Table of contents

FOURTH QUARTER

Module 6
Lesson III | Thermochemistry
Energy Changes in Chemical Reactions
First Law of Thermodynamics
Enthalpy of Chemical Reactions
Calorimetry
Standard Enthalpy of Formation and Reaction Hess’ Law
Lesson IV | Chemical Kinetics
The Rate of Reaction
Factors That Influence Reaction Rate
The Rate Law and Its Component
Collision Theory
Catalysis
Summary
Module 7
Lesson I | Chemical Thermodynamics
Spontaneous Processes
Entropy
The Second Law of Thermodynamics
Gibbs Free Energy and Chemical Equilibrium
Lesson II | Chemical Equilibrium
The Equilibrium Condition
Writing The Reaction Quotient/Equilibrium Constant
Expression
Predicting The Direction of a Reaction
Significance of the Equilibrium Constant
La Chatelier’s Principle
Summary
Module 8
Lesson III | Acid-Base Equilibria and Salt Equilibria
Bronsted Acids and Bases
The Acid-Base Properties of Water
pH: A Measure of Acidity
Conjugate Acid-Base Pairs
Strong and Weak Acids and Bases
The Relative Strengths of Conjugate Acid-Base Pairs
Summary

Vocabulary

Presentation (Group 4, Day 1)

Reflection

References

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module 6 THERMOCHEMISTRY
Energy transformation is the process of changing energy from one form to
another. Objects can affect other objects when they have energy. In line with this, we
have thermochemistry that shows the study of heat and energy changes that
accompany physical and chemical processes. Heat is the transfer of thermal energy
between two bodies at different temperature. Temperature is a measure of the thermal
energy (flow from higher temperature to lower temperature).

Every substance has certain amount of energy stored in the chemical bonds of a
substance. For thermodynamic studies we need to divide the universe into two parts:
the system (part we are investigating) and the surroundings (everything else). There are
three types of thermodynamics systems. Based on the possible heat and matter
transfer, they are classified as open, closed and isolated systems.

1. Open System
It can exchange mass and energy with the surroundings. It is the
one which freely allows energy and matter to be transferred in and out of
a system, from the system into the environment.

2. Closed System
It allows the transfer of energy but not mass. Does not allow the
exchange of matter but allows energy to be transferred. Heat is also
transferred to the surroundings.

3. Isolated System
This system is completely sealed. Matter is not allowed to be
exchanged with the surroundings. Heat can’t transfer to the
surroundings.

There are two forms of energy. Heat is when energy flows from the warmer body
to the cooler one. Work is when transfer of energy to or from a system by any means
other than heat. Both measured in energy units, so they must both represent energy.
They are processes and cannot be stored. Thermal energy can only flow from a higher
temperature to a lower temperature. It is the flow of heat that constitutes “heat”. “Flow”
of heat recalls the 18th century notion that heat is an actual substance called “caloric”
that could flow like a liquid.
 Heat can be transferred by means of
conduction and radiation. Conduction is transfer of
thermal energy that can be accomplished by
bringing two bodies into physical contact.
Radiation is another mechanism of
thermal energy transfer when hot objects
convey energy to anybody in slight via
electromagnetic radiation in the infrared
part of the spectrum.

Work is defined as the product of displacement and a parallel applied force.

Electrical work is done on a system by electrons. It is done when a body having a
charge moves through a potential difference. On the other hand, mechanical work is
force acting through a distance. It arises when an object moves a distance against an
opposing force.

Internal energy is simply the totality of all forms of kinetic and potential energy of
the system. It is the sum of the kinetic energy of motion of molecules, and the potential
energy represented by the chemical bonds between the atoms and any other
intermolecular forces that may be operative.

Enthalpy (H) is a thermodynamic quantity used to describe heat changes taking

place at constant pressure. It is used to quantify the heat flow into or out of a system in
a process that occurs at constant pressure.

∆H = H (products) – H (reactants)
∆H = heat given off or absorbed during a reaction at constant pressure

The first law of thermodynamics (Law of Conservation of Energy) states that

energy can be converted from one form to another, but cannot be created or destroyed.

ΔUsys + ΔUsurr = 0

Any change in the internal energy (ΔE) of a system is given by the sum of the
heat (q) that flows across its boundaries and the work (w) done on the system by the
surroundings.

(ΔE) = (q) + w
 Calorimetry is a method used to determine the heat involved in a physical or
chemical change. It relies on the law of conservation of energy. The measurement of
the amount of heat evolved or absorbed when a process or chemical reaction takes
place.

A device called a calorimeter may be used to measure the heat released from a
chemical reaction. Basically, what it does is measure the change in temperature of the
system when a reaction takes place.

Hess’s Law states that the change in enthalpy for any chemical reaction is
constant, whether the reaction occurs in one or several steps. An exothermic reaction at
constant pressure has a negative change in enthalpy, - ΔH and an endothermic reaction
at constant pressure have a positive change in enthalpy, + ΔH. For an exothermic
reaction, the heat content of the reactants is greater than the heat content of the
products heat is released. The value of ΔH < 0. For an endothermic reaction, the heat
content of the products is greater than the heat content of the reactants heat is
absorbed. The value of ΔH > 0.

Rate of reaction as a measure of how fast a reaction takes place. The rate of a
reaction is often expressed as a change in amount or concentration of a substance
(reactant or product) per unit time. Chemical kinetics is the study of rates of reactions
and factors that affect them.

Factors That Affect Rates of Reactions:

• Nature of reactants and ability of reactants to meet

• Concentration of reactants
• Temperature of reaction system
• Presence of a catalyst

Collision theory emphasize that for

a reaction to take place, reactant particles
must have activation energy or the
minimum amount of energy required and
the right orientation for effective collision to
bring about a chemical change. Activation
energy is the minimum energy required for
the electron clouds and nuclei of reactant
particles to overcome the repulsions and
form bonds.
Figure 1. Two reactant particles approach each other then fly apart because they
are not correctly oriented for a reaction to occur.

Figure 2. Slow moving particles approach each other then eventually fly apart.

Figure B3. Fast moving, energetic molecules correctly oriented form new
substances.

Over all, collision theory comes with two types. The effective and ineffective
which tells that chemical reaction has proper orientation and sufficient energy, and
conversely on the other hand. With regards, it has three assumptions stating that
molecules must collide, sufficient energy and proper orientation.
 chemical
module 7 thermodyna
mics
Under chemical thermodynamics, let’s first state what the three laws are of
included to it. The first Law – energy of the universe is constant. Energy can be
converted from one form to another but cannot be created or destroyed. The second
law – entropy of universe increases. The entropy of the universe increases in a
spontaneous process and remains unchanged in an equilibrium process. Lastly, the
third law – at absolute zero, the entropy of a perfect crystal is 0. The entropy of a perfect
crystalline substance is zero at the absolute zero of temperature (T = 0, K= -273oC).

Spontaneous processes come with

its characteristics such as it is a physical or
chemical change that occurs by itself.
These processes occur without requiring
an outside force and continue until
equilibrium is reached. For examples, heat
flows from a hotter object to a colder one,
an iron object rusts in moist air, and sugar
dissolves in a cup of coffee. A
spontaneous process is one that takes
place without energy from an external
source. For a chemical reaction to be spontaneous, it should proceed without an input
of energy.

Entropy, S, is a thermodynamic quantity that is a measure of how spread out or

dispersed the energy of a system is among the different possible ways that system can
contain energy. It is a quantity that is generally used to describe the course of a
process, that is, whether it is a spontaneous process and has a probability of occurring
in a defined direction, or a non-spontaneous process and will not proceed in the defined
direction, but in the reverse direction.

Process Order —> Disorder

Melting Solid —> Liquid
Vaporization Liquid —> Vapor
Dissolving Solute —> Solution
Heating System at T1 —> System at T2

The spreading out of more concentrated molecules and the spreading out of
more concentrated energy are changes from more order to more random. The changes
that occur are the ones that lead to an increasing randomness of the universe. Entropy
is sometimes referred as the measure of randomness and disorder.

At high enough temperature, the spontaneous change is from Solid Liquid Gas;
gas is more random than liquid and liquid is more random than solid. There is an
increase in entropy (S) of the system by going from solid to liquid to gas.

The Second Law of Thermodynamics deals with entropy. It tells whether a

process or chemical reaction can occur. The connection between entropy and the
spontaneity of a reaction is expressed by the second law of thermodynamics. It states
that: “The entropy of the universe increases in a spontaneous process and remains
unchanged in an equilibrium process.” Because the universe is made up of the system
and the surroundings, the entropy change in the universe (ΔSuniv) for any process is
the sum of the entropy changes in the system (ΔSsys) and in the surroundings (ΔSsur).

ΔSuniv = ΔSsys + ΔSsur > 0 Process is spontaneous.

ΔSuniv = ΔSsys + ΔSsur = 0 Process tends not to occur; equilibrium is attained.
ΔSuniv = ΔSsys + ΔSsur < 0 Reverse process occurs spontaneously.

It is possible for either ΔSsys or ΔSsur to be negative, as long as their sum is

greater than zero. At a stable equilibrium, ΔSuniv = 0, in this case, ΔSsys or ΔSsur must
be equal in magnitude but opposite in sign.

Another thermodynamic function is used in order to express the spontaneity of a

reaction more directly. This is called Gibbs free energy, G. The use of G predicts
changes that are focused on the system. Gibbs free energy is defined as: G = H – TS. If
the entropy of the universe increases then the ΔG of the system will decrease. The
direction of spontaneous change is negative ΔG for system. The ΔG tells us if a change
can occur for a chemical reaction.

The change in free energy (ΔG) of a system for a constant-temperature process

is ΔG = ΔH –TΔS. Free energy is the energy available to do work. If a particular reaction
is accompanied by a release of usable energy (ΔG is negative), the reaction is
spontaneous.
 A state of balance is also referred to as a state of equilibrium. In a reversible
reaction, when the reactants start to form the products, the products would then start to
reform the reactants. The two opposing processes happen at different rates but a
certain point in the reaction will be reached where the rates of the forward and
backward reactions are the same. This is the state of chemical equilibrium.

Changes in the rate of the forward and

backward reactions in a reversible reaction

The relationship between the concentrations of the reactants and products may
be expressed using the law of mass action expression/equilibrium constant expression.
For the general equilibrium reaction:

aA + bB cC + dD

the law of mass action expression is written as

Keq = [C]c[D]d
[A]a[B]b
where the [ ] is the concentration expressed in molarity and Keq is the equilibrium
constant. If molar concentrations are used, Keq may also be referred to as Kc. The law of
mass action is basically the ratio of the concentrations of the products raised to their
respective stoichiometric coefficients to that of the reactants.

When the mass of a certain pure solid substance is doubled, its volume is also
doubled. Therefore, when the mass and volume is related to get the concentration, a
constant value is obtained. Only reactants and products whose concentration varies
during a chemical reaction are included in the expression.
 The equilibrium constant, K, is the numerical value that is obtained when
equilibrium concentrations are substituted to the equilibrium constant expression. The
value of K may vary from very large to very small values. This value provides an idea of
the relative concentrations of the reactants and products in an equilibrium mixture.

The reaction quotient, Q, it is the value obtained when product and reactant
concentrations or partial pressures at any point of the reaction is plugged in the
equilibrium constant expression. It is calculated in the same way as K. The reaction
quotient may be used to determine if a particular reaction is at equilibrium, and if not, in
which direction the reaction will proceed to attain the equilibrium.

If Q = K, then the system is already at equilibrium;

If Q > K, the products dominate the reaction

mixture so the products must react to form the
reactants; reaction proceeds in the backward
direction until equilibrium is attained;

If Q < K, the reactants dominate the reaction

mixture so the reactants must react to form the
products; reaction proceeds in the forward
direction until equilibrium is attained.

Recalling the characteristics of a system at chemical equilibrium, we can tell that

state of balance – the rate of product formation is equal to the rate of reactant
reformation. Dynamic situation happens when the forward and the reverse processes
continue to take place even though it appears to have stopped because there is no
change in the relative concentrations of the reactants and products. It is mathematically
described by the law of mass action.

However, systems at chemical equilibrium may be disturbed by the changes in

various experimental conditions. The effect of any change in these conditions to a
system at chemical equilibrium can be described by the Le Chatelier’s Principle. It
states that if a stress (changes in reaction conditions) is applied to a system in
equilibrium, then the systems adjusts in order to reduce the effect of the stress applied.
The stress that may affect a system at chemical equilibrium include changes in the
concentration of either products or reactants, changes in temperature and changes in
pressure for gaseous equilibria.
 Increasing the concentration of a substance in an equilibrium mixture displaces
the equilibrium in the direction which consumes some of the added material.
Conversely, decreasing the concentration of a substance favors the reaction which
produces it. Le Chatelier’s principle, the stress referred here is the change in
concentration. When the concentration of either a reactant or a product is increased, the
equilibrium shifts into the direction that would consume that added component. If the
concentration is decreased, then the equilibrium shifts into the direction that replenishes
the lost component.

Le Chatelier’s Principle: Water Tank Analogy

When the temperature is increased, the reaction which consumes the applied
heat is favored like the reaction which is endothermic. When the temperature is
decreased, the reaction which produces heat is favored such as the reaction which is
exothermic.

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 Acid-base
module 8 and salt
Equilibria
equilibria
Robert Boyle and Svante Arrhenius are the prominent people in this equilibra
era. For they made such theories that change the present world and more of concluding
their essentials with acids, bases and even salts in terms of such condition.

Matters can first and foremost can be related with amphoteric, a general term for
substances that can react both as an acid and a base. On the other hand, amphiprotic
(protic refers to hydrogen ion) is a more specific term used to describe a substance
which can both donate and accept hydrogen ions (protons). All amphiprotic substances
are also amphoteric, but not all amphoteric substances are amphiprotic.

The products of the ionization of water molecules

include a hydrogen ion and a hydronium ion.

Protons do not exist as an identifiable species in water. All protons that might
form in water bond firmly to the electron pair of another water molecule to produce the
hydronium ion. After an acid has lost its proton, the resulting species is capable of
acting as a base. The same applies to Bronsted base.

The stronger the acid, the weaker the conjugate base. The weaker the acid, the
stronger the conjugate base. Acids and bases in the Bronsted model therefore exist as
conjugate pairs whose formulas are related by the gain or loss of a hydrogen ion.

As devised by Sorensen, pH stands for the “power of hydrogen.”

pH = -log10[H+]
= -log10[H3O+]
[H+] = [H3O+]
= 10-pH

We can you use the pH scale in differentiating acidic, neutral and basic solutions.
If pH > 7, then the solution is acidic. If pH = 7, then the solution is neutral. If pH < 7, then
the solution is basic. pH can also be determined using pH meter and acid-base
indicators. Common indicators such as phenolphthalein, methyl red, and bromothymol
blue are used to indicate pH ranges of about 8 to 10, 4.5 to 6, and 6 to 7.5, accordingly.
On these ranges, phenolphthalein changes from colorless to pink, methyl red from red
to yellow, and bromothymol blue from yellow to blue. For universal indicators, however,
the pH range is much broader and the number of color changes is much greater.
Usually, universal pH indicators are in the paper strip form.

It is important to take note of pH of

biological systems. For human survival, human
body works within the pH range of 7.0 to 7.8.
Living organisms can survive only in a narrow
range of pH. Large amount of acids are being
released in the stomach every time you eat. It
helps in the digestion of food without harming
the stomach. Tooth decay starts when the pH
of the mouth is lower than 5.5. Tooth enamel,
made up of calcium phosphate, is corroded
when the pH in the mouth is below 5.5.

In plants and animal survival, when pH of rain

water is less than 5.6, it is called acid rain. When acid
rain flows into the rivers, it lowers the pH of the river
water. Aquatic life cannot survive in acidic water.
Acid rain has indirect effects on plants. It
weakens the trees by damaging their leaves, limiting
the nutrients available to them, or poisoning them with
toxic substances slowly released from the soil. Trees
affected by acid rain do not grow as quickly as usual,
their leaves and needles turn brown and fall off when
they should be green and healthy.

In terms of the soil acidity, plants require a

specific pH range for their healthy growth. Soil pH
should be maintained at >5.5. Acidic soil prevents or
limits root development. Plants grown in acidic soil
cannot absorb water and nutrients, are stunted, and
exhibit nutrient deficiency symptoms (especially those
for phosphorus).
 Strong acids and bases conducts electricity due to large number of ions it
contains. Substance which conducts electricity weakly is weak acids and bases. They
contain less ions and mostly molecules. Acid strength refers to its ability to lose a
proton. A strong acid is one that completely ionizes (dissociates) in a solution yielding a
mole of hydronium ion. A strong base always gets the proton.

The proton is highlighted in red in the equation HA + H2O. After mixing, the
proton can go to either the H2O molecule or stick with A-. There are two possibilities for
this reaction:

If H2O is a strong base it will get the proton and

the reaction will yield high concentration of H3O+ and A-.

If A- has a stronger attraction to the proton

(low tendency to lose a proton) we say that it is a weak acid,
then the reaction will yield low concentration of H3O+ and A-..

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vii
 Vocabulary
Amphoteric – a molecule that can act as either an acid or a base depending on its
chemical environment
Curvature – the degree to which a bent shape is curved
Electronegativity – ability of an atom to attract towards itself a shared of pair electron
Energy – quantity that denotes the ability of a system to do work
Equilibrium – state of a reaction in which the rates of the forward and reverse reactions
are equal.
Dipole – generally occur between two nonmetals that share electrons as part of bond
Hydrogen bond – an intermolecular attraction between partially positively charged
hydrogen in one molecule and a partially negatively charged oxygen, nitrogen or
fluorine in a nearby molecule
Intermolecular – a type of interaction between two different molecules
Ion – an atom or group of atoms bearing electrical charge
Ion-dipole – an electrostatic interaction involving a permanent dipole in one molecule
and an ion
Ion-induced dipole force – an electrostatic interaction involving a temporary dipole in
one molecule and a permanently charged ion
Non-polar molecule – a molecule which has no separation of charge, so no positive or
negative poles are formed
Phase diagram – a graph showing the phase a sample of matter has under different
conditions of temperature and pressure
Polar – one that has uneven charge distribution
Polar bond – covalent bond between atoms where the electrons forming the bond are
unequally distributed
Polar molecule – a molecule that has a mostly positive charge on one side and a
mostly negative charge on the other
Tension – force transmitted through a rope, string, cable, or similar object

xiii
 presentatIon
Amphoteric – a molecule that can act as either an acid or a base depending on its
chemical environment
Curvature – the degree to which a bent shape is curved
Electronegativity – ability of an atom to attract towards itself a shared of pair electron
Energy – quantity that denotes the ability of a system to do work
Equilibrium – state of a reaction in which the rates of the forward and reverse reactions
are equal.
Dipole – generally occur between two nonmetals that share electrons as part of bond
Hydrogen bond – an intermolecular attraction between partially positively charged
hydrogen in one molecule and a partially negatively charged oxygen, nitrogen or
fluorine in a nearby molecule
Intermolecular – a type of interaction between two different molecules
Ion – an atom or group of atoms bearing electrical charge
Ion-dipole – an electrostatic interaction involving a permanent dipole in one molecule
and an ion
Ion-induced dipole force – an electrostatic interaction involving a temporary dipole in
one molecule and a permanently charged ion
Non-polar molecule – a molecule which has no separation of charge, so no positive or
negative poles are formed
Phase diagram – a graph showing the phase a sample of matter has under different
conditions of temperature and pressure
Polar – one that has uneven charge distribution
Polar bond – covalent bond between atoms where the electrons forming the bond are
unequally distributed
Polar molecule – a molecule that has a mostly positive charge on one side and a
mostly negative charge on the other
Tension – force transmitted through a rope, string, cable, or similar object

vii
xiii
 reflectIon
Amphoteric – a molecule that can act as either an acid or a base depending on its
chemical environment
Curvature – the degree to which a bent shape is curved
Electronegativity – ability of an atom to attract towards itself a shared of pair electron
Energy – quantity that denotes the ability of a system to do work
Equilibrium – state of a reaction in which the rates of the forward and reverse reactions
are equal.
Dipole – generally occur between two nonmetals that share electrons as part of bond
Hydrogen bond – an intermolecular attraction between partially positively charged
hydrogen in one molecule and a partially negatively charged oxygen, nitrogen or
fluorine in a nearby molecule
Intermolecular – a type of interaction between two different molecules
Ion – an atom or group of atoms bearing electrical charge
Ion-dipole – an electrostatic interaction involving a permanent dipole in one molecule
and an ion
Ion-induced dipole force – an electrostatic interaction involving a temporary dipole in
one molecule and a permanently charged ion
Non-polar molecule – a molecule which has no separation of charge, so no positive or
negative poles are formed
Phase diagram – a graph showing the phase a sample of matter has under different
conditions of temperature and pressure
Polar – one that has uneven charge distribution
Polar bond – covalent bond between atoms where the electrons forming the bond are
unequally distributed
Polar molecule – a molecule that has a mostly positive charge on one side and a
mostly negative charge on the other
Tension – force transmitted through a rope, string, cable, or similar object

vii
xiii
 references
Amphoteric – a molecule that can act as either an acid or a base depending on its
chemical environment
Curvature – the degree to which a bent shape is curved
Electronegativity – ability of an atom to attract towards itself a shared of pair electron
Energy – quantity that denotes the ability of a system to do work
Equilibrium – state of a reaction in which the rates of the forward and reverse reactions
are equal.
Dipole – generally occur between two nonmetals that share electrons as part of bond
Hydrogen bond – an intermolecular attraction between partially positively charged
hydrogen in one molecule and a partially negatively charged oxygen, nitrogen or
fluorine in a nearby molecule
Intermolecular – a type of interaction between two different molecules
Ion – an atom or group of atoms bearing electrical charge
Ion-dipole – an electrostatic interaction involving a permanent dipole in one molecule
and an ion
Ion-induced dipole force – an electrostatic interaction involving a temporary dipole in
one molecule and a permanently charged ion
Non-polar molecule – a molecule which has no separation of charge, so no positive or
negative poles are formed
Phase diagram – a graph showing the phase a sample of matter has under different
conditions of temperature and pressure
Polar – one that has uneven charge distribution
Polar bond – covalent bond between atoms where the electrons forming the bond are
unequally distributed
Polar molecule – a molecule that has a mostly positive charge on one side and a
mostly negative charge on the other
Tension – force transmitted through a rope, string, cable, or similar object

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