Question

The incorrect statement(s) among the following is/ are (a) For a system undergoing a cyclic change, \(\oint \frac{\mathrm{fq}}{\mathrm{T}} \geq 0 .\) (b) A real crystal has lower entropy than ideal crystal. (c) Pressure is an extensive property. (d) A reversible process is always dynamic in nature.

Short answer

Statements (b), (c), and (d) are incorrect.

Step-by-step solution

Understanding Cyclic Integral - Statement (a)

The statement given is \( \oint \frac{\mathrm{dq}}{\mathrm{T}} \geq 0 \). This is a form of the Clausius inequality which states that for a real, irreversible cycle, this inequality holds. However, for a reversible cycle, the equality holds \( \oint \frac{\mathrm{dq}}{\mathrm{T}} = 0 \). The inequality indicates that the integration of heat over temperature around a closed cycle is never positive.

Evaluating Entropy - Statement (b)

The second statement claims "A real crystal has lower entropy than an ideal crystal." Entropy is a measure of disorder. A perfect, ideal crystal at absolute zero has entropy very close to zero according to the third law of thermodynamics. Real crystals generally have imperfections, resulting in higher entropy compared to an ideal crystal.

Defining Intensive vs Extensive Properties - Statement (c)

Pressure is defined as force per unit area. It does not depend on the amount of substance or its extent, thus it is an intensive property, not an extensive property. Extensive properties depend on the system size or amount, like mass or volume.

Dynamics of Reversible Processes - Statement (d)

A reversible process is defined as a process that can be reversed without leaving any change in both the system and surroundings. It occurs at an infinitely slow rate. Hence, reversible processes are static in nature, not dynamic. The statement is incorrect.

Key concepts

Clausius Inequality

The Clausius inequality is a fundamental concept in thermodynamics that relates to the second law of thermodynamics. It is typically expressed as \(\oint \frac{\mathrm{dq}}{T} \leq 0\), where \(\mathrm{dq}\) is the infinitesimal amount of heat exchanged, and \(T\) is the absolute temperature at which the heat exchange occurs. This inequality signifies that for any real, irreversible cyclic process, the integration of heat over temperature is less than or equal to zero.

In the case of a reversible cycle, where the system is perfectly efficient and without friction or other losses, this turns into an equality: \(\oint \frac{\mathrm{dq}}{T} = 0\). The Clausius inequality is crucial for identifying the direction of spontaneous processes. It helps indicate that real processes, which are often irreversible, will always generate entropy.

Entropy

Entropy is a measure of the disorder or randomness in a system. It's a key thermodynamic property that gives us insight into the number of microscopic configurations that correspond to a thermodynamic system's macroscopic state. According to the third law of thermodynamics, the entropy of a perfect crystalline structure at absolute zero is zero.

However, real crystals have naturally occurring imperfections, which increase their entropy. These imperfections mean that real crystals have a higher entropy than the ideal, perfectly ordered crystal structures. Entropy increases with temperature as the molecules have more energy and thus more possible arrangements.

• Low entropy: Well-ordered state
• High entropy: More disorder or randomness in the system

Intensive and Extensive Properties

In thermodynamics, properties are classified as intensive or extensive based on their dependency on the amount of matter present in the system.

Intensive properties, such as pressure and temperature, do not depend on the system's size or the amount of material in it. They remain constant regardless of how much substance is present. For example, the pressure of a gas in a balloon remains the same regardless of whether the balloon is small or large.

In contrast, extensive properties, like mass and volume, vary with the size of the system. If you double the amount of substance, the extensive properties also double. Understanding the difference between these properties is essential for solving thermodynamic problems as it helps in identifying which factors will change with the system's scale.

Reversible Processes

A reversible process is an idealized or theoretical concept in thermodynamics. It describes a process that can be reversed without any increase in entropy or any change in both the system and the surroundings. This requires the process to occur infinitesimally slowly so that the system is always in thermodynamic equilibrium.

Reversible processes are considered static due to the infinitely slow rate at which they occur. This allows for the system to adjust its parameters smoothly, ensuring that each state of the process is in equilibrium. However, in practice, all real processes are irreversible to some extent because they occur over finite timescales and often involve friction or other dissipation mechanisms. Recognizing the difference between reversible and irreversible processes is critical for harnessing their properties effectively in engineering and scientific calculations.