous Equilibria and Homogeneous equilibria
Homogeneous equilibria: reactants and products exist in a single phase.
For the gas phase reaction: N 2 O 4 (g) 2NO 2 (g)
The equilibrium constant with the concentrations of reactants and products expressed in terms of
molarity, Kc, is:
[NO 2 ]2
Kc = [N
2O4]
Gas Phase Expressions can also be expressed by Kp

The Kp expression is written using equilibrium partial pressures of reactants & products.
For the reaction given above, the Kp expression is:
Kp =
[P [NO 2 ]2
[P N 2 O 4 ]
Kp is related to Kc
Since pressure and molarity are related by the Ideal Gas Law (PV = nRT), the following equation
relates Kp and Kc:
Kp = Kc(RT)n
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Where R = 0.0821 L.atm/ K mol, T = temperature in Kelvin

n = moles of gaseous products, moles of gaseous reactants
Note that Kc = Kp when the number of gas molecules are the same on both sides.
Example- Does Kc = Kp for (a) H 2 (g) + F2 (g) 2HF(g)? (b) 2SO 2 (g) + O 2 (g) 2SO 3 (g)?
Example- For the reaction, 2SO 2 (g) + O 2 (g) 2SO 3 (g) (a) write the equilibrium
constant expression, Kp. (b) What is the value for Kp if Kc = 2.8x102 at 1000 K?
Heterogeneous Equilibria and Solvents in Homogeneous Equilibria
Heterogeneous equilibria: reactants and products are present in more than one phase.
Pure solids and liquids: concentrations of pure solids and liquids are fixed by their density and
molar mass (both constants) and do not vary with the amount.
M=
Density
Molar mass
mol
L
ml
10 3 mL
1L
mol
g
Thus, the concentrations of solids and liquids are incorporated in the K c value; they are not part
of the variable K c expression:
Example: Write the K c expression for CaCO 3 (s) CaO(s) + CO 2 (g)
Omit concentration terms for solids and liquids from K c and K p expressions; only include
terms for gases (g) and aqueous substances (aq).
Example-Write the K c expression for the following reaction:
3Cu(s) + 2NO 3 -(aq) + 8H+(aq) 3Cu2+(aq) + 2NO(g) + 4H 2 O(l)
The relationship between chemical kinetics and chemical equilibrium
For the reaction N 2 O 4 (g) 2NO 2 (g)
Rate of forward reaction = Rate of reverse reaction
k f[N 2 O 4 ] = k r [NO 2 ]2
[NO 2 ]2
Rearrange: [N
2 O 4]
= K f = Kc
r
Thus, the equilibrium constant is simply the ratio of the forward and reverse rate constants which
are both constant values at a given temperature.
What does the equilibrium constant tell us?
Predicting the Direction of Reaction
The reaction quotient, Q, is the resulting value when we substitute reactant and product
concentrations into the equilibrium expression.
1. If Q > K, the reaction will go to the left.
The ratio of products over reactants is too large & the reaction will move toward
equilibrium by forming more reactants.
2. If Q < K, the reaction will go to the right.
The ratio of products over reactants is too small & the reaction will move toward
equilibrium by forming more products.
3. If Q = K, the reaction mixture is already at equilibrium, so no shift occurs.
Example: For the reaction, B 2A, Kc = 2. Suppose 3.0 moles of A and 3.0 moles of B are
introduced into a 2.00 L flask.
(a) In which direction will the reaction proceed to attain equilibrium?
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(b) Will the concentration of B increase, decrease or remain the same as the system
moves towards equilibrium?
Factors that affect chemical equilibrium
Le Chatelier's Principle: If a system at equilibrium is disturbed by an external stress, the system
adjusts to partially offset the stress as the system attains a new equilibrium position.
1. Changes in Concentration
Adding a reactant or product, the equilibria shifts away from the increase in order to
consume part of the added substance.
Removing a reactant or product, the equilibria shifts toward the decrease to replace part
of the removed species.
E.g. for H 2 + I 2 2HI, does the equilibria shift left or right if we:
a) add H 2 ? b) Remove I 2 ?
Changes in Volume and Pressure
Because the pressure of gases is related directly to the concentration changing the pressure by
increasing/decreasing the volume of a container will disturb an equilibrium system.
If P increases (V decreases), the system shifts to the side with a smaller number of gas
molecules (this effectively reestablishes equilibrium by decreasing the pressure).
If P decreases (V increases), the system shifts to the side with a greater number of gas
molecules.
Example: For N 2 (g) + 3H 2 (g) 2NH 3 (g), does the equilibrium shift left or right if the pressure
is increased?
Changes in Temperature
Heat can be considered a reactant in an endothermic rxn and a product in an exothermic rxn.
Endothermic (H > 0) R + Heat Products
Exothermic (H < 0) R Products + Heat
Recall that both Kc and the position of the equilibrium system will vary with temperature:
Kc is larger when the reaction shifts right. This occurs if T is increased for an
Endothermic Reaction or T is decreased for an exothermic reaction.
Kc is smaller when the reaction shifts left. This occurs if T is decreased for an
Endothermic Reaction or T is increased for an exothermic reaction.
Example: If the temperature is decreased for the reaction: 2CO 2 2CO + O 2 , H = 566 kJ.
a) Will the equilibrium shift left or right? b) Does Kc become larger or smaller?
Effect of a Catalyst
Catalysts lower Ea for the reaction, so a catalyst decreases the amount of time taken to
reach equilibrium for both the forward and reverse reactions.
The catalyst does not affect the equilibrium concentrations of reactants and products in
the equilibrium mixture; thus, the Kc value does not change.
4.4. Acid base equilibrium
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Acid-base reactions
We are going to be working with acid-base equilibria in aqueous solution, and we will use the
Brnsted-Lowry definitions that an acid is a source of H+ and a base is an acceptor of H+.
Acid ionization constant K a
A convenient way to write the reaction of an acid HA in water is
HA (aq) + H 2 O (l) H 3 O+ (aq) + A-(aq)
Here water is acting as a base, accepting the H+; the result, H 3 O+, called the conjugate acid of
H 2 O, since H 3 O+ can donate H+ to reform H 2 O. In a similar way, A- is called the conjugate base
of the acid HA, since A- can accept H+ to reform HA. The equilibrium constant is known as the
acid ionization constant K a ,
HA (aq) + H 2 O (l) H 3 O+ (aq) + A-(aq)
ka =
[H + ][A ]
[HA ]
With the understanding that [] stands for the numerical valuewithout unitsof the
concentration in mol/L. As usual, Ka is unit-less. An example acid ionization is
CH3COOH(aq)
Kc =
H+(aq) + CH3COO- (aq)
[H 3 O + ][ CH 3 COO ]
[CH 3 COOH ]
If Ka is much greater than 1, the acid is mostly dissociated and so is said to be a strong acid. If
Ka is much less than 1, the acid is dissociated only to a small extent and so is said to be a weak
acid.
Base ionization constant K b
Similarly, we can write the reaction of a base B in water as
H 2 O(l) + B(aq) HB+ (aq) + OH-(aq).
Here water is acting as an acid, donating the H+; the result, OH-, is called the conjugate base of
H 2 O, since OH- can accept H+ to reform H 2 O. Analogously, HB+ is called the conjugate acid of
the base B, since HB+ can donate H+ to reform B. The equilibrium constant is known as the base
ionization constant K b ,
kb =
[OH ][ HB + ]
[NH 3 ]
Here is an example base ionization

NH 3 + H 2 O NH 4 + + OH- ,
kb =
[OH ][ NH +
4]
[B]
If K b is much greater than 1, the base reacts nearly completely with water and so is said to be a
strong base. If K b is much less than 1, the base reacts hardly at all with water and so is said to be
a weak base.
Dissociation of water and pH of aqueous solutions
Fredrich Kohlrausch, around 1900, found that no matter how pure water is, it still conducts a
minute amount of electric current. This proves that water self-ionizes.
Since the water molecule is amphoteric, it may dissociate with itself to a slight extent.
Only about 2 in a billion water molecules are ionized at any instant!
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H 2 O(l) + H 2 O(l) H 3 O+(aq) + OH(aq)

The equilibrium expression used here is referred to as the autoionization constant for water
In pure water or dilute aqueous solutions, the concentration of water can be considered to be a
constant (55.6 M), so we include that with the equilibrium constant and write the expression as:
Kw = [H 3 O+][OH] = [H 3 O+]2 = [OH]2= 1.008 1014 at 25C = Ka K b
Knowing this value allows us to calculate the OH and H+ concentration for various situations.
[OH] = [H+] solution is neutral (in pure water, each of these is 1.0107)
[OH] > [H+] solution is basic
[OH] < [H+] solution is acidic
The pH Scale
The pH and pOH scales provide a convenient way to express the acidity and basicity of dilute
aqueous solutions. The pH scale ranges from 0 to 14. The pH and pOH of a solution are defined
as
pH = log [H+] pOH = log[OH] pH + pOH = 14
Calculate pH and concentration of OH- ion of a solution in which the concentration of H 3 O+ is
0.050mol/L.
Solution
pH = -log [H 3 O+] = -log [0.050]= 1.3 and pOH = 14 - pH = 13.7
[OH] = 10-pOH = 10-13.4 =
Exercise
1. Calculate either the [H+] or [OH] from the information given for each of the following
solutions at 25C, and state whether the solution is neutral, acidic, or basic.
1.0 105 M OH
b. 1.0 107 M OH
c. 10.0 M H+
Common Ion Effect
Addition of a substance having an ion in common with the equilibrium mixture of the common
ion causes the equilibrium to shift left; this suppresses the ionization of a weak acid or a weak
base. The source of the common ion is typically provided by adding a strong acid, a strong base
or a soluble salt to the equilibrium reaction mixture.
For example, ionization of weak acid, acetic acid is suppressed in the presence of sodium acetate
than when it is dissolved in pure aqueous solution.
Since acetate ion is common ion, according to Le-Chateliers Principle, the equilibrium of
CH 3 COOH shift to the left as CH 3 COO- combines with H 3 O+ to form non-ionized CH 3 COOH
and H 2 O. The result is a drastic decrease in [H 3 O+] in the solution and ionization of CH 3 COOH
also depressed.
What happens to the pH of the acetic acid solution if we add (a) HCl?
Page 67
Buffer Solutions
Buffers are a solution which resists changes in pH upon addition of small amounts of an acid or
base on to it. It contains a conjugate acidbase pair with both the acid and base in reasonable
concentrations, the acidic component reacts with added strong bases and the basic component
reacts with added strong acids H+.
A buffers solution can be classified either as an acidic or basic buffers.
Acidic buffers (pH<7) are those composed of weak acid plus a soluble ionic salt of the
weak acid (conjugate salt of acid) e.g., CH 3 COOH plus NaCH 3 COO.
Basic buffers (pH>7) are composed of weak base plus a soluble ionic salt of the weak
base (conjugate salt of base) e.g., NH 3 plus NH 4 Cl.
Calculating the pH of Buffered Solutions
The central equation in buffer calculations is the Henderson-Hasselbalch equation, which is
merely a rearranged form of the Ka expression. The HH equation always applies, but the correct
equilibrium concentrations have to be used!
Equilibrium expiration of buffer solution
Acidic buffer
Ka=
[H + ] [A ]
[HA ]
[H+] = Ka
[HA ]
[A]
pH= pKa + log
[base ]
[Acid ]
Acid-Base Titration
Acid-Base titration is based on the titration of bases by a standard acid (acidimetry) or titration of
acids by a standard base (alkalimetry). Acid-Base titration is also known as a neutralization
titration which is widely used to determine the amounts of acids and bases and it might also be
used to monitor the progress of reactions that produce or consume hydrogen ions.
The standard reagents used in acid/base titrations are always strong acids or strong bases, most
commonly HCl, HClO 4 , H 2 SO 4 , NaOH, and KOH. Weak acids and bases are never used as
standard reagents because they react incompletely with analytes. A titration curve in acid-base
titration is a plot of pH as ordinate versus the amount (usually volume) of acid or base added as
abscissa. It displays graphically the change in pH as acid or base is added to a solution and
shows how pH changes.
Titration curve is evaluated experimentally by determination of the pH at various stages during
the titration by a potentiometric method or it may be calculated from theoretical principles. In
order to construct the curve we have to calculate pH at three different stages: pre-equivalent
point, equivalence point, and post equivalent. In the titration of a:
strong acid and strong base the salt is neutral, pH at equivalence point = 7
strong acid and weak base the salt is acidic, pH at equivalence point < 7
strong base and weak acid the salt is basic, pH at equivalence point > 7
Acid-Base Titration Curves
Strong acid/Strong base Titration
For the reaction of a strong base with a strong acid the only equilibrium reaction of importance is
H 3 O+ (aq) + OH-(aq) H 2 O(aq)
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Example 1
Consider the titration of 50.0 mL of 0.100 M HCl with 0.200 M NaOH.
Pre-equivalent point
Before any base is added the pH is directly calculated from the concentration of the acid, HCl.
Initially the solution is 0.100 M in HCl, which, since HCl is a strong acid, means that the pH is
pH = -log[H 3 O+] = -log[HCl] = - log(0.100) = 1.00
After addition of some amount of base, before the equivalence point, HCl is present in excess
and the pH is determined by the concentration of excess HCl. For example, after adding 10.0 mL
of NaOH, the concentration of excess HCl is
[HCl] =
moles excess HCl
M a V a M b Vb
Va + Vb
total volume
(0.100M)(50.0mL ) (0.200M)(10.0mL )
[HCl] =
50.0mL +10.0mL
giving a pH of 1.30.
Equivalent point
At the equivalence point the moles of HCl and the moles of NaOH are equal. Since neither the
acid nor the base is in excess, the pH is determined by the dissociation of water.
K w = 1.00 x 10-14 = [H 3 O+][OH-], 1.00 x 10-7 = [H 3 O+]
Thus, the pH at the equivalence point is 7.00.
At the equivalence point moles of HCl is equal to that of moles NaOH. The volume of NaOH
needed to reach the equivalence point, therefore, is calculated as from the relationship
Ma Va = Mb Vb
V eq = V b =
Ma Va
Mb
(0.100mL )(50.0mL )
0.200M
25mL
Post-Equivalent point
At this point, there is an excess of NaOH, and pH is determined by the concentration of excess
OH. For example, after adding 30.0 mL of titrant the concentration of OH is
[NaOH] =
moles excess NaOH

total volume
M b V b M a V a
Va + Vb
(0.200mL )(30.0mL ) (0.100mL )(50.0mL )

50.0mL +30.0mL
= 0.0125M
To find the concentration of H 3 O+, we use the K w expression
1.00 x 10-14 = [H 3 O+][OH-], [H 3 O+] = [HCl] = 8.00 x 10-13 ,giving a pH of 12.10.
Calculating the titration curve for the titration of a strong base with a strong acid is handled in
the same manner, except that the strong base is in excess before the equivalence point and the
strong acid is in excess after the equivalence point.
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Figure (a) The titration curve for 100. mL of 0.100 M HCl with 0.100 M NaOH. (b) The
titration curve for 100. mL of 0.100 M NaOH with 0.100 M HCl.
Solubility Product Principle
2.2.1. Solubility, Solubility Equilibria and Solubility Product
Solubility-Solubility is the maximum concentration (in terms of the solid) of a substance that can
exist in solution before precipitation begins if sufficiently seeded.
Suppose we add one gram of solid barium sulfate, BaSO 4 , to 1.0 liter of water at 25C and stir
until the solution is saturated. Very little BaSO 4 dissolves and careful measurements of
conductivity show that one liter of a saturated solution of barium sulfate contains only 0.0025
gram of BaSO 4 , no matter how much more BaSO 4 is added. The BaSO 4 that does dissolve is
completely dissociated into its constituent ions.
BaSO 4 (s) Ba2+(aq) + SO 4 2-(aq)
In equilibria that involve slightly soluble compounds in water, the equilibrium constant is called
a solubility product constant, K sp . The activity of the solid BaSO 4 is one. Hence, the
concentration of the solid is not included in the equilibrium constant expression. For a saturated
solution of BaSO 4 in contact with solid BaSO 4 , we write
BaSO4(s) Ba2+(aq) + SO 42-(aq) and K sp = [SO 4 2-][Ba2+]
In general, the solubility product expression for a compound is the product of the
concentrations of its constituent ions, each raised to the power that corresponds to the number of
ions in one formula unit of the compound. The quantity is constant at constant temperature for a
Page 70
saturated solution of the compound. This statement is the solubility product principle. The very
small amount of solid zinc phosphate, Zn3 (PO 4 ) 2 , that dissolves in water gives three zinc ions
and two phosphate ions per formula unit.
Zn3 (PO 4 ) 2 (s) 3Zn2+ (aq) + 2PO 4 3-(aq) Ksp = [Zn2+]3 + [PO 4 3- ]2 = 9.1 x 10-33
Generally, we may represent the dissolution of a slightly soluble compound and its Ksp
expression as
MyXz(s) yMz+(aq) + zXy-(aq) and Ksp = [Mz+][Xy-]2
In some cases a compound contains more than two kinds of ions. Dissolution of the slightly
soluble compound magnesium ammonium phosphate, MgNH4PO4, in water and its solubility
product expression are represented as
MgNH 4 PO 4 (s) Mg2+(aq) + NH 4 +(aq) + PO 43-(aq) Ksp = [Mg2+][NH 4 +][PO 4 3-] = 2.5 x10-12
The molar solubility of a compound is the number of moles that dissolve to give one liter of
saturated solution. If the molar solubility of a compound is known, the value of its solubility
product can be calculated.
We know the molar solubility of BaSO 4 . The dissolution equation shows that each formula unit
of BaSO 4 that dissolves produces one Ba2+ ion and one SO 4 2- ion.
BaSO 4 (s)
Ba2+(aq)
+
SO 4 2-(aq)
1.1x10-5 mol/L
1.1x10-5 mol/L
1.1x10-5 mol/L
In a saturated solution [Ba2+] = [SO42-] = 1.1x10-5 M.
K sp = [SO 4 2-][Ba2+] = (1.1x10-5 mol/L) (1.1x10-5 mol/L) = 1.2 x 10-10
4.6. Electrochemistry
Redox Reactions, Reducing and Oxidizing Agents
Redox reactions
The term redox is used as an abbreviation for the processes of reduction and oxidation. These
two processes usually occur simultaneously. Redox reactions are electron transfer reactions. The
separate equations showing which substance gains electrons and which substance loses electrons
are known as half-equations. Oxidation is defined as the loss of electrons and reduction is
defined as the gain of electrons. Oxidizing agents are substances which accept electrons;
reducing agents are substances which donate electrons.
Example 1
When a piece of iron is immersed in copper (II) sulphate solution, it soon becomes coated with
copper. The reaction may be represented by the ionic equation:
Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s)
This shows that iron is the reducing agent and it is oxidized to Fe2+(aq) :
Oxidation half-equation: Fe(s) Fe2+(aq) + 2eThe oxidizing agent is Cu2+(aq) and it is reduced to copper :
Reduction half-equation: Cu2+(aq) + 2e- Cu(s)
We can write a generalized equation for a redox reaction as
Page 71
Disproportionation is a redox reaction in which a particular chemical species is simultaneously

oxidized and reduced.
Example- Iodine is oxidized to iodate (V) ion and reduced to iodide ion in alkaline medium.
3I 2 + 6OH- IO 3 - + 5I- + 3H 2 O
Redox Reactions in Electrochemical Cells and Electrode Potential

Electrochemical cell:
An electrochemical cell is a device which produces an electromotive force (e.m.f.) as a result of
chemical reactions taking place at the electrodes. An electrochemical cell is thus a device which
converts chemical energy into electrical energy. Each cell consists of two half-cells. In one halfcell an oxidation half-reaction takes place and in the other a reduction half-reaction takes place.
Cathode is the electrode at which reduction occurs. The
Anode is the electrode at which an oxidation takes place.
Galvanic, or voltaic, cells store electrical energy. The reactions at the two electrodes in such
cells tend to proceed spontaneously and produce a flow of electrons from the anode to the
cathode via an external conductor. An electrolytic cell, in contrast to a voltaic cell, requires an
external source of electrical energy for operation. Note that in the electrolytic cell, the direction
of the current is the reverse of that in the galvanic cell and the reactions at the electrodes are
reversed as well.
Examples
This combination of half-cells is an electrochemical cell (galvanic cells or voltaic cells).
Fig. Movement of charge in a galvanic cell

Salt bridge:
Simple electrochemical cells used in a laboratory often consist of two half-cells separate by a salt
bridge. It may consist of an inverted U-tube containing salt solution. It is plugged at both ends by
cotton wool. Alternatively it may consist of strip of filter paper soaked in salt solution. Salts used
for this purpose include NH 4 NO 3 , KNO 3 and KCl. The salt used is chosen so that it does not
react with the ions in either half-cell.
Salt bridge thus serves two main functions:
It completes the circuit by allowing ions carrying charge to move towards one half-cell
from the other.
It provides cations and anions to replace those consumed at the electrodes.
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Difference between galvanic and Electrolytic Cells

Electrochemical cell (Galvanic Cell)
Electrolytic cell
A Galvanic cell converts chemical energy into

electrical energy.
An electrolytic cell converts electrical energy into

chemical energy.
Here, the redox reaction is spontaneous and is

responsible for the production of electrical energy.
The redox reaction is not spontaneous and

electrical energy has to be supplied to initiate the
reaction.
The two half-cells are set up in different containers,

being connected through the salt bridge or porous
partition.
Both the electrodes are placed in a same container

in the solution of molten electrolyte.
Here the anode is negative and cathode is the positive Here, the anode is positive and cathode is the
electrode. The reaction at the anode is oxidation and negative electrode. The reaction at the anode is
that at the cathode is reduction.
oxidation and that at the cathode is reduction.
The electrons are supplied by the species getting
The external battery supplies the electrons. They
oxidized. They move from anode to the cathode in the enter through the cathode and come out through
the anode.
external circuit.
Measurement of electromotive force (e.m.f.) in electrochemical cells:

By using a high resistance voltmeter, the current in the external circuit is virtually zero and the
cell registers its maximum potential difference. This maximum p.d. is called the e.m.f. This
e.m.f. gives a quantitative measure of the likelihood of the redox reaction taking place in the cell.
E cell is the e.m.f. of the cell in volts. Changes that occur spontaneously have positive e.m.f.,
while changes that do not occur spontaneously have negative e.m.f. We can set up
electrochemical cells with the Cu (s)|Cu2+(aq) half-cell as the oxidation half-cell another metalmetal ion (Ag+(aq)/Ag(s)) half-cells as the reduction half-cell. E.m.f.
Short-Hand Cell notation: Convention: Anode on Left
Cu (s) /Cu2+(aq) (0.1M) Ag+(aq)(0.1M) / Ag(s) Liquid-liquid interface
Electrode Potential
Standard Reduction Potentials
Each half-reaction has a cell potential
Each potential is measured against a standard which is the standard hydrogen electrode
[consists of a piece of inert Platinum that is bathed by hydrogen gas at 1 atm].
The hydrogen electrode is assigned a value of zero volts.
Standard conditions1 atm for gases, 1.0M for solutions and 25C for all (298 K)
Naught, -we use the naught to symbolize standard conditions [Experiencing a thermo
flashback?] That means
Ecell, Emf, or cell become Ecello, Emfo , or cello when measurements are taken at standard
conditions. Youll soon learn how these change when the conditions are nonstandard!
The diagram below (c) illustrates what really happens when a Galvanic cell is constructed from
zinc sulfate and copper (II) sulfate using the respective metals as electrodes.
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(c)
Notice that 1.0 M solutions of each salt are used

Notice an overall voltage of 1.10 V for the process
Reading the reduction potential chart
Elements that have the most positive reduction potentials are easily reduced (non-metals)
Elements that have the least positive reduction potentials are easily oxidized (metals)
The table below used to tell the strength of various oxidizing and reducing agents.
The electrochemical series
When redox systems are arranged in order of their standard electrode potentials, the
electrochemical series is obtained. The following table shows standard electrode potentials of
some common redox systems:
Uses of the standard electrode potential values
1. To compare the strength of oxidizing/reducing agents
The standard electrode potential of a half-cell is a measure of the oxidizing or reducing power of
the species in it, i.e. their ability to compete electrons. In general the stronger an oxidizing agent,
the more positive its electrode potential and a strong reducing agent has a large negative
electrode potential.
Examples
Ozone gas is a more powerful oxidizing agent than chlorine gas:
O 3 (g) + 2H+(aq) + 2e- O 2 (g) + H 2 O(l) EO = + 2.08 V
Cl2 (g) + 2e- 2 Cl- (aq) EO = + 1.36 V
Calcium metal is a more powerful reducing agent than lead metal:
Pb2+(aq) + 2e- Pb(s) EO = - 0.13 V
Ca2+(aq) + 2e- Ca(s) EO = - 2.87 V
Page 74
2. To calculate the e.m.f. of cells:

Calculating Standard Cell Potential Symbolized by Ecell or Emf ORcell
1. Decide which element is oxidized or reduced using the table of reduction potentials.
Remember: The more positive reduction potential gets to be reduced.
2. Write both equations AS IS from the chart with their voltages.
3. Reverse the equation that will be oxidized and change the sign of the voltage [this is now
E oxidation]
4. Balance the two half reactions do not multiply voltage values
5. Add the two half reactions and the voltages together.
6. Ecell = E oxidation + E reduction (E cathode - Eanode ) means standard conditions Devices that
come in handy when constructing spontaneous cell--one that can act as a battery:
Oxidation occurs at the anode (may show mass decrease)
Reduction occurs at the cathode (may show mass increase)
The electrons in a voltaic or galvanic cell always flow from the Anode to the cathode the cathode
is positive in galvanic (voltaic) cells
Page 75
Example 1
Zn|ZnSO4 ( aZn2+ = 1.00 )||CuSO4(a Cu2+ =1.00 )|Cu
Anode
cathode
2+
Zn + 2e Zn
E0 = -0.763 V
E0 = +0.337V
Cu2+ + 2e- Cu
Zn reaction spontaneously backward - forms negative electrode - place of oxidation - anode
If a=1.00 M, E = E 0 :
Ecell = E cathode - E anode
= +0.337 - (-0.763) = +1.100 V
Applications of Galvanic Cells
Batteries: cells connected in series; potentials add together to give a total voltage.
Examples:
Lead-storage batteries (car)--Pb anode, PbO 2 cathode, H 2 SO 4 electrolyte
Dry cell batteries
Acid versions: Zn anode, C cathode; MnO 2 and NH 4 Cl paste
Alkaline versions: some type of basic paste, ex. KOH
Nickel-cadmium anode and cathode can be recharged
Fuel cells
Reactants continuously supplied (spacecraft hydrogen and oxygen)
Electrolysis and Electrolytic Cells
Electrolysis- the use of electricity to bring about chemical change, Literal translation split with
electricity
Electrolytic cells [NON spontaneous cells]:
Used to separate ores or plate out metals.
Important differences between a voltaic/galvanic cell and an electrolytic cell:
1) Voltaic cells are spontaneous and electrolytic cells are forced to occur by using an electron
pump or battery or any DC source.
2) A voltaic cell is separated into two half cells to generate electricity; an electrolytic cell
occurs in a single container.
3) A voltaic [or galvanic] cell is a battery; an electrolytic cell NEEDS a battery
4) AN OX and RED CAT still apply BUT the polarity of the electrodes is reversed. The
cathode is Negative and the anode is Positive (remember E.P.A electrolytic positive
anode). Electrons still flow FATCAT.
5) Usually use inert electrodes
Predicting the Products of Electrolysis:
If there is no water present and you have a pure molten ionic compound, then:
the cation will be reduced (gain electrons/go down in charge)
the anion will be oxidized (lose electrons/go up in charge)
If water is present and you have an aqueous solution of the ionic compound, then:
Page 76
Youll need to figure out if the ions are reacting or the water is reacting.
you can always look at a reduction potential table to figure it out but, as a rule of thumb:
no group IA or IIA metal will be reduced in an aqueous solution
Water will be reduced instead.
no polyatomic will be oxidized in an aqueous solution
Water will be oxidized instead.
*Since water has the more positive potential, we would expect to see oxygen gas produced at the
anode because it is easier to oxidize than water or chloride ion. Actually, chloride ion is the first
to be oxidized.
The voltage required in excess of the expected value (called the overvoltage) is much greater for
the production of oxygen than chlorine, which explains why chlorine is produced first. Causes of
overvoltage are very complex. Basically, it is caused by difficulties in transferring electrons from
the species in the solution to the atoms on the electrode across the electrode-solution interface.
Therefore, E values must be used cautiously in predicting the actual order of oxidation or
reduction of species in an electrolytic cell.
Half Reactions for the electrolysis of water
If Oxidized: 2H 2 O O 2 + 4H+ + 4e
If Reduced: 2H 2 O + 2e H 2 + 2OHApplications of electrolytic cells:
production of pure forms of elements from mined ores
Aluminum from Hall-Heroult process
Separation of sodium and chlorine (Down's cell)
Purify copper for wiring
electroplatingapplying a thin layer of an expensive metal to a less expensive one
Jewelry --- 14 K gold plated
Bumpers on cars --- Chromium plated
Page 77
Charging a battery --- i.e. your car battery when the alternator functions
Corrosionprocess of returning metals to their natural state, the ores.
Involves oxidation of the metal which causes it to lose its structural integrity and
attractiveness.
The main component of steel is iron.
20% of the iron and steel produced annually is used to replace rusted metal!
Most metals develop a thin oxide coating to protect them, patinas, tarnish, rust, etc.
Chemical
Kinetics
Note.
2014
Rate = k[A]m[B]n
Page 78
1 - The Rate Expression

Rate = k[A]m[B]n
Where: k is a constant, and m, n show the orders of the reaction with respect to each reactant.
It is an experimentally determined equation in that the information (n,m,k etc) can only be found
through experimentation and not through theoretical considerations. The rate equation shows the
relationship between the speed of a reaction and the concentrations of the individual reactants.
Once the orders are found then they provide information regarding the mechanism of the specific
reaction.
The overall order of reaction is the total of m+n above.
K is the rate constant. This gives a measure of how fast the reaction proceeds. External factors
such as temperature, pressure, particle size and catalysts affect the value of the rate constant.
Graphing results
If a graph of reaction concentration against time is plotted a curve is obtained as the reactant is
used up in the course of the reaction. The rate of any reaction is at its greatest at the beginning
(time=0). As the reactants are used up the rate decreases.
If a graph of rate against time is plotted then the shape obtained will depend on the overall order
of the reaction.
0th order graph:- straight flat line

1st order graph:- straight line
All other orders: curve
If a curve is obtained then further mathematical treatment of the results is necessary.

as: Rate = k[A]m[B]n
if [B] is kept constant, then: log Rate = log k' + m log[A]
And a plot of log Rate against log [A] will give a straight line of gradient m (the graph has the
form y = mx + c)
Keeping [A] constant and treating the results of rate when [B] varies will allow a similar
determination of the order with respect to B. Once the two orders are ascertained then the rate
constant k can be found.
Page 79
Half Life
The half life is the time taken for the concentration of reactants to reach half of its original value.
For most reactions the half life changes as the reaction procedes but this is not the case for first
order reactions where the half life is constant. (Short half life= fast rate)
Using the half life to find the rate constant
The rate constant can be found from a concentration/time graph by taking a point, finding its
concentration, then finding a point on the graph which corresponds to half this concentration.
The half life is the time between these two points. The half life is also equal to ln2/ k where k is the
rate constant (equation given in data book).
Solving the rate equation by inspection

If a series of experimental results are obtained for rate at different reactant concentrations the
change in rate can be ascertained for those reactions when the concentration of one of the
reactants is kept constant while the other reactant concentration is changed.
Rate of reaction
Throughout this topic it is essential to keep in mind that this is an experimentally determined
science. There are no theories that can determine the rate expression by merely considering the
chemicals reacting.
By observation we can see that varying certain conditions changes the rate with which the
reactants are used up (or the products formed). Kinetics investigates this and in doing so gives us
clues as to the mechanism of the reaction.
Some definitions
Rate: Measured as the concentration, mass or volume (or anything else that can be directly
related to one of these) of a reactant or product changes with time. Conventionally, we define
rate in terms of concentration change with time... mol dm-3 s-1 (moles per litre per second) is the
'usual' unit
Mechanism: Is the actual route taken by reacting particles in order to make the products. It may
be that there are several stages or steps between reactants and products involving the formation
Page 80
of intermediates. These intermediates have a varying lifespan and are often undetectable. One of
the aims of kinetics is to build up a picture of the actual mechanism involved in a reaction.
Factors affecting the rate of a reaction
Concentration of reactants
Temperature
Particle size (in the case of solids)
Catalysts
Effect of concentration
When all other factors are kept constant we can investigate how the rate of a reaction depends on
the concentration of the reactants.
A + B --> Products
To allow for any possibility we can express the effect of the concentrations of A and B on the
rate of the reaction by the expression:
Rate = k [A]x[B]y
Where does this equation come from?
Mathematically, it allows for all possible effects of changing [A] and [B]. For example, if
changing the concentration of A has no effect on the rate then the value of x=0, If the rate is
directly proportional to the concentration of A then x=1. If there is some other effect then x will
take another number. The equation then is ust a method of expressing the rate in terms of the
concentrations. It is called the rate expression, also the rate equation or law.
Rate = k [A]x[B]y
The 'k' is called the rate constant. As the name implies, it has a constant value for any specific
reaction at constant temperature. The value of the rate constant for a reaction gives us a measure
of how fast the reaction is. A very small value for k means a very slow reaction and vice versa.
The order of reaction
Page 81
The numbers to which the concentrations are raised in the rate expression are called the orders of
reaction with respect to the individual concentrations.
Rate = k [A]x[B]y
X is the order with respect to [A] and Y is the order with respect to [B]. The total order of the
reaction is the sum of the individual orders, in this case X + Y.
The order of the reaction with respect to a specific reagent provides information about the
number of particles of this reagent involved in the rate determining step of the mechanism. The
rate determining step is the slowest step.
Note: If equilibrium feeds into the rate determining step then this will also influence the order
with respect to any particles that appear on the left hand side (reactants) of the equilibrium.
Units of the rate constant

The units of the rate constant depend on the total order of the reaction.
For order = 1 (first order reaction)
The rate expression is:
Rate = k [A]1
Substituting the units in each part we get:
mol dm-3 s-1 = k [mol dm-3]1
Cancelling out from both sides gives:
s-1 = k
For a second order reaction:

Rate = k [A]2
Substituting the units in each part we get:
Page 82
mol dm-3 s-1 = k [mol dm-3]2

Rearranging and cancelling out from both sides gives:
dm3 mol-1 s-1 = k
16.1.2: Deduce the rate expression for a reaction from experimental data. AIM 7: Virtual
experiments can be used here
Measurement of rate
The rate of a reaction MUST be determined by experimental measurements. These can involve
following the disappearance of reactants or the generation of products. There are many
techniques that may be used.
Measuring the evolution of a gas volume with time

Measuring the decreasing mass of a reaction vessel as a gas is evolved
Measuring the changing characteristics of a solution in terms of colour (using a
colourimeter), conductivity, pH etc.
Procedure to determine the rate expression
Measure the rate for a known series of initial reactant concentrations

Change one of the concentrations keeping the other constant and measure the rate again
Change the concentration of the one previously kept constant, and measures the initial
rate again.
Repeat this procedure until enough data is obtained
Solving problems
The majority of problems involve processing a set of data and obtaining the orders of reaction:
Experiment
[A] / mol dm-3
[B] / mol dm-3
[C] / mol dm-3
Rate/ mol dm-3 s-1
0.1
0.1
0.1
6.2 x 10-4
0.1
0.2
0.1
1.2 x 10-3
0.1
0.1
0.2
6.2 x 10-4
Page 83
0.2
0.1
0.2
2.5 x 10-3
From the above set of data it may be seen that when the concentration of B doubles (all other
concentrations remaining constant) the rate also doubles. This tells us that the order with respect
to [B] is 1.
If the rate should multiplies by a factor of four while the concentration only doubles, the order
would be 2.
Once all orders are obtained the rate constant can be determined by 'plugging' values into any
one of the experimental data sets.
16.1.4: Sketch, identify and analyse graphical representations for zero, first and second order
reactions. Students should be familiar with both concentration-time and rate-concentration
graphs
Graphing results
The simplest plot is the concentration (of reactants or products) against the time. This is always a
curve, the gradient of which is the rate of the reaction. A typical experimental set-up to obtain
the results is shown below:
gas collection apparatus
graph of gas volume against time
The gradient of this graph at any point gives the rate of the reaction at that time. It would be
possible to select several points on the graph and then calculate the corresponding rates. These
can then be plotted on a second graph of rate against concentration (volume of gas, in this case).
The shape of concentration / rate graphs depends on the overall order of the reaction.
Page 84
0th order reactions

There is no correlation between the rate and the concentration of a zeroth order reaction. A flat
line is obtained.
This is in keeping with the rate law expression: Rate = k[A]0
1st order reactions

There is direct proportionality between the rate and the concentration. A straight line is obtained
passing through the origin.
This is in keeping with the rate law expression: Rate = k[A]1

The gradient (slope) of the graph gives the rate constant k, whose units are now s-1
Page 85
2nd order reactions

When rate is plotted against concentration a curve is obtained. However, when the order is any
other than 0th or 1st a curve is also given. The graph is of limited value in this case and the data
must be further processed.
Inspection of the rate expression for a second order reaction

Rate = k[A]2
Shows that a plot of rate against concentration would give a curve. If logs are taken throughout
however this gives:
log Rate = log k + 2log[A]
This has the same form as a straight line graph y = mx +c
Consequently, a plot of log rate against log[A] gives a straight line graph whose intercept is the
value for log k and the gradient is equal to the order of the reaction.
This treatment is valid for any order values. The gradient (slope) of the graph line is always
equal to the order.
Page 86
Activation energy
Arrhenius equation:
k = Ae(-Ea/RT) (data book)
where:
A is a constant related to the number, orientation and frequency of collisions occurring

between the particles in the reaction.
k is the rate constant
R is the universal gas constant
T is the absolute temperature
Determination of the activation energy from practical results

If rates experiments are carried out at different temperatures the results can be plotted on a graph
to obtain a value for the activation energy for a specific reaction.
k = Ae(-Ea/RT)
therefore:
ln k = lnA Ea/RT
A plot of natural log of k against (1/T) will give a straight line of gradient - Ea/R
Enthalpy level diagrams
Page 87
These show a curve representing the path between the reactants and products in terms of energy.
Energy is shown on the y-axis. The reactants and products are of different chemical energies and
the curve goes between the two levels (the reactants and products) having an energy maximum
between them (with the distance between the highest point and the reactants being equal to the
activation energy of the forward reaction).
An energy graph showing an exothermic reaction
Reactions only occur when the reacting particles have energy greater than the activation energy
and are able to get over the activation energy barrier.
Catalysis
Catalysts provide an alternative mechanism with lower activation energy. This means that a
greater number of collisions will be successful and the reaction procedes at a faster rate
Homogeneous catalysts -- catalysts in the same state (phase -- ie solid, liquid or gas) as the
reactants. Hetrogeneous catalysts -- catalysts in a different phase (usually a solid) from the
reactants.
Homogeneous catalysts operate by reacting with the reactants and eventually producing a
reaction pathway of lower activation energy (and also being regenerated at the end of this
process). Hetrogeneous catalysts provide a reactive site on which an activated complex forms,
weakening the bonds and increasing the rate of collisions thus increasing the rate of reaction.
Examples of catalysed processes
Page 88
Process
catalyst used
type
Contact (sulphur trioxide)
Vanadium pentoxide
heterogenous
Haber (ammonia)
Iron
heterogenous
Hydrogenation of alkenes
Nickel
heterogenous
Polymerisation
Pt (Zeigler Natta)
heterogenous
Polymerisation
Oxygen
homogeneous
Describe qualitatively the relationship between the rate constant (k) and temperature (T).
Effect of temperature on the reaction rate
Direct observations make it clear that increasing the temperature increases the rate of a chemical
reaction. In approximate terms, most reactions double in rate for a ten degree increase in
temperature.
This effect was first quantified by Arrhenius who produced the equation:
rate constant k = Ae-Ea/RT
quantity
description
meaning
A-
the Arrhenius constant
This is a measure of the

proportion of molecules that
collide with enough energy to
react AND which have the
correct
orientation
for
successful collision.
e-
the natural number on which the natural

2.303
logarithms is based
Ea -
the activation energy
This is the minimum energy

that a molecular collision
must have before it can be
successful and lead to
Page 89
reaction - units kJ mol-1

R-
the universal gas constant
8.314 in SI units
T-
the Absolute temperature in Kelvin (K)
Equal to the temperature in

Celsius + 273
Determine activation energy values from the Arrhenius equation by a graphical method.
The Arrhenius equation: and its logarithmic form are provided in the chemistry data booklet .
Use of simultaneous equations will not be assessed.
Using the Arrhenius equation

Although it is not easy to see the relationship between the rate constant and the absolute
temperature from the equation, if we break it down into steps perhaps it will help.
The temperature appears in the term Ea/RT

If T increases then the term Ea/RT gets smaller
However in the Arrhenius equation Ea/RT has a negative value, therefore as T increases
Ea/RT gets LESS negative.
So as -Ea/RT is the power to which 'e' is raised then the term e-Ea/RT gets larger (as the
power gets less negative) as the temperature increases.
The rate constant is directly proportional to the term e-Ea/RT and so the rate constant gets
larger as T gets larger.
Example: Calculate the rate constant when T = 300K (A = 0.3, Ea = 50kJ mol-1)
k = Ae-Ea/RT
Ea/RT = 50000/(8.314 x 300) = 20.05
e-Ea/RT = 1.97 x 10-9
k = Ae-Ea/RT
k = 5.90 x 10-10
Notes:
Page 90
1. Why is the slowest step of a mechanism said to be rate determining?

It acts like a bottleneck in that it prevents the other processes from reaching the end of the
reaction and in this way determines the overall rate. It is similar to the idea of a car journey that
has to pass through an area of roadwork. The car will be slowed right down by the roadworks
and this is therefore the crucial factor in determining the overall time of the journey. return
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1.

Introduction to study of modern chemistry

1.1. The atom in modern chemistry

Breathing O 2 binds to Fe in Hemoglobin in red blood cells and thousands of other

We get energy for industry by combustion:

General Chemistry L. Note for Pre-Engineering Students

Modern Chemistry 1790 to present day

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He then measured the deflection of beams of e- to determine the charge-to-mass ratio

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The modern view of atomic structure: an introduction element

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Elements and Compounds

2Na + Cl2 2NaCl

3. Single Displacement Reactions (Sometimes called oxidation-reduction equations)

4. Metathesis or Double Displacement Reactions

General Chemistry L. Note for Pre-Engineering Students

General Chemistry L. Note for Pre-Engineering Students

Notice: Always theoretical yield is greater than or equal to actual yield.

Actual yield (g)

Theoretical yield (g)

Exercise1: When 5.00 g of KClO 3 is heated it decomposes according to the equation:

General Chemistry L. Note for Pre-Engineering Students

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Fig.2: The wave length of a waveis the peak-to-peak distance.

For wave characteristics: E = h = hc/

For particles: E = mc2 (Einstein)

particles is called the de Broglie wavelength.

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, Where h (Planck's constant) = 6.63x1034Js.

Where n = 1, 2 ... (only discrete energies).

c. The wave number?

where c = the speed of light = 3.00x108 m/s; units = s1, = m

Examples: Calculate the frequency of light with a wavelength of 500 nm?

Schrdinger applied: idea of an electron behaving as a wave to the problem of electrons in

For 1 electron, corresponds to an orbital the region of space within which an

Does not describe the exact location of the electron.

2 are proportional to the probability of finding an electron at a given point.

Uncertainty Principle: Problem of defining nature of electrons in atoms solved by Werner

is proportional to the probability of finding an electron at a given point.

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Single valued, Continuous, Continuous first derivative, Quadratically integrable

, where is volume element (i. e. = , , )

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-2, -1, 0, +1, + 2

-3, -2, -1, 0, +1, +2, +3

The concept of atomic orbital

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one ess, star").

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2.6. Bonding in transition metals compounds and coordination complexes

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Complex Ion and Ligands

[Pt(H 2 NCH 2 CH 2 NH 2 ) 2 Cl2 ]Cl2