Objectives

• Understand the fundamental principles governing energy transformations.

• Apply the laws of thermodynamics to analyze and predict the behavior of physical and chemical systems.

• Solve problems related to heat, work, internal energy, enthalpy, and entropy.

• Explain the limitations on energy conversion imposed by the Second Law.

• Understand the concept of reversibility and irreversibility.

• Relate the laws of thermodynamics to real-world applications (e.g., power generation, refrigeration, chemical
reactions).

THERMODYNAMICS

Basic Concepts

• Thermodynamics: The study of energy and its transformations, particularly the relationships between heat, work,
and internal energy.

Concept of Temperature

Temperature is a measure of the average kinetic energy of the particles in a substance. It determines how hot or cold an
object is and influences many physical and chemical processes.

Key Aspects of Temperature

1. Measurement
o Temperature quantifies the thermal energy of a substance.
o It is measured in degrees using scales such as:
▪ Celsius (°C) – Commonly used in most countries and scientific studies.
▪ Fahrenheit (°F) – Used mainly in the United States.
▪ Kelvin (K) – The SI unit of temperature, often used in physics and engineering.
2. Temperature and Particle Motion
o Higher temperatures mean particles move faster due to increased kinetic energy.
o Lower temperatures indicate slower-moving particles.
o At absolute zero (0 K or -273.15°C), all molecular motion theoretically stops.
3. Heat vs. Temperature
o Temperature is a measure of kinetic energy, while heat is the transfer of energy from one object to
another due to a temperature difference.
o Example: A cup of hot coffee and a bathtub full of lukewarm water—the bathtub has more heat energy
because it has more mass, but the coffee has a higher temperature.
o Heat transfer is the process by which thermal energy moves from one place to another. This movement
can occur through several different mechanisms.
o 1. Conduction:
o Definition: Conduction is the transfer of heat through a material by direct contact of particles. It occurs
when a temperature difference exists within a solid or between two solids in physical contact.
o Heat energy is transferred from more energetic particles to less energetic ones through collisions and
vibrations.
 o Examples:
o A metal spoon heating up when placed in a hot cup of tea.
o Heat transferring through the wall of a house.
o 2. Convection:
o Definition: Convection is the transfer of heat through the movement of fluids (liquids or gases).
o Warmer, less dense fluid rises, while cooler, denser fluid sinks, creating a circulating current that transfers
heat.
o Types:
o Natural convection: Driven by buoyancy forces caused by temperature differences.
o Forced convection: Driven by external means, such as a fan or pump.
o Examples:
o Boiling water.
o The circulation of warm air in a room.
o Wind.
o 3. Radiation:
o Definition: Radiation is the transfer of heat through electromagnetic waves.
o It can occur through a vacuum and does not require a medium.
o Examples:
o The sun's heat warming the Earth.
o Heat from a fireplace.
o Heat from a lightbulb.
o Adiabatic Heating:
o Definition: Adiabatic heating is a process where the temperature of a gas increases due to a change in
pressure, without any heat being exchanged with the surroundings.
o This typically occurs when a gas is compressed rapidly.
o The term adiabatic means that there is no heat transfer into or out of a system.
o Explanation:
o When a gas is compressed, work is done on it, increasing its internal energy.
o This increase in internal energy manifests as a rise in temperature.
o Because the process is adiabatic, this temperature increase is not due to heat transfer from an external
source.
o Examples:
o The heating of air as it is compressed in a bicycle pump.
o The warming of air as it descends a mountain range (a phenomenon known as a foehn wind).
o The compression of gasses within a diesel engine cylinder, which causes the gasses to reach a temperature
that ignites the fuel.
o In essence, adiabatic heating is a temperature increase resulting from work being done on a system, rather
than from the addition of heat.
4. Applications of Temperature
o Weather and Climate: Temperature affects weather patterns and ecosystems.
o Thermal Expansion: Materials expand or contract based on temperature changes.
o States of Matter: Temperature determines whether a substance is solid, liquid, or gas.
o Biological Processes: Enzymes and metabolism are temperature-dependent.

• System: The specific part of the universe that is being studied (e.g., a chemical reaction in a flask).

• Surroundings: Everything outside the system that can exchange energy and/or matter with it.

• Universe: The system and surroundings together.

• Open System: A system that can exchange both energy and matter with its surroundings (e.g., a boiling pot of
water).
 • Closed System: A system that can exchange energy but not matter with its surroundings (e.g., a sealed container
with a gas).

• Isolated System: A system that cannot exchange either energy or matter with its surroundings (e.g., a perfectly
insulated container).

Properties and States

• State Function: A property of a system that depends only on its current state, not on how it reached that state
(e.g., temperature, pressure, internal energy).

• Intensive Property: A property that does not depend on the amount of substance present (e.g., temperature,
density).

• Extensive Property: A property that depends on the amount of substance present (e.g., mass, volume).

• Thermodynamic Equilibrium: A state where the system's properties (temperature, pressure, etc.) are not changing
over time.

• Spontaneous Process: A process that occurs without any external input of energy.

• Non-spontaneous Process: A process that requires an external input of energy to occur.

• Exothermic Process: A process that releases heat to the surroundings (ΔH < 0).

• Endothermic Process: A process that absorbs heat from the surroundings (ΔH > 0).

• Thermodynamic System: This refers to a specific quantity of matter that we're studying (e.g., a gas in a container, a
cup of coffee).

• Thermal Equilibrium: Two systems are in thermal equilibrium when they have the same temperature and there is
no net flow of heat between them when they are in contact.

LAWS OF THERMODYNAMICS

The laws of thermodynamics are fundamental principles that govern the behavior of energy and its transformations. They
provide a framework for understanding how energy flows in physical systems, from microscopic particles to the entire
universe.

1. Zeroth Law of Thermodynamics: The Zeroth Law of Thermodynamics is a fundamental principle that deals with thermal
equilibrium. It might seem a bit obvious, but it's essential for establishing the concept of temperature and how we
measure it.

The Basic Idea

The Zeroth Law states:

If two thermodynamic systems are each in thermal equilibrium with a third system, then they are in thermal equilibrium
with each other.

Let's break that down:

Why is this important?

 • Temperature: The Zeroth Law provides the basis for the concept of temperature. It tells us that temperature is a
property that determines whether systems are in thermal equilibrium with each other. If two systems are in
equilibrium with a third, they must have the same temperature.

• Measurement: This law allows us to compare the temperatures of different objects using a thermometer. A
thermometer acts as the "third system." If it's in equilibrium with two other systems, those systems must have the
same temperature.

Analogy

Think of it like this:

If Alice is friends with Bob, and Alice is also friends with Carol, then Bob and Carol must also be friends with each other.

In simpler terms:

If two objects are both at the same temperature as a third object, then they are at the same temperature as each other.

Key Points

• The Zeroth Law might seem obvious, but it's a fundamental principle that lays the groundwork for understanding
temperature and heat transfer.

• It allows us to define temperature as a property that determines thermal equilibrium.

• It justifies the use of thermometers to compare temperatures.

Historical Note:

Interestingly, this law was named the "Zeroth Law" even though it logically comes before the First and Second Laws of
Thermodynamics. This is because it was recognized and formulated after the other laws were already named, but it was
realized that it was a more fundamental principle.

* Concept: * This law defines thermal equilibrium. It states that if two systems are each in thermal equilibrium with a
third system, then they are in thermal equilibrium with each other.

* Significance: * It establishes the concept of temperature as a measurable property and provides the basis for
constructing thermometers. Essentially, it allows us to determine if two objects are at the same temperature.

2. First Law of Thermodynamics:

* Concept: * This law is essentially the principle of conservation of energy. It states that energy cannot be created or
destroyed, but it can be transferred from one form to another.

* Mathematical Expression: *

Often expressed as: ΔU = Q - W,

where:

* ΔU is the change in internal energy of a system.

* Q is the heat added to the system.

* W is the work done by the system.

Important Notes:

• Sign Conventions: Be careful with signs!

• Q = Heat added to the system is positive, heat released is negative.

• W = Work done on the system is positive, work done by the system is negative.

• Units: Make sure to use consistent units for all calculations (e.g., Joules for energy, Kelvin for temperature).

* Significance: * It tells us that the total energy of an isolated system remains constant. It governs energy transformations
in all physical processes.
• It is the amount of heat energy released or taken in, per mole of substance, during a physical or chemical
change.

Enthalpy is a fundamental concept in thermodynamics that represents the total heat content of a system. It's a state
function, meaning its value depends only on the current state of the system, not how it reached that state.

Here's a breakdown of enthalpy:

• Definition: Enthalpy (H) is the sum of a system's internal energy (U) and the product of its pressure (P) and volume
(V): H = U + PV

• Significance: Enthalpy is particularly useful because it simplifies the study of heat changes in processes that occur
at constant pressure, which is a common condition in many chemical and physical transformations.

• Enthalpy Change (ΔH): The change in enthalpy during a process is what's typically measured and is equal to the
heat absorbed or released by the system at constant pressure.

o ΔH = Q (at constant pressure)

o ΔH > 0: Endothermic process (heat absorbed)

o ΔH < 0: Exothermic process (heat released)

Applications: Enthalpy is used extensively in various fields:

o Chemistry: Calculating heats of reaction, bond energies, and phase transitions.

o Engineering: Designing heat exchangers, power plants, and chemical reactors.

o Physics: Studying thermodynamic properties of materials.

Key Points to Remember:

• Enthalpy is a state function.

 • Enthalpy change (ΔH) is what's usually measured.

• ΔH = q at constant pressure.

• Enthalpy is crucial for understanding heat changes in chemical and physical processes.

• Hess's Law of Enthalpy, also known as Hess's Law of Constant Heat Summation, is a fundamental principle in
thermodynamics.

• It states that the total enthalpy change for a chemical reaction is independent of the pathway taken, whether it
occurs in one step or multiple steps. In simpler terms, the overall enthalpy change depends only on the initial and
final states of the reaction, not on the intermediate steps.

3. Second Law of Thermodynamics:

* Concept: * This law introduces the concept of entropy, which is a measure of the disorder or randomness of a system. It
states that the total entropy of an isolated system can only increase over time or remain constant in ideal cases; it never
decreases.

* Key Implications: * Heat cannot spontaneously flow from a colder body to a hotter body.

We can use Hess’s law in this way:

* Not all heat can be converted into work.

* Natural processes tend to increase disorder.

H =  n Hf(products) - m Hf(reactants)
* Significance: *

where n and m are the stoichiometric

1. It defines the direction of spontaneous processes and explains why certain processes are irreversible. 2. It sets limits on
the efficiency of energy conversion.
coefficients.
Process Energy Transformation Efficiency Notes

Up to 50% (turbine), lower in One of the most efficient

Wind Power Kinetic (wind) to Electrical wind farms renewable sources

Potential (water) to Very high efficiency, but depends

Hydropower Electrical Up to 95% on location

15-20% (typical), up to 40% Efficiency varies greatly with

Solar Power Light (sun) to Electrical (advanced) technology and conditions
 Nuclear to Thermal to Lower than some renewables, but
Nuclear Power Electrical ~35% consistent output

Fossil Fuel Power Chemical (fuel) to Thermal 30-40% (coal), up to 60% Lower efficiency, also produces
Plants to Electrical (combined cycle gas) greenhouse gases

Internal Combustion Chemical (fuel) to 15-30% (cars), up to 50% Relatively low efficiency, lots of
Engines Mechanical (motion) (some engines) waste heat

Light (sun) to Chemical 0.1-2% (average), up to 6% (in Low efficiency overall, but essential
Photosynthesis (sugars) theory) for life

4. Third Law of Thermodynamics:

* Concept: * This law states that the entropy of a perfect crystal at absolute zero (0 Kelvin) is zero.

* Significance: * It implies that it is impossible to reach absolute zero in a finite number of steps. It also provides a
reference point for measuring entropy.

In summary: * The zeroth law defines temperature. * The first law deals with the conservation of energy. * The second
law addresses the direction of energy flow and the increase of entropy. * The third law defines the entropy at absolute
zero.

These laws are fundamental to many scientific disciplines, including physics, chemistry, and engineering, and have wide-
ranging applications in areas such as power generation, refrigeration, and materials science.