GENCHEM: COURSE MATERIAL 1 - It also describes the effects of temperature and

Kinetic Molecular Model pressure on matter

Particle (intramolecular & intermolecular)
Matter - anything that takes up space and has mass.
Energy – is what makes the matter moves. Intramolecular
- “within”
What is Matter? - can hold particles together
Made up of atom (smallest particle) -Not strongly affected by physical changes
Molecule (formed by the combination of 2 or more - Chemical bond
atoms.) - Determine chemical behavior of substance
Intermolecular
Matter > Possess energy - “between”
>Energy transforms matter - can hold together identical particles
- Solid - Strongly affected by physical changes
-Liquid - Attractive forces
-Gas - Determine the state of matter
-and other states of matter
>Changes in temperature & pressure change the phase Intermolecular forces
of matter -exist among all the particles that compose matter
● Releases energy - Responsible for the very existence of the condensed
-Freezing states (solid & liquid)
-Deposition - In the condensed states, the constituent particles are
-Condensation close together and exert moderate to strong attractive
● Requires energy forces on one another
-Melting - The state of matter depends on the magnitude of
-Evaporation Intermolecular forces among the constituent particles
-Sublimation relative to the amount of thermal energy in the sample.
Matter - Made up of tiny particles known as atoms -At room temperature,
-Particles are in constant motion
-Particles in motion have kinetic energy, and their
motion increases as they gain energy.
-There is a transfer of energy between particles (atoms
& molecules) as these particles collide with each other.
-Molecular motion is greatest in gases, less in liquids,
and least in solids
Properties of Solids
Kinetic Molecular Model
-It is used to explain why states of matter differ in Density
movements and arrangements. The ratio of mass per unit volume.
- It describes the forces between molecules and the Solid has greater density than liquids and gases
energy that they posses

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 Can you explain why ice float
on water?
=Water is less dense as a solid
than it is as a liquid.
=The three- dimensional
structure of ice keeps water
molecules farther apart than
they are in liquid.
=The water molecule in ice are less closely packed
together than in liquid water.
=There are more spaces between the molecules.
- Liquids are less fluid than gases;
- Liquid can diffuse through another liquid.
Viscosity
- A measure of the resistance of a fluid to flow;
- The viscosity of a liquid is determined by the type of
intermolecular forces involved, the shape of the
molecules, and the temperature.
- The stronger the intermolecular force, the higher the
viscosity.
- Size and shape of particles affect the viscosity.

Crystalline solids -The individual pieces of crystalline Surface tension

solids are called crystals.
-A solid whose atoms, ions, or molecules are arranged
in an orderly, geometric, three-dimensional structure.

-The energy required to increase the surface area of a

liquid by a given amount.
- It is a measure of the
inward pull by particles in
the interior.
-Its shapes determined by the type of unit cell is built.
- The stronger the
-A unit cell is the smallest arrangement of connected
attraction among the
points that can be repeated in three dimensions to form
particles, the greater the
the lattice.
surface tension.
- F = 2γL = 2γ2πr = 4γπr
Metallic solids
They possess luster
Capillary action
Malleable
- The ability of a liquid to flow in narrow spaces without
Ductile
the assistance of, or even in opposition to, external
Good conductors of heat and electricity
forces like gravity.
Two forces at work:
Amorphous solids
Cohesion is the force of attraction between identical
-Means “without shape” in Greek
molecules.
-Particles are not arranged in a regular, repeating
Adhesion is the force of attraction between different
pattern.
molecules.
-Forms when a molten metal cools too quickly to allow
enough time for crystals to form.
Density
-Examples: glass, rubber, and plastic.
-Liquids have densities that vary according to their
weight.
Properties of Liquids
-The greater the weight, the higher the density.
Fluidity
-Ability to flow;

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 Properties of Gases - Determine chemical behavior of substance
Intermolecular
Volume - “between”
-Do not have definite volume - can hold together identical particles
- Molecules move freely - Strongly affected by physical changes
- Mixture of gas, such as air, the various gases will - Attractive forces
coexist within the same volume - Determine the state of matter
Coulomb’s Law
Pressure 1 𝑞1 𝑞2
E = 4𝜋𝜀 𝑟
0
- It is the movements of the molecules exerted force
(When q1 and q2 are opposite in sign, E is negative.)
over the area.
- The more gas molecules present, the more frequent
The potential energy (E) of two oppositely charged
the collision with the side of the container, the more
particles (with charges q1 and q2) decreases (becomes
force against the side of the container, which all result
more negative) with increasing magnitude of charge
to more pressure.
and with decreasing separation (r) between them.
Temperature
Bonding forces - are the result of large charges (the
charges of protons and electrons) interacting at very
close distances.

Intermolecular
Forces are the result of smaller charges (as we shall see
in the following discussion) interacting at greater
-It is the measure of the average kinetic energy of the distances.
particles in matter.
- Likely proportional to pressure Types of Intermolecular Forces
-Dispersion Forces
-Dipole-dipole Forces
-Hydrogen Bonds
-Ion-dipole Forces

Dispersion Force
-also called the London force or London-Dispersion
Force
GENCHEM: COURSE MATERIAL 2 - result of fluctuations in the electron distribution within
molecules or atoms.
Intermolecular Forces & Solids & Liquids -present in all molecules and atoms

Intermolecular Forces:
The Forces that Holds Condensed States Together
These are generally attractive forces, and the basis of
these forces is simply electrostatic attraction (positive &
negative attract)

Particle (intramolecular & intermolecular) Instantaneous dipole or a temporary dipole.

Intramolecular An instantaneous dipole on any one helium atom

- “within” induces instantaneous dipoles on neighboring atoms,
- can hold particles together which then attract one another.
-Not strongly affected by physical changes
- Chemical bond
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 Molar mass can serve as a guide when comparing
dispersion forces within a family of similar elements or
compounds,
The boiling points of the n-alkanes rise with increasing
molar mass and the consequent stronger dispersion
forces.

Dipole-Dipole Force
- exists in all molecules that are polar.
- Polar molecules have electron-rich regions (which
have a partial negative charge) and electron-deficient
The magnitude of the dispersion force depends on how regions (which have a partial positive charge).
easily the electrons in the atom or molecule can move or
polarize in response to an instantaneous dipole, which in
turn depends on the size (or volume) of the electron
cloud.
A larger electron cloud results in a greater dispersion
force because the electrons are held less tightly by the
nucleus and can therefore polarize more easily.
The red-pink areas indicate electron-rich regions in the
molecule and that the blue-green areas indicate
Dispersion Force and Molecular Shape
electron-poor regions

Dipole-Dipole Interaction
- The positive end of a polar molecule is attracted to the
negative end of its neighbor.
The straight shape of n-pentane molecules allows them
to interact with one another along the entire length of
the molecule.

Acetone has a permanent dipole, which can interact

with other acetone molecules

Dipole Moment and Boiling Point

The nearly spherical shape of neopentane molecules
Polar molecules have higher melting and boiling points
allows for only a small area of interaction. Thus,
than nonpolar molecules of similar molar mass.
dispersion forces are weaker in neopentane than they
are in n-pentane, resulting in a lower boiling point.

Boiling Points of the n-Alkanes

Formaldehyde is polar and therefore has a higher

melting point and boiling point than nonpolar ethane,
even though the two compounds have the same molar
mass.

4|THE BOOK LOUNGE PH

 The hydrogen of one HF molecule, with its partial
positive charge, is attracted to the fluorine of its
neighbor, with its partial negative charge. This dipole–
dipole interaction is an example of a hydrogen bond.

Melting and boiling points of ethanol and dimethyl ether

These molecules all have similar molar masses but
different dipole moments. The boiling points increase
with increasing dipole moment. The colored regions
around each molecule are electrostatic potential maps:
Red indicates electron rich regions; yellow indicates
intermediate regions; and blue>green indicates electron-
poor regions.
Substances composed of molecules that form hydrogen
Polar and Nonpolar Compounds
bonds have higher melting and boiling points than
substances composed of molecules that do not form
hydrogen bonds.

Hydrogen Bonding in Ethanol

The partially
positive charge on H
is strongly attracted
Water and pentane do not mix because water to the partially
molecules are polar and pentane molecules are negative charge on
nonpolar. O.
The polarity of molecules composing liquids is also
important in determining the miscibility—the ability to
mix without separating into two phases—of liquids. In
general, polar liquids are miscible with other polar
liquids but are not miscible with nonpolar liquids. Melting and boiling points of ethanol and dimethyl ether

Hydrogen Bonding
Polar molecules containing hydrogen atoms bonded
directly to small electronegative atoms – F,O,and N. (HF,
NH3, and H2O.

The hydrogen bond is a sort of super dipole–dipole

force.

The large electronegativity difference between

hydrogen and these electronegative elements means
that the H atom has a fairly large partial positive charge
(δ+) when bonded to F, O, or N, while the F, O, or N
atom has a fairly large partial negative charge (δ-).

Hydrogen Bonding in HF

5|THE BOOK LOUNGE PH

 Hydrogen Bonding in Water
Does not exhibit hydrogen bonding because the oxygen
atom is not bonded directly to hydrogen, resulting in
lower boiling and melting points.
Because of hydrogen bonding, the boiling point of water
is anomalous compared to the boiling points of other
hydrogen containing compounds
Ion-Dipole Force
-occurs when an ionic compound is mixed with a polar
compound and is especially important in aqueous
solutions of ionic compounds.
- These forces are responsible for the ability of ionic
substances to form solutions with water.
The positively charged end of a polar molecule such as
H2O is attracted to negative ions, and the negatively
charged end of the molecule is attracted to positive
ions.
Intermolecular Forces in Action
• Surface Tension
• Viscosity
• Capillary action
Surface Tension
The surface tension of a liquid is the energy required to
increase the surface area by a unit amount.
The tendency for liquids to minimize their surface
creates a kind of skin at the surface that resists
penetration.
Molecules at the liquid surface have a higher potential
energy than those in the interior. As a result, liquids
tend to minimize their surface area, and the surface
behaves like a membrane or skin.
Viscosity
Viscosity is measured in a unit called the poise (P),
defined as 1 g/cm.s
Viscosity is greater in substances with stronger
intermolecular forces because if molecules are more
strongly attracted to each other they do not flow
around each other as freely.
Spherical Water - the resistance of a liquid to flow
Tiny water droplets are not distorted much by gravity
and form nearly perfect spheres held together by
intermolecular forces between water molecules.
Viscosity also depends on molecular shape; it increases
in longer molecules that can interact over a greater area
and possibly become entangled.
Viscosity of Liquid Water at Several Temperatures
Viscosity also depends on temperature because thermal
energy partially overcomes the intermolecular forces,
allowing molecules to flow past each other more easily
Nearly all liquids become less viscous as temperature
increases.
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Capillary Action
- The ability of a liquid to flow against gravity up a
narrow tube
Results from a combination of two forces:
Cohesive forces - the attraction between molecules in a
liquid
Adhesive forces- the attraction between these
molecules and the surface of the tube
The adhesive forces because the liquid to spread out
over the interior surface of the tube, while the cohesive
forces cause the liquid to stay together.
Meniscuses of Water and Mercury
The meniscus of water (dyed red for visibility at left) is
concave because water molecules are more strongly
attracted to the glass wall than to one another. The
meniscus of mercury is convex because mercury atoms
are more strongly attracted to one another than to the
glass walls
Vaporization and Vapor Pressure
Vaporization is the process by which thermal energy
can overcome intermolecular forces and produce a
state change from liquid to gas.
The higher the temperature, the
greater the average energy of the
collection of molecules.
Some molecules in an open beaker
have enough kinetic energy to
vaporize from the surface of the
liquid.
The molecules at the high end of the distribution curve
have enough energy to break free from the surface—
where molecules are held less tightly than in the
interior due to fewer neighbor–neighbor interactions—
and into the gas state.
The thermal energies of the molecules in a liquid are
distributed over a range. The peak energy increases
with increasing temperature.
Summarizing the process of Vaporization
-The rate of vaporization increases with increasing
temperature
- The rate of vaporization increases with increasing
surface area.
-The rate of vaporization increases with decreasing
strength of intermolecular forces.
Crystalline Solids: Unit Cells & basic Structures
Crystalline solids are composed of atoms or molecules
arranged in structures with long-range order.
The geometric shape that you see on the macroscopic
scale is the result of a specific structural arrangement—
called the crystalline lattice—on the molecular and
atomic scale.
The crystalline lattice can be represented by a small
collection of atoms, ions, or molecules called the unit
cell.
Three types:
- molecular, ionic, and Atomic
Based on the individual units that compose the solid.
Fundamental Types of Crystalline Solids: Molecular
- are solids whose composite units are molecules.
-are held together by the kinds of intermolecular
forces—dispersion forces, dipole–dipole forces, and
hydrogen bonding. Molecular solids as a whole tend to
7|THE BOOK LOUNGE PH
have low to moderately low melting points. However, GENCHEM: COURSE MATERIAL 3
strong intermolecular forces (such as the hydrogen
SOLUTIONS
bonds in water) increase the melting points of some
molecular solids.

Molecular solids as a whole tend to have low to

moderately low melting points. However, strong
intermolecular forces (such as the hydrogen bonds in
water) increase the melting points of some molecular
solids.

Fundamental Types of Crystalline Solids: Ionic

-whose composite units are ions
Objectives:
Ionic solids are held together by the coulombic - Use different ways of expressing concentration
interactions that occur between the cations and anions of solutions:
occupying the lattice sites in the crystal • Percent by mass,
Because the forces holding ionic solids together are
• Mole fraction,
strong coulombic forces (or ionic bonds), and because
• Molarity,
these forces are much stronger than the intermolecular
• Molality,
forces, ionic solids tend to have much higher melting
• Percent by volume,
points than molecular solids.
• Percent by mass, ppm
Perform stoichiometric calculations for reactions in
Fundamental Types of Crystalline Solids: Atomic solution
Whose composite units are individual atoms Majority component of a solution is usually called the
solvent
Nonbonding atomic solids, a group that consists of only Minority component is usually called the solute.
the noble gases in their solid form, are held together by
relatively weak dispersion forces. Types of Solution
-Gaseous solution, Aqueous solution, Solid solution
Metallic atomic solids, such as iron or gold, are held
together by metallic bonds, which in the simplest model Solution Phase Gaseous Solution
are represented by the interaction of metal cations with Solute Phase Gas
the “sea” of electrons that surrounds them. Solvent Phase Gas
The Electron Sea Model Example Air
the metal cations exist in a “sea” of electrons
Solution Phase Liquid Solution
Network covalent atomic solids, the crystal structures of Solute Phase Gas
these solids are restricted by the geometrical
Solvent Phase Liquid
constraints of the covalent bonds (which tend to be
more directional than intermolecular forces, ionic Example Soda (CO2 & Water)
bonds, or metallic bonds), so they do not tend to form
closest-packed structures.
Solution Phase Liquid Solution
Solute Phase Liquid
Solvent Phase Liquid
Example Vodka (ethanol &
water)

8|THE BOOK LOUNGE PH

 Solution Phase Liquid Solution Entropy is a measure of energy randomization or
Solute Phase Solid energy dispersal in a system.
Solvent Phase Liquid
Example Seawater (sea & The pervasive tendency for all kinds of energy to spread
water) out, or disperse, whenever it is not restrained from
doing so is the reason that two ideal gases mix.
Solution Phase Solid Solution
Solute Phase Solid Nature’s tendency toward mixing together with the
selective permeability of the cell membranes causes a
Solvent Phase Solid
flow of water out of the body’s cells and into the
Example Brass (copper & zinc) seawater.

Solubility - The solubility of a substance is the amount
of the substance that dissolves in a given amount of
solvent.
For example, the solubility of sodium chloride in water
at 25 °C is 36 g NaCl per 100 g water.
As seawater moves through the intestine, it flows past
cells that line the digestive tract. These cells consist of
largely fluid interiors surrounded by membranes.
Cellular fluids also contain dissolved ions, including
sodium and chloride, but the concentrations of these
ions in cellular fluids are more dilute than the
concentrations of these ions in seawater

The Effect of Intermolecular Forces

Intermolecular forces may either promote or prevent
the formation of a solution, depending on the nature of
the forces in the particular combination of solute and
The solubility of one solvent.
substance in another
depends both on nature’s
tendency toward mixing
and on the types of
intermolecular forces.

Spontaneous Mixing of Two

Intermolecular forces exist between each of the
Ideal Gases (a) Neon and
following:
argon are separated by a
barrier. (b) When the barrier
is removed, the two gases
spontaneously mix to form a
uniform solution.

Nature’s Tendency toward Mixing: Entropy

When the barrier between the compartments is
removed, each gas—along with its kinetic energy—
becomes spread out or dispersed over a larger volume.
Therefore, the mixture of the two gases has greater All three interactions are of similar magnitude, and the
energy dispersal, or greater entropy than the separated two substances are soluble in each other in all
components (even though their potential energy proportions—they are miscible.
remains constant).

9|THE BOOK LOUNGE PH

 Relative Interactions and Solutions Formation
We can use the rule of thumb that like dissolves like:
Similar kinds of solvents dissolve similar kinds of
solutes.
If the disparity is small, the tendency to mix results in
the formation of a solution even though the process is
energetically uphill. If the disparity is large, however, a
solution does not form.
A solution does not form when hexane and water are
mixed. Although the tendency to mix is strong, it cannot
overcome the large energy disparity between the
powerful solvent–solvent interactions and the weak
solvent–solute interactions.
The water molecules have strong hydrogen-bonding
attractions to each other but cannot hydrogen-bond to
hexane. The energy required to pull water molecules
away from one another is too great, and too little energy
is returned when the water molecules interact with
hexane molecules.
Solution Equilibrium & Factors Affecting Solubility
Saturated solution - a solution in which the dissolved
solute is in dynamic equilibrium with the solid (or
undissolved)
Unsaturated solution - a solution containing less than
the equilibrium amount of solute.
Super-saturated solution - one containing more than
the equilibrium amount of solute—may form –
unstable.
Precipitation from a Supersaturated Solution
When a small piece of solid sodium acetate is added to
a supersaturated sodium acetate solution, the excess
solid precipitates out of the solution.
Solubility & Temperature
The solubility of solids in water can be highly dependent
on temperature. Although several exceptions exists, the
solubility of most solids in water increases with
increasing temperature.
Recrystallization - A common way to purify a solid is a
technique. In this technique, enough solid is added to
water (or some other solvent) to create a saturated
solution at an elevated temperature. As the solution
cools, it becomes
Super-saturated and the excess solid precipitates out of
solution. If the solution cools slowly, the solid forms
crystals as it comes out of solution. The crystalline
structure tends to reject impurities, resulting in a purer
solid.
Solubility of Gases in Water
The solubility of a gas in a liquid is affected by both
temperature and pressure.
The bubbling that occurs when a can of soda is opened
results from the reduced pressure of carbon dioxide
over the liquid. At lower pressure, the carbon dioxide is
less soluble and bubbles out of solution.
10 | T H E B O O K L O U N G E P H
 Molarity (M)

The pressure of carbon dioxide increases, causing the

rate of molecules entering the solution to rise. The
number of molecules in solution increases until
equilibrium is established again.
Preparing a Solution of Known Concentration: To make
Expressing Solution Concentration a 1 M NaCl solution, add 1 mol of the solid to a flask and
Dilute solution - contains small quantities of solute dilute with water to make 1 L of solution.
relative to the amount of solvent
Molality (M)
Concentrated solution - contains large quantities of
solute relative to the amount of solvent

Stoichiometry Molality is particularly useful when we compare

-It is the quantitative study of reactants and products in concentrations over a range of different temperatures.
a chemical reaction.
-The mole (mol) is the amount of a substance that
contains as many elementary entries as there are atoms
in exactly 12 g of the C – 12 atom.
-Avogadro’s number is approximately 6.022 x 10^23
atoms of 12 g of the isotopes 12C

Molar mass is the mass, of a substance that is

numerically equal to the substance’s formula mass.

One mole = 6.022 x 10^23 atoms in g = amu (µ)

Formula mass is the sum of the atomic masses of all the

atoms represented in the chemical formula of a
substance.

Solution Concentration Terms

11 | T H E B O O K L O U N G E P H
 GENCHEM: COURSE MATERIAL 4
CHEMICAL REACTION AND THERMOCHEMISTRY
Evidences of Chemical Reaction
- Release of light and/or heat.
- Evolution of gas.
- Formation of precipitate
Law of Conservation of mass
The total quantity of mass of substance remains
constant regardless of any change that takes place.
Chemical Reaction
Chemical changes occur when substances undergo
changes in their composition
It is the process in which one set of new substances
called reactants converted to a new set of substance
called products.
Reactant > Product
Reactants are the starting materials in a chemical
reaction.
Product is the new substance formed.
Chemical Equation Symbols
Balancing Chemical Equation
Thermochemistry
- It is the science of the relationships between
heat and other forms of energy.
- It concerns the study of the quantity of heat
absorbed or evolved (given off) by chemical
reactions.
Energy
- Is defined as the potential or capacity to move
matter
- It is not a material thing but rather a property of
matter.
Kinetic Energy
It is the energy associated with an object by virtue of its
motion. An object of mass (m) and speed or velocity (v)
has kinetic energy 𝐸𝑘 equal to:
1
𝐸𝑘 = 2 𝑚𝑣 2
𝑚2
The SI unit of energy, kg. 𝑠2 , joule (J)
Named after James Prescott Joule
Other unit for energy
Potential Energy
It is the energy of an object has by virtue of its position
in a field of force.
𝑬𝒑 = mgh
Potential energy and kinetic energy
Water at the top of the dam has potential energy. As
the water falls over the dam, this potential energy is
converted to kinetic energy.
Internal Energy
The sum of the kinetic and potential energies of the
particles making up a substance
𝑬𝒕𝒐𝒕𝒂𝒍 = 𝑬𝒌 + 𝑬𝒑 + 𝑼
12 | T H E B O O K L O U N G E P H
Water is made up of molecules, which are made up of hydrated copper(II) ion (blue color). The thermometer
smaller particles, electrons and nuclei. Each of these now registers 90.2C, because the hydration process is
particles also has kinetic and potential energy. exothermic.

1st Law of Thermodynamics: Law of Conversion of The heat of reaction (at a given temperature) is the
Energy value of q required to return

Energy may be converted from one form to another,

but the total quantity of energy remains constant.

The total energy, 𝐸𝑡𝑜𝑡𝑎𝑙 , of the water, however, remains

constant, equal to the sum of the kinetic energy(
𝐸𝑘 ) the potential energy (𝐸𝑝 ) and the internal energy
(U) of the water.

Heat
It is defined as the energy that flows into or out of a
system because of a difference in temperature between
the thermodynamic system and its surroundings.

Heat is denoted by the symbol q.

q is positive if heat is absorbed by the system
q is negative if heat is evolved

Heat of Reaction
The substance or mixture of substances under study in
which a change occurs is called the thermodynamic
system (or simply system).

The system consists of the portion of the universe that

we choose to study; in this case, it is a solution of
Ba(OH)2 and NH4NO3. Everything else, including the
reaction vessel, constitutes the surroundings.

A kinetic-theory explanation of heat the vessel on the

left contains oxygen molecules at a higher temperature
than the oxygen molecules on the right. Molecules
collide with the vessel walls, thereby losing or gaining
energy. The faster molecules tend to slow down, and
the slower molecules tend to speed up. The net result is
that energy is transferred through the vessel walls from Consider a reaction in which crystals of barium
the hot gas to the cold gas. We call this energy transfer hydroxide octahydrate 𝐵𝑎(𝑂𝐻)2 *8𝐻2 O react with
heat. crystals of ammonium nitrate 𝑁𝐻4 𝑁𝑂3.

An exothermic process: When 1 mol Ba (OH)28H2O reacts with 2 mol NH4NO3,

The test tube contains an hydrous copper(II) sulfate the reaction mixture absorbs 170.8 kJ of heat. The
(white crystals) and a thermometer that registers 26.1C. reaction is endothermic. Therefore, the heat of
The graduated cylinder contains water. reaction, q, is + 170.8 kJ.

Water from the graduated cylinder has been added to

the test tube, where the copper(II) sulfate forms

13 | T H E B O O K L O U N G E P H
 Enthalpy
It is an extensive property of a substance that can be
used to obtain the heat absorbed or evolved in a
chemical reaction (denoted as H).
Enthalpy is a state function.
An extensive property is a property that depends on the
amount of substance. Other examples
of extensive properties are mass and volume.
A state function is a property of a system that depends
only on its present state, which is determined by
variables such as temperature and pressure, and is
independent of any previous history of the system.
This means that a change in enthalpy does not depend
on how the change was made, but only on the initial
state and final state of the system.
Thermochemical Equations
It is the chemical equation for a reaction (including
phase labels) in which the equation is given a molar
interpretation, and the enthalpy of reaction for these
molar amounts is written directly after the equation.
2Na(𝑠) + 2𝐻2 𝑂(𝑙) → 2𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐻2 ; ᐃH = -368.6
kJ
Consider the reaction of hydrogen and oxygen to
produce water. If the product is water vapor, 2 mol of
𝐻2 burn to release 483.7 kJ of heat.
2𝐻2 (𝑔) + 𝑂2 (𝑔) → 2𝐻2 𝑂(𝑔); ᐃH = -483.7kJ
If the product is liquid water, the heat released is 571.7
kJ.
𝟐𝑯𝟐 (𝒈) + 𝑶𝟐 (𝒈) → 𝟐𝑯𝟐 𝑶(𝒍); ᐃH = -571.7 kJ
In this case, additional heat is released when water
vapor condenses to liquid.
Manipulating Thermochemical Equations
1. When a thermochemical equation is multiplied
by any factor, the value of ᐃH for the new
equation is obtained by multiplying the value of
ᐃH in the original equation by that same factor.
2. When a chemical equation is reversed, the
value of H is reversed in sign.
Consider the thermochemical equation for the synthesis
of ammonia.
𝑁2 (𝑔) → 3𝐻2(g); ᐃH = -91.8 kJ
Suppose you want the thermochemical equation to
show what happens when twice as many moles of
nitrogen and hydrogen react to produce ammonia.
2𝑁2 (𝑔) + 6𝐻2(g) → 4𝑁𝐻3 (g) ; ᐃH = -184 kJ
Because double the amounts of substances are present,
the enthalpy of reaction is doubled (enthalpy is an
extensive quantity).
Suppose you reverse the first equation we wrote for the
synthesis of ammonia.
4𝑁𝐻3 (g) → 2𝑁2 (𝑔) + 6𝐻2 (g); ᐃH = +91.8 kJ
Applying Stoichiometry to Heats of Reaction
Grams of A (reactant or product) x Conversion factor: A
to mol A (using molar mass) x Conversion factor: mol A
to kJ (using enthalpy of reaction) = Kilojoules of heat
The enthalpy change for the reaction of 1 mol of
methane:
𝐶𝐻4 (𝑔) + 2𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙); ᐃH = -890.3
kJ
The calculation involves the ff conversions:
Grams of 𝐶𝐻4 → moles of 𝐶𝐻4 → kilojoules of heat
1 𝑚𝑜𝑙𝐶𝐻 −890.3 𝑘𝐽
10.0 g 𝐶𝐻4 x 16.0 𝑔𝐶𝐻4 x 1 𝑚𝑜𝑙𝐶𝐻 = -556 kJ
4 4
GENCHEM: COURSE MATERIAL 5
CHEMICAL KINETICS
Chemical Kinetics - It is the study of reaction rates, how
reaction rates change under varying conditions, and
what molecular events occur during the overall reaction
Collision Theory
It is a theory that assumes that, for reaction to occur,
reactant molecules must collide with an energy greater
than some minimum value and with the proper
orientation.
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 𝑨𝟐(𝒈) + 𝑩𝟐(𝒈) → 𝑨𝑩(𝒈)
Types of Collision
- Effective collision happen if it causes chemical
reactions and forms a product
Factors for a collision to be effective
- Sufficient energy
- Right orientation at the moment of impact to break
the existing bonds
Ineffective collisions happen if the collision does not
cause any reaction and does not lead to the formation
of products.
Activation Energy (𝑬𝒂 )
- The minimum energy of collision required for two
molecules to react.
- The value of 𝐸𝑎 depends on the particular reaction.
- Reactant particles must have an energy equal to or
higher than the activation energy. To produce a
reaction.
Maxwell-Boltzmann Distribution
A plot of the number of particles vs. a particular energy.
The particles present in any system will have a very
wide range of energies
Reaction Rate
Factors Affecting Rates of Reaction
Concentration of Reactants
Often the rate of reaction increases when the
concentration of a reactant is increased.
Catalytic decomposition of hydrogen peroxide. The
hydrogen peroxide decomposes rapidly when
hydrobromic acid is added to an aqueous solution. One
of the products is oxygen gas, which bubbles vigorously
from the solution. In addition, some HBr is oxidized to
Br2, as can be seen from the red color of the liquid and
vapor.
Concentration of catalyst
A catalyst is a substance that increases the rate of
reaction without being consumed in the overall
reaction. Because the catalyst is not
consumed by the reaction, it does not appear in the
balanced chemical equation (although its presence may
be indicated by writing its formula over the arrow).
2𝐻2 𝑂2 (aq) > 2𝐻2 𝑂 (𝑙)𝑂2 (g)
Temperature at which the reaction occurs
Usually reactions speed up when the temperature
increases
It takes less time to boil an egg at sea level than on a
mountaintop, where water boils at a lower
temperature. Reactions during cooking go faster at
higher temperature.
Surface area of a solid reactant or catalyst.
If a reaction involves a solid with a gas or liquid, the
surface area of the solid affects the reaction rate.
Because the reaction occurs at the surface of the solid,
the rate increases with increasing surface area.
Effect of large surface area on the rate of reaction
Lycopodium powder (from the tiny spores of a club
moss) ignites easily to produce a yellow flame. The
powder has a large surface area per volume and burns
rapidly in air.
Applications of the Factors Affecting Rate of Reaction
Food and pharmaceutical products preservation
- High temperatures cause higher collision and reactions
produced by microorganisms, that is why most food
medicinal products are stored in low temperatures.
Preservation or decomposition of specimens
Biochemical laboratories make use of liquid nitrogen as
a cryogenic freezer in preserving laboratory sample and
specimens – cryopreservation.
Cells and tissues are preserved by cooling to sub-zero
temperatures (-196ºC).
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Medication or poisoning the body
Some drugs are more effective if taken in higher
concentrations
There are also drugs that may poison our bodies if we
take an amount more than the prescribed
concentration.
Dating, restoration, and preservation of artifacts
To preserve wood and leather artifacts, these must be
soaked in polyethylene glycol. - a waxy substance that is
absorbed into wood and leather and makes wood
stronger, and makes leather flexible again.
Power companies
The total surface area of an object increases as it is
crushed to a powder.
This concept is applied in some power companies that
burn coal. They grind the coal first before blowing it into
the combustion chamber, where it reacts almost
explosively
Control of fires
Gases have higher surface area and spreads out easily.
In gasoline stations, smoking is strictly prohibited since
a single spark of fire may come in contact with the gas
molecules in the air, causing an explosion.
REACTION RATE
It is the increase in molar concentration of product of a
reaction per unit time or the decrease in molar
concentration of reactant per unit time
- It is the amount of product formed or the amount of
reactant used up per unit of time
So that a rate calculation does not depend on the total
quantity of reaction mixture used, you express the rate
for a unit volume of the mixture.
The usual unit of reaction rate is moles per liter per
second, mol/(Ls).
Expressing Reaction Rates
If the time interval is very short, the equation gives the
instantaneous rate—that is, the rate at a particular
instant of time.
Because the amounts of products and reactants are
related by stoichiometry, any substance in the reaction
can be used to express the rate of reaction.
Note the negative sign. It always occurs in a rate
expression for a reactant in order to indicate a decrease
in concentration and to give a positive value for the
rate.
To equate the rates, you must divide the rate of
decomposition of 𝑁2 𝑂5 by 2 (its coefficient in the
balanced chemical equation).
RATE LAW
It is an equation that relates the rate of a reaction to
the concentrations of reactants (and catalyst) raised to
various powers.
Consider the reaction of nitrogen dioxide with fluorine
to give nitryl fluoride, 𝑁𝑂2 𝐹:
2𝑁𝑂2 (g) + 𝐹2 (g) → 2𝑁𝑂2 F (g)
Rate = k [𝑁𝑂2 ][𝐹2 ]
k = rate constant, is a proportionality constant in the
relationship between rate and concentrations
Reaction Mechanism
Elementary Reactions
- It is a single molecular event, such as a collision
of molecules, resulting in a reaction.
- Consider the reaction of nitrogen dioxide with
carbon monoxide
The set of elementary reactions whose overall effect is
given by the net chemical equation.
It is the description of the path, or sequence of steps, by
which a reaction occurs.
It is an educated guess based on experiments and
theory.
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Reaction Intermediate
It is a species produced during a reaction that does not
appear in the net equation because it reacts in a
subsequent step in the mechanism.
Often the reaction intermediate has a fleeting existence
and cannot be isolated from the reaction mixture.
GENCHEM: COURSE MATERIAL 6
CHEMICAL EQUILIBRIUM
Oxygen Exchange between the Maternal and Fetal
Circulation
In the placenta, the blood of the fetus comes into close
proximity with that of the mother without mixing.
Because the reaction of fetal hemoglobin with oxygen
has a larger equilibrium constant than the reaction of
maternal hemoglobin with oxygen, the fetus receives
oxygen from the mother’s blood.

Have you ever wondered how a baby in the womb gets
oxygen?
Fetal Hemoglobin and Equilibrium
After we are born, we inhale air into our lungs; that air
diffuses into capillaries, where it comes into contact.
Within our red blood cells, a protein called hemoglobin
(Hb) reacts with oxygen:
Chemical Equilibrium–A Dynamic Equilibrium
A dynamic equilibrium consists of a forward reaction, in
which substances react to give products, and a reverse
reaction, in which products react to give the original
reactants.
Both have same rate and speed.
Change of rates as reaction proceeds

𝐻𝑏 + 𝑂2 = 𝐻𝑏𝑂2

The equilibrium constant for the reaction between

hemoglobin and oxygen is such that hemoglobin
efficiently binds oxygen at typical lung oxygen
concentrations, but can also release oxygen under the
appropriate conditions.

- As blood flows through the lungs where oxygen

concentrations are high, the equilibrium shifts to the
right—hemoglobin binds oxygen.
- As blood flows out of the lungs and into muscles and
organs where oxygen concentrations have been
depleted (because muscles and organs use oxygen), the
equilibrium shifts to the left—hemoglobin releases
oxygen.
A fetus has its own circulatory system. The mother’s
blood never flows into the fetus’s body, and the fetus
cannot get any air in the womb.
A fetus has the properties of fetal hemoglobin (HbF),
which is slightly different from adult hemoglobin.
(A) Initially, only the reaction CO + 3H2 → occurs,
because the concentrations of CH4 and H2O are zero.
(B) Later, as this reaction proceeds, the concentrations
of CH4 and H2O increase, and the reaction CH4 + H2O
→ begins. The rate of the reaction CH4 + H2O→steadily
increases, whereas the rate of the reaction CO +
3H2→decreases. Eventually, the two rates become
equal.
Catalytic methanation reaction approaches
equilibrium

𝑯𝒃𝑭 + 𝑶𝟐 = 𝑯𝒃𝑭𝑶𝟐

However, the equilibrium constant for fetal hemoglobin

is larger than the equilibrium constant for adult
hemoglobin, meaning that the reaction tends to go
farther in the direction of the product.

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A) The experiment begins with 1.000 mol CO and 3.000
mol H2 in a 10.00-L vessel. Note that the amounts of
substances become constant at equilibrium.
(B) The forward rate is large at first but steadily
decreases, whereas the reverse rate starts at zero and
steadily increases. Eventually both rates become equal
(at equilibrium).
Chemical Equilibrium is the state reached by a reaction
mixture when the rates of forward and reverse
reactions have become equal.
The Equilibrium Constant (𝑲𝒄)
We can quantify the relative concentrations of
reactants and products at equilibrium with a quantity
called the equilibrium constant (K).
aA + bB = cC + dD
Where:
A and B – reactants
C and D - products
a, b, c, and d - coefficients
The relationship between the balanced chemical
equation and the expression of the equilibrium constant
is the law of mass action.
Exercise: Writing the Equilibrium Constant & the
Chemical Equation
a. Write the equilibrium-constant expression Kc for the
equation
2𝑁𝑂 + 7𝐻 2𝑁𝐻 + 4𝐻 𝑂 2(𝑔) 2(𝑔) 3(𝑔) 2 (𝑔)
b. Write the equilibrium-constant expression Kc when
this reaction is written
𝑁𝑂 = 7 𝐻 𝑁𝐻 + 2𝐻 𝑂 2(𝑔)22 3(𝑔) 2(𝑔)
Equilibrium: A Kinetics Argument
The law of mass action was first stated by the
Norwegian chemists Cato Guldberg and Peter Waage in
1867.
They were led to this law by
a kinetics argument. To
understand the argument, consider the decomposition
of dinitrogen tetroxide, N2O4.
𝑵𝟐 𝑶𝟒(𝒈) → 𝟐𝑵𝑶𝟐(𝒈)
At equilibrium, you can write: Rate of forward reaction
rate of reverse reaction, or
𝑘𝑓 [𝑁2 𝑂4 ] = 𝑘𝑟 [𝑁𝑂2 ]2
𝑘𝑓 [𝑁𝑂2 ]2
=
𝑘𝑟 [𝑁2 𝑂4 ]
If the overall reaction occurs by a multistep mechanism,
one can show that the equilibrium constant equals a
product of ratios of rate constants—one ratio for each
step in the mechanism.
Obtaining Equilibrium Constants for Reactions
Within the precision of the data, these values (3.93 and
3.91) of the equilibrium expression for different starting
mixtures of these gases at 1200 K are the same.
Moreover, experiment shows that when you start with
CH4 and H2O, instead of CO and H2, an equilibrium
mixture is again reached that yields the same value of
Kc.
the equilibrium constant for catalytic methanation at
1200 K is to be 3.92
Example: Obtaining Equilibrium Constants for
Reactions
Hydrogen iodide, HI, decomposes at moderate
temperatures according to the equation
𝟐𝑯𝑰(𝒈) 𝑯𝟐(𝒈) + 𝑰𝟐(𝒈)
The amount of I2 in the reaction mixture can be
determined from the intensity of the violet color of I2;
the more intense the color, the more I2 in the reaction
18 | T H E B O O K L O U N G E P H
vessel. When 4.00 mol HI was placed in a 5.00-L vessel
at 458C, the equilibrium mixture was found to contain
0.442 mol I2. What is the value of Kc for the
decomposition of HI at this temperature?
Carbon monoxide and hydrogen react according to the
following equation
𝐶𝑂(𝑔) + 3𝐻2(𝑔) 𝐶𝐻4 + 𝐻2 𝑂(𝑔)
When 1.000 mol CO and 3.000 mol H2 are placed in a
10.00-L vessel at 927C (1200 K) and allowed to come to
equilibrium, the mixture is found to contain 0.387 mol
H2O. What is the molar composition of the equilibrium
mixture? That is, how many moles of each substance
are present?
Equilibrium Constants 𝑲𝒑
In discussing gas-phase equilibria, it is often convenient
to write the equilibrium constant in terms of partial
pressures of gases rather than concentrations. Note
that the concentration of a gas is proportional to its
partial pressure at a fixed temperature.
You can see this by looking at the ideal gas law, PV nRT,
and solving for n/V, which is the molar concentration of
the gas.
You get n/V = P/RT
When you express an equilibrium constant for a
gaseous reaction in terms of partial pressures, you call it
the equilibrium constant Kp.
𝑪𝑶(𝒈) + 𝟑𝑯𝟐(𝒈) 𝑪𝑯𝟒(𝒈) + 𝑯𝟐 𝑶(𝒈)
ᐃn is the sum of the coefficients of gaseous product in
the chemical equation minus the sum of the coefficients
of gaseous reactants.
The Significance of the Equilibrium
When the equilibrium constant is large, the forward
reaction is favored.
The equilibrium constant is large, so the equilibrium
point for the reaction lies far to the right—high
concentrations of products, low concentrations of
reactants.
Summarizing the Significance of the Equilibrium
Constant:
K < 1 Reverse reaction is favored; forward reaction does
not proceed very far.
K ≈ 1 Neither direction is favored; forward reaction
proceeds about halfway
K > 1 Forward reaction is favored; forward reaction
proceeds essentially to completion
Heterogenous Equilibria; Solvents in Homogenous
Equilibria
A homogeneous equilibrium is an equilibrium that
involves reactants and products in a single phase
Example: Catalytic methanation; it involves only
gaseous reactants and products.
A heterogeneous equilibrium is an equilibrium involving
reactants and products in more than one phase
Example: the reaction of iron metal filings with steam to
produce iron oxide (𝐹𝑒3 𝑂4 ), and hydrogen involves
solid phases, Fe and 𝐹𝑒3 𝑂4 in addition to gaseous
phases.
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Using the Equilibrium Constant

Ways in which an equilibrium constant can be used to

answer important questions:

1. Qualitatively interpreting the equilibrium

constant.
2. Predicting the direction of reaction
3. Calculating equilibrium concentrations.

Predicting the Direction of Reaction

The reaction quotient, Qc, is an expression that has the

same form as the equilibrium-constant expression but
whose concentration values are not necessarily those at
equilibrium

[𝐶𝐻4 ]𝑖 [𝐻2 𝑂]𝑖

For catalytic methanation: 𝑄𝑐 =
[𝐶𝑂]𝑖 [𝐻2 ]3𝑖

substitute the concentrations of the gaseous mixture

(0.00100)(0.00100)
𝑄𝑐 = = 6.25
(0.0200)(0.0200)3

Qualitatively Interpreting the Equilibrium Constant

Summarizing to know in what direction the reaction will

go as it approaches equilibrium

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