GENERAL

CHEMISTRY
ENGR. KIMBERLY D. VERGARA
 TOPICS:
1. Basic Concepts of Matter and its classification
2. Mass Relationships in Chemical Reactions
3. Properties of Gas, Liquids and Solids
4. Concepts on Thermochemistry
5. Quantum theory and Electronic Behavior
6. Periodic Relationship of Elements in the Periodic Table
7. Intramolecular Forces
8. Solutions
MATTER
 MATTER
●Matter is anything that takes up space and has mass. It is composed of tiny
particles called atoms. This can be classified into three states or phases – solid,
liquid and gas.

●Matter can also be classified according to its properties into pure substances
and mixtures.
 MATTER
PURE SUBSTANCES MIXTURES

ELEMENTS COMPOUNDS HOMOGENEOUS HETEROGENEOUS

TWO OR MORE
METALS ACIDS SAME DISTINCT PHASES,
PROPERTIES EACH WITH ITS
THROUGHOUT OWN SET OF
BASES PROPERTIES
NONMETALS

SALTS
 Particles
Composing Matter

Smallest Particle Composed of Atoms Particles with Charges

 Matter
ELEMENTS COMPOUNDS MIXTURES

- simplest type of matter - are substances formed - mixture consists of two

with unique physical when two or more or more substances
and chemical elements combine (elements and/or
properties. through a chemical compounds) that are
- It consists of only one change. mixed.
kind of atom, and, - its properties are - Because a mixture is
therefore, cannot be different from the NOT a substance, the
broken down into a properties of its components of a
simpler type of matter compound elements. mixture can vary in their
by any physical or parts by mass.
chemical methods.
 Kinetic Molecular Model
of Liquids and Solids
The experimental findings about the behavior of gases can be explained with a
simple theoretical model known as the kinetic molecular theory. This theory is
based on the following assumptions:

● All matter is made of tiny particles.

● These particles are in constant motion.
● The speed of particles is proportional to temperature. Increased temperature
means greater speed.
● Solids, liquids, and gases differ in distances between particles, in the freedom of
motion of particles, and in the extent to which the particles interact.
 Molecular or particle level view
of a solid, liquid and a gas

SOLID LIQUID GAS

Image retrieved from https://www.slideserve.com/tate/solids-liquids-gases-and-solutions

 Properties of Gas,
Liquid and Solid
Properties of Molecular Behavior
Matter
Gas Liquid Solid

Volume/Shape Assumes the volume Assumes the shape of Has a definite shape
and shape of its its container and has a and volume
container definite volume
Density Low High High

Compressibility Very compressible Slightly compressible Virtually

incompressible
Motion of Vibrate and move Vibrate, move about Vibrate but generally
Molecules freely at high speeds and slide past each do not move from one
other place to another
 Mass Relationships
in Chemical Reactions
 Stoichiometry
● It is the quantitative study of reactants and products in a chemical
reaction.

● It is a section of chemistry that involves using relationships between

reactants and/or products in a chemical reaction to determine desired
quantitative data.

● Chemical equations must obey the Law of Conservation of Mass.

 Example: the formation of
table salt or NaCl
𝟐𝑵𝒂 (𝒔) + 𝟐𝑯𝑪𝒍 (𝒂𝒒) → 𝟐𝑵𝒂𝑪𝒍 (𝒂𝒒) + 𝑯𝟐 (g)

2 moles of Na react with 2 moles of HCl to form

2 moles of NaCl and 1 mole of H2

mole-mole factor 2 moles Na ≅ 2 moles NaCl

The symbol ≅ means "equivalent to“

2 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎 2 𝑚𝑜𝑙𝑒𝑠 𝐻𝐶𝑙 2 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎 2 𝑚𝑜𝑙𝑒𝑠 𝐻𝐶𝑙 2 moles Na𝐶𝑙 1 𝑚𝑜𝑙𝑒 𝐻2

2 moles Na𝐶𝑙
𝑜𝑟 2 moles Na𝐶𝑙
𝑜𝑟 1 𝑚𝑜𝑙𝑒 𝐻2
𝑜𝑟 1 𝑚𝑜𝑙𝑒 𝐻2
𝑜𝑟 2 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎
𝑜𝑟 2 moles Na𝐶𝑙
 Basic Stoichiometric
Calculations

1. Mole-to-mole relationship
2. Mole-to-mass relationship
3. Mass-to-mass relationship
 Mole-to-mole
relationship
● In the mole-to-mole relationship, use the stoichiometric
coefficients (SC) from the balanced chemical equations to derived
conversion factors called as mole ratio.

𝑺𝒕𝒐𝒊𝒄𝒉𝒊𝒐𝒎𝒆𝒕𝒓𝒊𝒄 𝒄𝒐𝒆𝒇𝒇𝒊𝒄𝒊𝒆𝒏𝒕𝒖𝒏𝒌𝒏𝒐𝒘𝑛
𝑀𝑅 =
𝑺𝒕𝒐𝒊𝒄𝒉𝒊𝒐𝒎𝒆𝒕𝒓𝒊𝒄 𝒄𝒐𝒆𝒇𝒇𝒊𝒄𝒊𝒆𝒏𝒕𝒈𝒊𝒗𝒆𝑛

It is the ratio between the numbers of moles of any substances in a

balanced chemical equation.
Sample problem #1
Ammonia, NH3 is a leading industrial chemical used in the production
of agricultural fertilizers and synthetic fibers. It is produced by the
reaction of nitrogen and hydrogen gases.

3 H2 (g)+ N2 (g) → NH3 (g)

a. How many moles of H2 are needed to produce 26.5 moles of NH3?

Ans: # of moles H2 = 39.8 moles of H2

Sample problem #2
Ammonia, NH3 is a leading industrial chemical used in the production
of agricultural fertilizers and synthetic fibers. It is produced by the
reaction of nitrogen and hydrogen gases.

3 H2 (g)+ N2 (g) → NH3 (g)

b. How many moles of NH3 will be produced if 33.7 moles of N2 reacts
completely with H2 ?

Ans: # of moles NH3 = 67.4 moles of NH3

 Mole-to-mass
relationship
● The mole-to-mass relationship deals with the given number of moles of a
reactant or a product in a reaction and required the mass of a reactant and a
product.
● In order to convert moles to grams or grams to moles, you have to make use of
the molar mass of the given compound.
Sample Problem #3:
How grams of N2 are needed to react with 10 moles of H2 ?

3 H2 (g)+ N2 (g) → NH3 (g)

Ans: mass of N2 = 93.3 g N2

Mass-to-mass relationship
● The mass-to-mass relationship is utilized when carrying out a reaction in
the laboratory or in the real-world set – up. The masses of the substances
are given while the unknown are also the masses.

● With this relationship, utilize the ratio of the theoretical masses of the
unknown and given substances.
Sample problem #4
If 80.0 g of aqueous iron (III) chloride is the desired amount of the product,
how many grams of solid iron must react with hydrochloric acid?

2 Fe(s) + 6 HCl (aq) → 3 H2 (g) + 2 FeCl3 (aq)

Ans: mass of Fe = 27.55 g Fe

The Quantum Mechanical
Model of the Atom
 Quantum theory

● Quantum theory, also called wave mechanics, describes the

arrangement and space occupied by electrons.
● We do not know the detailed pathway of an electron.
● The electrons move in regions of probability around the nucleus called
ORBITALS.
 Quantum Numbers

● ALL ELECTRONS have FOUR QUANTUM NUMBERS which describes

the location of electrons in the electron cloud of an atom and can be
used to determine the electron configuration of an atom.
 Quantum Numbers
describes the distribution
● Principal Quantum Number of electrons in hydrogen
● Secondary Quantum Number and other atoms
describe atomic orbitals
● Magnetic Quantum Number
● Spin Quantum Number

describes the behavior of

a specific electron and
completes the description
of electrons in atoms
Principal Quantum Number (n)
▪ describes the energy of the electron
▪ designates the main energy level (floor) or shell

Size and energy of an orbit/shell – n=1,2,3,4, ....

n=1 is closest to the nucleus – low energy

n=2 is farther than n=1, slightly more energy
n=3 is farther than n=1 and n=2, still increasing in energy
n=4 .....

Greater value of n represents bigger orbital

with high energies
 Secondary Quantum Number (l)
• This gives the total numbers of sublevels or subshells possible in a given
main energy level or shell.
• It also describes the “type” of orbital where the electron is ranging from 0 to
n -1.
• Also called the azimuthal quantum number, l can have values ranging from 0
n – 1.
l = 0, 1, 2, 3, …. (n-1)
The type of orbital for a given l – value is summarized as follows:

l - value 0 1 2 3

Type of orbital s p d f
The Type and Number of Orbitals
per Given l - Value
Shell Number Number of Value of l Type of Orbital
Subshell
1 One 0 s

2 two 0 s
1 p
3 Three 0 s
1 p
2 d
4 Four 0 s
1 p
2 d
3 f
 Magnetic Quantum Number (ml)

The magnetic quantum number ml describes the possible orientations of an

orbital in space. The value of ml depends on the value of l and can range from
- l to + l with zero included.

ml = 0, ±1 , ±2 , ±3 ….. ± l
Magnetic Quantum Number (ml)

l- Value Orbital Type ml Number of Orientations

0 s 0 1

1 p -1 3
0
1
2 d -2 5
-1
0
1
2
Spin Quantum Number ms

• refers to the spin of the electron which can either be up or down.

 SUMMARY OF QUANTUM NUMBERS

Principal Quantum Secondary Quantum Magnetic Quantum Orbital Spin Quantum

Number n Number l Number ml Type Number ms
1 1
1 0 0 s +2, -2
2 1 1
0 0 s +2,-2
1 1
1 -1 p +2,-2
0 p 1 1
+ ,-
2 2
1 p 1 1
+ ,-
2 2
 SUMMARY OF QUANTUM NUMBERS
Principal Quantum Secondary Quantum Magnetic Quantum Orbital Spin Quantum
Number n Number l Number ml Type Number ms
1 1
3 0 0 s +2,-2
1 1
1 -1 p +2,-2
1 1
0 p +2,-2
1 1
1 p +2,-2
1 1
+2,-2
2 -2 d
1 1
+2,-2
-1 d 1 1
+2,-2
0 d 1 1
+ ,-
2 2
1 d 1 1
+ ,-
2 2
2 d
 Electron
Configuration
 Electron Configuration
● the distribution of electrons among the orbitals of an atom

AUFBAU PRINCIPLE

● In an atom, electrons occupy the orbitals in the order of increasing energy.

Lowest energy levels are filled up before going to the next level.
AUFBAU PRINCIPLE

The mnemonic device presented can guide

us to determine the order of increasing
energy of the orbitals.
 Hund’s Rule
● “the most stable arrangement of electrons in subshells is the
one with the greatest number of parallel spins”

When electrons are placed in a set of orbitals of equal energy, every orbital
in a sublevel is singly occupied before any orbital is doubly occupied.
 EXAMPLE

● All the electrons in singly occupied orbitals have the same spin
(to maximize total spin).
PAULI EXCLUSION PRINCIPLE

No more than two electrons in an atom can occupy an orbital, and that
these two electrons must have opposite spins.
Pauli exclusion principle serves as the basis for having any set of s
orbitals holding a maximum of two electrons; any set of p orbitals
having a maximum of six electrons; for d orbitals, 10 electrons; for f, 14
electrons; and so on.
Sample Problem #5:

Write the electronic configuration and orbital diagram of the following

atoms:

1. Na
2. N
3. Fe
1. Na 1s 2 2s 2 2p6 3s1

2. N 1s 2 2s 2 2p3

3. Fe 1s2 2s2 2p6 3s2 3p6 4s2 3d6

Periodic Relationship of
Elements in the Periodic
Table
 PERIODIC TABLE OF
ELEMENTS
● The periodic table is like a map that gives a picture if the relationships
among the elements. Elements with similar properties are placed in
columns, groups or families.
● In the modern periodic table, elements are arranged in the order of
increasing atomic numbers. The organization of the table is related to
the electronic structure of the elements.
 ACROSS → DOWN ↓
CATION
METALLIC PROPERTY
DECREASE INCREASE
ATOMIC SIZE
REACTIVITY
IONIZATION ENERGY
ELECTRON AFFINITY INCREASE DECREASE
ELECTRONEGATIVITY
ANION
Intramolecular
Forces
 Intramolecular Forces

● Intramolecular forces hold atoms together in a molecule.

Intramolecular forces stabilize individual molecules,
whereas intermolecular forces are primarily responsible
for the bulk properties of matter.
Types of intramolecular
forces of attraction
● Ionic bond

● Covalent bond

● Metallic bonding
 Ionic bond
● This bond is formed by the complete transfer of valence electron(s) between
atoms. It is a type of chemical bond that generates two oppositely charged ions.
In ionic bonds, the metal loses electrons to become a positively charged cation,
whereas the nonmetal accepts those electrons to become a negatively charged
anion.
 Covalent Bond
● This bond is formed between atoms that have similar electronegativities—the
affinity or desire for electrons. Because both atoms have similar affinity for
electrons and neither has a tendency to donate them, they share electrons in order
to achieve octet configuration and become more stable.
 Metallic bonding:
This type of covalent bonding specifically occurs between atoms of metals, in which
the valence electrons are free to move through the lattice. This bond is formed via the
attraction of the mobile electrons—referred to as sea of electrons—and the fixed
positively charged metal ions. Metallic bonds are present in samples of pure elemental
metals, such as gold or aluminum, or alloys, like brass or bronze.
SOLUTIONS
Concentration of Solutions
1. Qualitative Expressions of Concentration - A solution can be
qualitatively described as
• Dilute: a solution that contains a small proportion of solute relative to
solvent,
• Concentrated: a solution that contains a large proportion of solute
relative to solvent.

2 .Semi-Quantitative Expressions of Concentration - A solution can

be semi-quantitatively described as
• unsaturated: a solution in which more solute will dissolve,
• saturated: a solution in which no more solute will dissolve.
 Concentration of
Solutions
Quantitative study of a solution requires knowing its concentration,
that is, the amount of solute present in a given amount of solution.
Examples of units of concentration are:

• percent by mass
• mole fraction
• Molarity
• Molality
• percent by volume
• parts per million (ppm)
 Percent by mass
1. Percent by mass
This expresses the mass of solute per 100g of solution. Mass of solution is equal to
the mass of solute plus the mass of solvent. A solution that contains 30% by mass of
sugar means that the solution contains 30g of sugar and 70g of water. It also means
that there are 30g of sugar per 100g of solution. The formula for percent by mass is:

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝑏𝑦 𝑚𝑎𝑠𝑠 = × 100
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 + 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
 Sample Problem #6
A sample of 30 grams (g) of sodium chloride (NaCl) is dissolved in 105 grams
of water. What is the percent by mass of NaCl in the solution?

Ans. % 𝑏𝑦 𝑚𝑎𝑠𝑠 = 𝟐𝟐. 𝟐𝟐 %

 Mole Fraction
2. Mole Fraction
Another method of expressing concentration of solution is the mole fraction. It is the
ratio of the number if mole of one component to the total number of moles in a
solution. It is represented by a capital letter X.

𝑚𝑜𝑙𝑒𝑠 𝑠𝑜𝑙𝑢𝑡𝑒 𝑚𝑜𝑙𝑒𝑠 𝑠𝑜𝑙𝑣𝑒𝑛𝑡

𝑀𝑜𝑙𝑒 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑋 𝑆𝑜𝑙𝑢𝑡𝑒 𝐴 = 𝑚𝑜𝑙𝑒𝑠 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑀𝑜𝑙𝑒 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑋 𝑆𝑜𝑙𝑣𝑒𝑛𝑡 𝐵 = 𝑚𝑜𝑙𝑒𝑠 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑠𝑜𝑙𝑢𝑡𝑒 + 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑠𝑜𝑙𝑣𝑒𝑛𝑡

𝑀𝑜𝑙𝑒 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 + 𝑀𝑜𝑙𝑒 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = 1
𝑋𝐴 + 𝑋𝐵 = 1
Sample Problem #7
A solution is made by dissolving 1.25 g of Na2SO4 in 65.0 g water. Calculate
the mole fraction of the solute and the solvent.

Ans. 𝑋𝑠𝑜𝑙𝑢𝑡𝑒 = 0.0024

𝑋𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = 0.997
 Molarity (M)
3. Molarity (M)
Concentration of solution may also be expressed in terms of molarity. Molarity is the
ratio of the number of moles of solute per liter of solution which is mathematically
expressed as

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦(𝑀) =
𝑙𝑖𝑡𝑒𝑟 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Sample Problem #8
Determine the molarity of the solution with 0.2 mol of NaOH in 100 mL
of solution.

Ans. M = 2 mol/L
 Sample Problem #9
Calculate the number of moles of solute in each of 100mL of 0.5 M of H2SO4. The first
conversion factor is to convert mL and the second conversion factor is the molality of the
solution.

Ans. 𝑛𝑠𝑜𝑙𝑢𝑡𝑒 = 0.05 mol

 Molality
4. Molality (m)
This is defined as the number of moles of solute per kilogram of solvent. It can also be
mathematically expressed as

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑀𝑜𝑙𝑎𝑙𝑖𝑡𝑦(𝑚) =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 (𝑘𝑔)
Sample Problem #10
How many moles of solute is present in 4.0m Mg(OH)2 in 550 g water?

Ans. 𝑛𝑠𝑜𝑙𝑢𝑡𝑒 = 2.2 mol

Sample Problem #11
The density of a 2.45 M aqueous solution of methanol (CH 3OH) is 0.976 g/mL. What is
the molality of the solution? The molar mass of methanol is 32.04 g.

Ans. 𝑛𝑠𝑜𝑙𝑢𝑡𝑒 = 2.73 m

 Percent by volume
5. Percent by volume
If the solution involves a solute and a solvent that are both liquids, then percent by
volume is used instead of mass. The percent by volume is used to express the
concentration of a solution when the volume of a solute and the volume of a solution
are given, multiplied by 100.

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝑏𝑦 𝑣𝑜𝑙𝑢𝑚𝑒 = × 100
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 + 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
 Sample Problem #12
In a solution, there is 120.6 mL solvent and 4.94 mL solute present. Find the percent by
volume.

Ans. %v/v = 3.94%

 Parts per million
6. Parts per million
In some cases when the concentration of solute present is very low, it is more
convenient to use parts per million. A concentration of a solution that contained
1 g solute and 1000000 mL solution (same as 1 mg solute and 1 L solution)
would create a very small percentage concentration. Because a solution like this
would be so dilute, the density of the solution is well approximated by the
density of the solvent; for water, that is 1g/mL (other solvents are different
case). So, after solving and converting the mL of solution into grams of solution
(assuming that the solvent is water):

1 𝑔 𝑠𝑜𝑙𝑢𝑡𝑒 1 𝑚𝐿 1 𝑔 𝑠𝑜𝑙𝑢𝑡𝑒
× =
1000000 𝑚𝐿 𝑠𝑜𝑙𝑛 1𝑔 1000000 𝑔 𝑠𝑜𝑙𝑛
 ● We get (1g solute)/(1000000 g solution). Because both the solute
and the solution are now expressed in terms of grams, it could
now be said that the solute concentration is 1 part per million
(ppm).
1 𝑚𝑔 𝑠𝑜𝑙𝑢𝑡𝑒
1 𝑝𝑝𝑚 =
1 𝐿 𝑠𝑜𝑙𝑛

The ppm unit can also be used in terms of volume/volume (v/v) instead.
Sample Problem #13
A solution has a concentration of 1.24 g/L. What is its concentration in
ppm?

Ans. 1240 ppm

 Sample Problem #14
What is the concentration in ppm of a solution that is 0.000077% by mass
solute?

Ans. 0.77 ppm

THERMODYNAMICS
 Thermochemistry

Thermodynamics is the study of energy. Thermochemistry is part of a

broader subject called thermodynamics, which is the scientific study of
the interconversion of heat and other kinds of energy. The laws of
thermodynamics provide useful guidelines for understanding the
energetics and directions of processes.
 First Law of
Thermodynamics

● The first law of thermodynamics which is based on the law of conservation of

energy states that energy can neither be created nor destroyed; it can only be
transformed from one form to another. For example, the flow of electron
produces light in a bulb, it appears (light) energy is produced in a bulb,
however, it is through the conversion of electrical energy to light.
● The energy contained within the system, referred to as internal energy, U, is
simply the sum of the kinetic and potential energy of all the components of
the system. Internal energy is a state function, meaning it does not depend on
the path of the process. The value is the same regardless of the pathway and
depends only on the initial and final states of the system.

∆𝑼 = 𝑼𝒇𝒊𝒏𝒂𝒍 − 𝑼𝒊𝒏𝒊𝒕𝒊𝒂𝒍
● Change in Internal Energy is used in expressing the first law of
thermodynamics, wherein change in the internal energy (ΔU) is
the sum of the heat (Q) that flows across its boundaries and the
work (W) done on the system by the surroundings.

● Mathematically it is expressed as:

∆U=Q+W
● As the equation says, we have two kinds of processes, heat and work,
that defines the change in the internal energy of the system. Since
both heat and work can be measured and quantified, it is similar in
saying that change in the energy of the system must result in a
change in the energy of the surroundings.
● If the heat flows into a system or the surroundings do work on it (on
the system), internal energy increases and the values of Q and W are
positive.
● On the other hand, heat flow out of the system or work done by the
system (on the surroundings), the internal energy decreases because
Q and W are both negative. If heat is absorbed during the process,
the reaction is endothermic. If heat is evolved, the change is
exothermic.
● Q and W are positive (+) when heat or work enters the system
from the surroundings, i.e., heat is absorbed by the system and
work is done on the system.
● Q and W are negative (-) when heat or work transfers from the
system to the surroundings, i.e., heat is evolved, and work is done
by the system.
● If both Q and W are (+), sign of ΔU is also (+); internal energy
increases
● If both Q and W are (-), sign of ΔU is also (-); internal energy
decreases
● If Q is (+) and W is (-), or, if Q is (-) and W is (+), sign of ΔU
depends on the magnitudes of Q and W.
To Summarize:
Sample Problem #15

1. 100 J of energy is absorbed by the system ________________

2. 50J of heat is evolved to the surroundings ________________
3. Gas absorbs 28kJ of heat _________________
4. 13kJ of work is done on the gas _________________
5. 30 kJ of work is done by the system _________________
Sample Problem #16
1. Calculate ΔU if 100 kJ of heat energy is absorbed by the system and 30 kJ of
work is done on the surroundings.

Ans. ΔU = 70 kJ
Sample Problem #17
1. When 100 kJ of work is done on a closed system during a process, the total
energy of the system increases by 55.0 kJ. Calculate how much heat is either
added or removed from the system?

Ans. -45 kJ
Sample Problem #18

Consider the following reaction in a container with a movable piston:

A(l) + B(l) = C(g)

The ΔU for this reaction is 760 J. As the piston moves up, the system absorbs
839 J of heat from its surroundings.
a. Is work done on the system?
b. How much work was done?

Ans. No, -79 kJ

 Enthalpy of Chemical
Reactions
The term enthalpy originates from the Greek word enthalpein that means “to
warm”. Enthalpy is the energy transferred under constant pressure, represented
by the symbol H. Also, it is known as the heat content. Just like (U) internal
energy, H is also a state function which is defined by the change from the final to
the initial state.

𝛥𝐻 = 𝐻𝑓𝑖𝑛𝑎𝑙 −𝐻𝑖𝑛𝑖𝑡𝑖𝑎𝑙
 Heat of Reaction
Enthalpy change is called heat of reaction which is based on the net energy
change from the breaking and making of bonds. It represents heat absorbed or
released when the reactants are converted intro products, at a constant
pressure.

𝛥𝐻 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 −𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
𝛥𝐻 = 𝑞 (at a constant pressure)
The enthalpy of chemical reactions is composed of the reactants and products
and their corresponding bond energies, the amount of energy to break the bonds
or released in forming the bonds. The sign of ΔH determines the direction of
heat transfer. A positive ΔH means an absorption of heat from the surroundings,
also known as endothermic reaction. A negative value of ΔH indicates an
exothermic reaction, a heat releasing process.
 Hess’ Law
Hess’ Law states that…

1. Reverse reaction – reverse sign (If we reverse the reaction, we have to

reverse the sign in that change in enthalpy)

2. Enthalpy of the reaction is equal to the sum of the parts.

A thermochemical equation can be expressed as the sum of two or more

equations,
overall equation=equation 1+equation 2 +⋯
and, ΔH for the overall equation is the sum of the ΔH for the individual equations:
∆𝐻 = ∆𝐻1 + ∆𝐻2 + ⋯
 Sample Problem #19
What is the heat of reaction of Carbon Monoxide if the following reaction are
used?
𝐶(𝑠) + 𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) 𝛥𝐻 = −393.5 𝑘𝐽

𝐶𝑂(𝑔) + ½ 𝑂2 → 𝐶𝑂2 𝛥𝐻 = −283.0 𝑘𝐽

(𝑔) (𝑔)

Target: 𝐶(𝑠) + ½ 𝑂2 (𝑔) → 𝐶𝑂(𝑔)

Ans. 𝜟𝑯 = −𝟏𝟏𝟎. 𝟓 𝒌𝑱
 Sample Problem #20
1. Find the enthalpy change for the reaction.
𝐶𝑆2 (𝑙) + 3 𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) + 2 𝑆𝑂2 (𝑔)
when:
𝐶(𝑠) + 𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) 𝛥 𝐻𝑓 = −393.5 𝑘𝐽/𝑚𝑜𝑙

𝑆(𝑠) + 𝑂2 (𝑔) → 𝑆𝑂2 (𝑔) 𝛥𝐻𝑓 = −296.8 𝑘𝐽/𝑚𝑜𝑙

𝐶(𝑠) + 2 𝑆(𝑠) → 𝐶𝑆2 (𝑙) 𝛥𝐻𝑓 = 87.9 𝑘𝐽/𝑚𝑜𝑙

Ans. 𝜟𝑯 = −1075 𝒌𝑱/mol

 Enthalpies of formation
• Enthalpies of formation can be used to calculate standard enthalpy of
reaction. The standard enthalpy of a reaction, ΔH°, is the enthalpy change
when all the reactants and products are in their standard states.
• The standard enthalpy change for a given reaction is equal to the sum of the
standard enthalpies of formation of the products minus the sum of the
enthalpies of formation of the reactants, as shown in the following
mathematical expression.

∆𝐻° = ෍ 𝑛∆𝐻𝑓 ° 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ෍ 𝑛∆𝐻𝑓 ° 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

• Elements in their standard states that are involved in the reaction are usually
omitted since their heats of formation are equal to zero. Let us consider the
following reaction to illustrate this.

𝐴𝑙 𝑠 + 𝐹𝑒2 𝑂3 → 𝐹𝑒 𝑠 + 𝐴𝑙2 𝑂3
𝑠 𝑠
Applying the formula to get the standard enthalpy change:

∆𝐻° = ∆𝐻𝑓 °𝐴𝑙2 𝑂3 (𝑠) − ∆𝐻𝑓 °𝐹𝑒2 𝑂3 (𝑠)

Note that elements Al(s) and Fe(s) are not included.
Sample Problem #21
Given the standard enthalpies of formation for the following:
Compounds ΔHf°
C6H12 (l) -151.9 kJ/mol
CO2(g) -393.5 kJ/mol
H2O (l) -285.8 kJ/mol

Calculate the ΔH° for the combustion of hexane as shown in the following
equation.
𝐶6𝐻12(𝑙) + 9𝑂2(𝑔) → 6𝐶𝑂2(𝑔) + 6𝐻2𝑂(𝑙)

Ans. ∆𝑯° = −𝟑𝟗𝟐𝟑. 𝟗 𝒌𝑱

Sample Problem #22
Calculate the standard enthalpy of formation, ΔH° for methane gas, CH4,
produced from graphite and hydrogen gas according to the following reaction:

𝐶(𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒) + 2𝐻2(𝑔) → 𝐶𝐻4(𝑔)

Analysis: Since this reaction that forms methane does not happens as written,
ΔH° of methane is determined indirectly using the following set of reactions,
whose ΔH° have been accurately determined and applying Hess’ Law.

𝐶(𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒) + 𝑂2(𝑔) → 𝐶𝑂2(𝑔) ∆𝐻° = −393.5 𝑘𝐽

𝐻2(𝑔) + 1/2𝑂2(𝑔) → 𝐻2𝑂(𝑙) ∆𝐻° = −285.8 𝑘𝐽
𝐶𝐻4(𝑔) + 2𝑂2(𝑔) → 𝐶𝑂2(𝑔) + 2𝐻2𝑂(𝑙) ∆𝐻° = −890.4 𝑘𝐽

Ans. ∆𝑯° = −𝟕𝟒. 𝟕 𝒌J

 Relating ΔH to quantities of reactants and
products

Since the change in enthalpy is an extensive property, changing the amount

of the reactants will also change the amount of the products and the value of
ΔH.
Sample Problem #23
The following equation shows the absorption of heat in the evaporation of
water.
2 𝐻2 𝑂(𝑙) → 2 𝐻2 𝑂(𝑔) 𝛥𝐻 = +88 𝑘𝐽

a. How many moles of water results in the absorption of 88kJ of heat? Ans. 2 moles
b. If 3 moles of water will evaporate, what is ΔH? Ans. 132 kJ
c. If 50g of water will evaporate, how much energy is needed? Ans. 122 kJ
 Spontaneous Processes

1. Spontaneous: process that does occur under a specific set of

conditions
2. Nonspontaneous: process that does not occur under a specific set of
conditions
Spontaneous vs
Nonspontaneous
 Entropy

Entropy, S, can be viewed as a measure of randomness, or disorder.

The change in entropy, ΔS, depends only on the entropies of the final and initial
states of the system.
∆𝑺 = 𝑺𝒇𝒊𝒏𝒂𝒍 − 𝑺𝒊𝒏𝒊𝒕𝒊𝒂𝒍
There are several factors that influence the amount of entropy present in a
system at a particular state. These factors are the following:

1. Change in Phase

2. Change in Temperature

3. Number of particles
 Entropy Change
Determination

ΔS is change in entropy in J/K (it is negative if heat is released by the system and
positive if heat is absorbed by the system),
q = heat transferred at a particular temperature, in J and
T = temperature in Kelvin, (K)
Sample Problem #24:
Calculate the entropy change, ΔSvap, when 1 mole water in liquid state is
converted to 1 mole steam at 1 atm pressure?
Given: qrev= heat of vaporization, ΔHvap (amount of heat transferred to the system),
equal to +40.7kJ/mol
T = temperature at which the process occurs is the boiling point (100 oC or 373 K)

Ans. +𝟏𝟎𝟗 𝐉/K

 Standard Molar Entropy
Standard Molar Entropy or standard entropy, S0 , is defined as the entropy of one
mole of a substance at standard condition, 25oC and 1 atm pressure. The
entropy of a substance can be obtained from the tabulated values of standard
molar entropies, and entropy change can be calculated using this equation,

The superscript o in the symbol indicates standard conditions (25oC and 1 atm
pressure) while letters y and z, represent the number of moles.
Sample Problem #25
Calculate the entropy change when graphite burns in sufficient supply of oxygen
as shown in the equation below,
𝑪 𝒈𝒓𝒂𝒑𝒉𝒊𝒕𝒆(𝒔) + 𝑶𝟐(𝒈) → 𝑪𝑶𝟐

Solution: Given: S0 of C graphite (s) = 5.7 J/mol-K

S0 O2 (g) = 205 J/mol-K
S0 CO2 (g) = 213.6 J/mol-K

Ans. ∆𝑺° = +𝟐. 𝟗 𝑱/K

 Second Law of
Thermodynamics

The second law of thermodynamics expresses the relationship between

spontaneity of a process. It states that the natural processes proceed in
the direction that maintains or increases the total entropy of the
universe, and in any spontaneous change, there is a net increase in
entropy.
Since the universe consists of two parts, the system and the
surroundings, it makes sense that entropy change of the universe is the
sum of the changes in entropy of the system and the surroundings as
expressed by the following equation:

Under standard conditions, the entropy change for the universe, ΔSo
universe is
Sample Problem #26:
Show quantitatively, that the process for dissolving NaCl in water at 25 oC, has a
positive entropy change value, ΔSo universe.

𝑁𝑎𝐶𝑙(𝑠) → 𝑁𝑎𝐶𝑙(𝑎𝑞)

Given:
So NaCl (s) = 72.1 J/mol-K T = 25 oC or 298 K
So NaCl (aq) = 115.5 J/mol-k
ΔHfo NaCl (s) = - 411.1 kJ/mol
ΔHfo NaCl (aq) = - 407.3 kJ/mol Ans. ∆𝑺° = +30.65 𝑱/K
 Gibbs Free Energy
In predicting the spontaneity of a process, the enthalpy factor is considered in
conjunction with the entropy factor. The balance between these two quantities is
given by another state function called free energy or Gibbs free energy,
represented by G, named after the proponent, William Gibbs.

Gibbs free energy, G, is defined mathematically as

𝑮 = 𝑯 − 𝑻S

H is enthalpy, T is temperature in Kelvin, and S is entropy

Every substance possesses free energy, but the actual amount is seldom known,
hence, what will be considered is the change free energy, of a system. For a
process occurring at constant temperature, the change in free energy of the
system is given by the expression

∆𝑮 = ∆𝑯 − 𝑻∆S

This equation is valid in all conditions.

If both temperature and pressure are constant, the relationship
between the sign of ΔG and spontaneity of a reaction is as follows:

ΔG < 0, reaction is spontaneous in the forward direction

ΔG > 0, nonspontaneous in the forward direction, work must be
supplied to make it occur
ΔG = 0, reaction is at equilibrium
If application is limited to standard condition, 25oC and 1 atm pressure, the new
equation will be in the form:

∆𝑮° = ∆𝑯° − 𝑻∆S°

Standard state means that solid and liquid substance are pure, gaseous
substance is at 1 atm pressure, and for substances in solution, concentration is
normally 1M.
Sample Problem #27:
A drying agent has the chemical composition CaSO4. Calculate the ΔGo at 25oC,
for the following reaction, which has ΔSo value of -139.7 J/K.

𝐶𝑎𝑆𝑂4(𝑆) → 𝐶𝑎2−(𝑎𝑞) + 𝑆𝑂42−(𝑎𝑞) ∆𝐻° = −18.0 𝑘J

Ans. ∆G° = 23.63 kJ

The table below shows the relationship between temperature, ΔGo, and spontaneity.
 Effect of Temperature on the
Spontaneity of the Reactions
Sample Problem #28
Calculate the standard free energy change for the following reaction at 25 oC.
𝟐𝑯𝒈𝑶(𝒔) → 𝟐𝑯𝒈(𝒍) + 𝑶𝟐(𝒈)

Given: standard entropy values, So values at 25oC are as follows,

So Hg(l) = 76.0 J/mol-K ΔHfo of Hg(l) = 0
So O2(g) = 205.1 J/mol-K ΔHfo of O2(g) = 0
So HgO(s) = 70.3 J/mol-K ΔHfo of HgO(s) = -90.8 kJ

Ans. ∆G° = 117083 𝑱

Thank you for
Listening!
End of General Chemistry Lecture