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The Principles of the First Law of Thermodynamics

The First Law of Thermodynamics, a cornerstone of energy conservation, asserts that energy within an isolated system is neither created nor destroyed. It explores energy transformations, the significance of internal energy, and the law's applicability to both reversible and irreversible processes. Carathéodory's formulation, empirical evidence from Joule's experiments, and the mathematical expression of the law are discussed, highlighting the universality of this fundamental principle.

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1

The ______ Law of Thermodynamics is also known as the principle of ______ conservation.

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First energy

2

The total energy of an isolated system remains ______, as per this fundamental thermodynamic concept.

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constant

3

In thermodynamics, the symbol 'U' stands for ______ energy, which is the total of all kinetic and potential energies.

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internal

4

Transformations like potential to kinetic energy within a system do not alter the system's overall ______ ______.

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energy balance

5

Carathéodory's focus in First Law formulation

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Emphasizes adiabatic processes; no heat exchange with surroundings.

6

Criticism of Carathéodory's formulation

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Incorporates Second Law elements; suggests not all states adiabatically reachable.

7

Münster's argument against Carathéodory

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Claims intertwining First and Second Laws can lead to confusion of distinct principles.

8

The ______ Law of Thermodynamics is based on experimental evidence, particularly the experiments of ______ ______ ______.

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First James Prescott Joule

9

The increase in a system's internal energy from work is often seen as a rise in ______.

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temperature

10

The findings of ______ ______ ______ provide empirical evidence for the principle of energy ______ in the First Law of Thermodynamics.

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James Prescott Joule conservation

11

First Law of Thermodynamics: Internal Energy and Work

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States that the change in internal energy of a system equals the heat added to the system minus the work done by the system.

12

Non-Adiabatic Process: Heat and Work Relationship

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In non-adiabatic processes, heat is the portion of internal energy change not explained by work done.

13

Heat Definition by Kittel and Kroemer

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Heat is defined as energy transferred through thermal contact with a reservoir, as per Kittel and Kroemer.

14

In an ______ process, energy is transferred only through work, not heat, and depends on the system's initial and final states.

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adiabatic

15

When heat is added in adynamic processes, it results in an increase in the system's ______ ______.

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internal energy

16

Both adiabatic and adynamic processes demonstrate that internal energy is a ______ ______.

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state function

17

The First Law of Thermodynamics states that changes in internal energy do not depend on the ______ taken.

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path

18

Characteristics of reversible processes in thermodynamics

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Idealized, no friction/dissipation, precise work/heat calculations.

19

Equation representation in the First Law for reversible processes

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Relates work and heat transfers to change in internal energy.

20

First Law's application to irreversible processes

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Valid for all processes; internal energy change depends only on initial and final states.

21

Internal energy, as a ______ function, is defined by the system's current ______ and not by the process of reaching it.

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state state

22

The acknowledgment of ______ energy as crucial enables the expansion of thermodynamic studies to include ______ changes in systems.

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internal state

23

Understanding ______ energy as a fundamental quantity has significantly improved our grasp of energy ______ and their principles.

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internal transformations

24

First Law of Thermodynamics for closed systems

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Energy conservation: δQ = dU + δW, heat change equals change in internal energy plus work done.

25

Meaning of dU in thermodynamics

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Exact differential of internal energy, representing total energy change in a system.

26

Expansion of fundamental thermodynamic relation for complex scenarios

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Includes chemical potentials and particle numbers to account for chemical reactions and phase transitions.

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The Principles of the First Law of Thermodynamics

The First Law of Thermodynamics, also known as the principle of energy conservation, states that within an isolated system, energy can neither be created nor destroyed, only transformed from one form to another. This fundamental concept in thermodynamics is derived from empirical observations and asserts that the total energy of an isolated system is constant. Energy transformations within the system, such as the conversion between potential and kinetic energy, do not affect the overall energy balance. The internal energy, symbolized by 'U', is a key term in this law, representing the sum of all kinetic and potential energies of the particles within the system.
Polished brass cylindrical steam engine with glass section showing the internal piston, mounted on a dark wooden base.

Carathéodory's Formulation and Its Critique

Carathéodory's formulation of the First Law focuses on adiabatic processes, which are characterized by the absence of heat exchange with the surroundings. His approach has been subject to criticism for prematurely incorporating elements of the Second Law of Thermodynamics, particularly the concept that not all states are adiabatically accessible from a given state. Critics, including Münster, argue that this intertwines the First and Second Laws in a way that may confuse the distinct principles they each represent.

Empirical Evidence Supporting the First Law

The First Law of Thermodynamics is grounded in experimental evidence, notably the work of James Prescott Joule, who demonstrated the interconvertibility of work and heat. Joule's experiments, such as stirring water with paddles, showed that work done on a system results in an equivalent increase in the system's internal energy, often observed as a rise in temperature. These findings confirm that energy transferred as work or heat alters the internal energy of a system, providing empirical support for the law's assertion of energy conservation.

Different Interpretations of the First Law

The First Law of Thermodynamics is articulated in various ways, with some formulations emphasizing the roles of internal energy and work, while others highlight heat as a mode of energy transfer. For example, certain texts describe heat as the change in internal energy not accounted for by work in non-adiabatic processes. Others, following the approach of Kittel and Kroemer, define heat in terms of energy exchange through thermal contact with a reservoir. Despite these differences in presentation, all interpretations uphold the fundamental principle of energy conservation.

Adiabatic Versus Adynamic Processes

Adiabatic processes are characterized by the transfer of energy solely as work, with no heat exchange, and are defined by the work being dependent only on the initial and final states of the system. In contrast, adynamic processes involve the transfer of energy exclusively as heat, without any work being performed. In these cases, the heat added to the system equates to the increase in internal energy. Both process types illustrate the concept of internal energy as a state function and affirm the First Law's principle that changes in internal energy are independent of the path taken.

Applicability to Reversible and Irreversible Processes

The First Law of Thermodynamics is applicable to both reversible and irreversible processes. Reversible processes, which are idealized scenarios without friction or other dissipative effects, allow for precise calculations of work and heat transfers, and the law is represented by a straightforward equation relating these quantities to the change in internal energy. In irreversible processes, which are more common in practical situations, the calculations are less direct, but the First Law remains valid, ensuring that the change in internal energy depends only on the system's initial and final states, not the specific path of the process.

The Significance of Internal Energy in Thermodynamics

Internal energy is a central concept in thermodynamics, encapsulating the total energy of a system. As a state function, its value is determined solely by the system's current state, independent of the path by which the system arrived there. The recognition of internal energy as a key property allows thermodynamics to extend its reach beyond cyclic processes to the analysis of state changes in systems. This understanding of internal energy as a fundamental thermodynamic quantity has greatly enhanced our comprehension of energy transformations and the governing principles.

Mathematical Expression of the First Law

In mathematical terms, the First Law of Thermodynamics for closed systems is expressed using infinitesimal quantities of heat (δQ) and work (δW), with the change in internal energy (dU) being an exact differential. For reversible processes, the law is formulated as dU = TdS - PdV, where T is temperature, S is entropy, P is pressure, and V is volume. This equation, known as the fundamental thermodynamic relation, succinctly captures the relationship between heat, work, and changes in internal energy. In more complex scenarios involving chemical reactions or phase transitions, the equation is expanded to include terms for chemical potentials and particle numbers to accommodate these additional factors.