THERMODYNAMICS

• ENERGY CHANGES IN CHEMICAL REACTIONS

• FIRST LAW OF THERMODYNAMICS
• CALORIMETRY
• ENTHALPY OF A CHEMICAL REACTION: THERMOCHEMICAL EQUATIONS
• HESS’S LAW
 ENERGY CHANGES IN CHEMICAL
REACTIONS
• Thermochemistry is the study of energy or heat flow that
accompanies a chemical reaction and/or physical
transformations.
• Heat is a form of energy transfer between two objects as a
result of their temperature difference.
-flows from a higher to a lower temperature
 SYSTEM VS SURROUNDINGS
• System – the part of the universe being studied or to which
attention is focused.
• Surrounding – include everything in the universe
• Example
Consider a cup of hot coffee where a teaspoon is dipped. If the coffee is to be
taken as the system, then everything that is directly in contact with it is its surroundings
which include the cup, the teaspoon, and the air above the surface of the liquid. The
surroundings will absorb the energy from the hot coffee. And since they are colder than
the coffee, heat will flow from the coffee to the cup, the teaspoon, and the air above it.
Example
• Melting of ice is endothermic because the ice (system) absorbs the heat
from its surroundings.
• Freezing is exothermic because ice releases heat to its surroundings
• The combustion of gasoline is exothermic because it produces heat.
• Photosynthesis is endothermic because it requires energy from the sun,
while cellular respiration is exothermic because it breaks glucose
molecules to produce energy in the form of adenosine triphosphate (ATP).
IDENTIFY WHETHER THE FOLLOWING PROCESSES ARE
ENDOTHERMIC OR EXOTHERMIC. JUSTIFY YOUR ANSWER.
1. Explosion of a firecracker triggered by a spark
2. Melting solid salts
3. Solidifying solid salts
4. Splitting of an atom
5. Evaporating liquid water
6. Baking bread
7. Burning of coal
8. Solid lead chloride dissolves only in hot water
9. Heating causes sodium bicarbonate to decompose
10. Splitting a gas molecule
According to the law of conservation of energy, energy can neither be created nor destroyed. It can only
be transferred between the system and the surroundings.

The energy of the system (∆𝐸𝑠𝑦𝑠 ) and the

energy of its surroundings (∆𝐸𝑠𝑢𝑟𝑟 )

∆𝐸𝑠𝑦𝑠 = −∆𝐸𝑠𝑢𝑟𝑟
the negative sign indicates the flow of
energy

As the system releases energy, the

surroundings absorb it.

It states that energy cannot be created nor

destroyed, which means that energy is constant.
 Thermochemistry is a branch of thermodynamics, which deals with the
interconversion of energy between two forms: heat and work.

The study of energy and its transformations is known as thermodynamics.

Thermodynamic quantities always consist of two parts:
• A number, giving the magnitude of the change.
• A sign, indicating the direction of the flow.

The first law of thermodynamics states that in any process, the change in
energy of a system is equal to the heat absorbed (q) by the system and the
work (w) done on it.

∆𝐸𝑠𝑦𝑠 = 𝑞 + 𝑤

The law implies that the net energy flow to or from any system comes in the
form of either work or heat.
 The Nature of
Energy

Energy - the capacity to do work or transfer heat.

Work is the energy used to cause an object to move against a force.

Heat is the energy used to cause the temperature of an object to

increase.
 Energy

Potential Kinetic
- “stored” energy -energy in motion
• As a convection, heat is represented
by q.
-q = when heat flows from a system
to its surroundings (exothermic)
+q= when the system absorbs heat
from the surroundings (endothermic)

• Work is represented by w.
-w = when the system does the work, uses up, and transfers energy (expansion)
+w = when work is done on the system, and gains energy (compression)
SAMPLE
Calculate the change in energy for the following process. Identify if the
process is endothermic or exothermic.
1. A gas releases 35 J of heat as 84 J of work was done to compress
it.
Answer: ∆𝐸𝑠𝑦𝑠 = −q + +w = −35 J + 84 J = 49 J
endothermic
2. A gas absorbs 48 J of heat as it does 72 J of work by expanding.
Answer: ∆𝐸𝑠𝑦𝑠 = +q + −w = 48 J + −72 J = −24 J
Exothermic
A positive △ 𝐸 means that energy was gained from the surroundings. A
negative △ 𝐸 means that the energy was lost to the surroundings.

From this, we can say that when heat is absorbed by the system and the
surroundings are doing work on the system, the changes in internal energy is
positive. On the other hand, in a system releasing heat and doing work, is △ 𝐸
is negative.

EXERCISE1
What is the value of △ 𝐸 in a system wherein a car
engine that releases heat pushing the piston, doing 451 J
of work and losing 325 J to the surroundings?
 CALORIMETRY
The flow of energy (as heat) between the system and
its surroundings is measured through calorimetry.
• Calorimetry is the amount of heat absorbed or
released by the system as a function of its
temperature change.

It is the science of measuring heat based on the change in

temperature of an observed body when it releases or
absorbs heat.
The apparatus which determines the heat flow is called
calorimeter.
The magnitude of q (heat) can be computed using the
equation,
q = 𝑚𝑐 △ 𝑇

Where q = heat absorbed or released, 𝐉

𝑚 = mass of the substance, 𝐠
𝑐 = specific heat of the substance, 𝐉/𝐠°𝐂
△ 𝑇 = change in the temperature,°𝐂
△ 𝑇 = 𝑡𝑓𝑖𝑛𝑎𝑙 − 𝑡𝑖𝑛𝑖𝑡𝑖𝑎𝑙
 The specific heat of a
substance is constant.

Note: different states of the same

substance (e.g. water) have different
values of specific heat
Problem:
How much heat is absorbed by liquid water that weights
550 grams as it is heated from 25⁰C to 95⁰C?
q = 𝑚𝑐 △ 𝑇

q = (550 g)(4.18 J/g.⁰C)(95 ⁰C -25 ⁰C)

= 160930 J or 161 kJ

Exercise
How much heat is released by a 76-gram piece of
aluminum as it cools from 450⁰C to 28⁰C?
Exercise:
A 1.00-g sample of Octane (C8H18) was
burned in a bomb calorimeter with 1300 g of
water (H2O). The temperature increases from
25°C to 34.10°C. Calculate the heat absorbed
by the water, 𝑞𝐻2 𝑂 .

The specific heat of water is 4.184 J/g°C.

ENTHALPY OF A CHEMICAL REACTION:
THERMOCHEMICAL EQUATION
 ∆H = 𝑯𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − 𝑯𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
positive ∆H = product has a greater enthalpy than the reactant,
chemical reaction endothermic

For an endothermic reaction, the heat content of the products is

greater than the heat content of the reactants because heat is
absorbed. The value of 𝜟𝑯 > 0.

negative ∆H = product has a lower enthalpy than the reactant,

chemical reaction exothermic

For an exothermic reaction, the heat content of reactants is

greater than the heat content of the products since heat is released.
The value of 𝜟𝑯 < 0.
 Steps in Calculating Enthalpy of
Reaction

1. Find the enthalpies of formation for all

chemical components of the reaction
using a Table of Heat Formation.
2. Multiply each enthalpy value on the
corresponding reaction coefficient and
sum up the enthalpies of formation.
3. Do the same to the final reagents
(products).
4. Subtract the enthalpy of formation of
the initial reagents (reactants) from the
final reagents (products).
Examples: Calculating the Enthalpy of Reaction
If heat is absorbed in a reaction, it is written as a reactant. If heat
is released, it is written as a product.
Sample Problem
Using the enthalpy/heats of formation.
Find the ∆𝑯 of this reaction.
Practice Exercise

Substance 𝑪𝟑 𝑯𝟖 (g) 𝑶𝟐 (g) 𝑪𝑶𝟐 (g) 𝑯𝟐 𝑶 (g)

° 𝑘𝐽
∆𝐻 ( ) −104.0 0 −393.5 −241.8
𝑓 𝑚𝑜𝑙

𝑪𝟑 𝑯𝟖 𝒈 + 5 𝑶𝟐 (g) → 3 𝑪𝑶𝟐 (g) + 4 𝑯𝟐 𝑶 (g)

 Example of the Change in
Enthalpy for a Reaction Using
HESS’s LAW Steps in Calculating Change in
Enthalpy (no definite steps)

1. Balance the individual equation

2. If necessary, look up standard
enthalpies
3. Flip equations around if
necessary to cancel out terms on
opposite sides
4. Changing the equation around
requires a sign change of the H
of that individual step
5. Sum up the individual steps
 2𝐻2 (𝑔) + 𝑂2 (𝑔) → 2 𝐻2 𝑂(𝑙)
∆𝐻𝑟𝑥𝑛 = −572 𝑘𝐽
What is the enthalpy change when 3 moles of 𝑂2 are consumed in the
reaction above?

−572 𝑘𝐽
3 𝑚𝑜𝑙𝑒𝑠 × = −1716 𝑘𝐽
1 𝑚𝑜𝑙𝑒
What is the enthalpy change when 9 g of 𝐻2 𝑂(𝑙) are produced in the
reaction above?

1 𝑚𝑜𝑙𝑒 −572 𝑘𝐽
9 𝑔 𝐻2 𝑂(𝑙) × × = -143 kJ
18 𝑔 2 𝑚𝑜𝑙𝑒𝑠 𝐻2 𝑂(𝑙)
1. Enthalpy of combustion – the change in enthalpy that occurs during combustion
reaction. Enthalpy changes have been measured for the combustion of virtually
any substance that will burn in oxygen; these values are reported as the enthalpy
of combustion per mole of a substance.

2. Enthalpy of fusion – the enthalpy change that accompanies the melting (fusion)
of 1 mol of a substance. The enthalpy change that accompanies the melting, or
fusion of 1 mol of a substance; these values have been measured for almost all
the elements for most simple compounds.

3. Enthalpy of vaporization – the enthalpy change that accompanies the

vaporization of 1 mol of a substance; these values have also been measured for
nearly all the elements and most volatile compounds.

4. Enthalpy of solution – the change in enthalpy that occurs when a specified

amount of solute dissolves in a given quantity of solvent. The enthalpy changes
when a specified amount of solute is dissolved in a given quantity of solvent.
Summary
During a chemical reaction, the
energy of the system changes as
bonds in the reactant are broken
and the atoms rearrange to
form the new bonds of the
products. These new bonds are
typically higher or lower in
energy. If the products store
more energy in their bonds, that
energy must come from
somewhere, and so it is
transferred into the system from
the surroundings.
 Summary
The First Law of Thermodynamics or simply
the Law of Conservation of Energy applies to
all chemical reactions, in which the total
amount of energy is constant and it's just
changed from one form to another. Just like in
an Endothermic process, like in photosynthesis
where the plants take Energy from the
surroundings to store more energy.
 Summary
❖ Combustion–the rapid chemical combination of a substance
with oxygen, involving the production of heat and light
❖ Enthalpy (H) – the amount of change in energy in a
chemical reaction
❖ Enthalpy of a reaction 𝑯𝒓𝒙𝒏 − the difference in enthalpy
between products and reactants
❖ Thermodynamics – the scientific study of the
interconversion of heat and other kinds of energy
❖ Hess’s law states that the overall enthalpy change in a
reaction is equal to the sum of enthalpy changes for the
individual steps that make up the overall reaction.