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Chapter 1 Thermodynamics

What is Thermodynamics ?

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The branch of physical science that deals with the relations between heat and other forms of energy (such as mechanical, electrical, or chemical energy), and, by extension, of the relationships between all forms of energy.

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Properties of Substance in Thermodynamic

Temperature:-

Temperature is “a measure of the average kinetic energy of the particles in a sample

of matter, expressed in terms of units or degrees designated on a standard scale," according to the American Heritage Dictionary.

Conversion between Fahrenheit and Celsius

If we know Celsius and want Fahrenheit

F

9

5

C

32

If we know Fahrenheit and want Celsius

C

5

9

F

32

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Pressure

Pressure

Force

Area

Example

120 lb woman putting all her weight on 2 in 2 of heals.

Pressure = 120 lb/2in 2 = 60 lb/in 2 .

Is that a lot?

Comparison: 1 atm = 14.7 lb/in 2 . Thus of heals is

approximately 4 atm. This is the pressure you would feel at a depth of approximately 133 ft of water.

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Enthalpy :- a thermodynamic quantity equivalent to the total heat content of a system. It is equal to the internal energy of the system plus the product of pressure and volume.

Entropy :- a thermodynamic quantity representing the unavailability of a system's thermal energy for conversion into mechanical work, often interpreted as the degree of disorder or randomness in the system.

Mass:-

the property of matter that measures its resistance to acceleration. Roughly, the mass of an object is a measure of the number of atoms in it. The basic unit of measurement for mass is the kilogram.

Volume :- The amount of space occupied by a three-dimensional object or region of space. Volumes are expressed in cubic units.

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examples of entropy

On the large scale, the ice “looks” more disordered.

On the small scale, the solid phase severely limits where the molecules could be.

The ice crystal molecules are much more ordered than the free moving liquid water molecules.

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Thermodynamic systems

To understand the laws of thermodynamics and how they work, first we need to get the terminology right. Some of the terms may look familiar (as they are used in everyday language as well)- but their meanings are more ‘technical’ and ‘precise’, when used in TD and hence we should not use them ‘casually’. System is region where we focus our attention (Au block in figure). Surrounding is the rest of the universe (the water bath at constant ‘temperature’). Universe = System + Surrounding More practically, we can consider the ‘Surrounding’ as the immediate neighborhood of the system (the part of the universe at large, with which the system ‘effectively’ interacts). In this scheme of things we can visualize: a system, the surrounding and the universe at large.

Thermodynamic systems  To understand the laws of thermodynamics and how they work, first we need
In TD we usually we do not worry 8 about the universe at large!
In TD we usually we do not worry
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about the universe at large!

Open, closed and isolated systems

To a thermodynamic system two ‘things’ may be added/removed:

energy (heat, work) matter. An open system is one to which you can add/remove matter (e.g. a open beaker to which we can add water). When you add matter- you also end up adding heat (which is contained in that matter). A system to which you cannot add matter is called closed. Though you cannot add/remove matter to a closed system, you can still add/remove heat (you can cool a closed water bottle in fridge). A system to which neither matter nor heat can be added/removed is called isolated. A closed vacuum ‘thermos’ flask can be considered as isolated.

Type of boundary

Interactions

Open

All interactions possible

Closed

Matter cannot enter or leave

Semi-permeable

Only certain species can enter or leave

Insulated

Heat cannot enter or leave

Rigid

Mechanical work cannot be done*

Isolated

No interactions are possible**

* By or on the system ** Mass, Heat or Work

 
Mass

Mass

 
 
Mass Interactions possible Work Heat
   

Interactions possible

Work

Mass Interactions possible Work Heat
 
Heat

Heat

 

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The Zeroth Law states that if two bodies are in thermal equilibrium with some third body, then they are also in equilibrium with each other. This establishes temperature as a fundamental and measurable property of matter.

The First Law states that the total increase in the energy of a system is equal to the increase in thermal energy plus the work done on the system. This states that heat is a form of energy and is therefore subject to the principle of conservation.

The Second Law states that heat energy cannot be transferred from a body at a lower temperature to a body at a higher temperature without the addition of energy. This is why it costs money to run an air conditioner.

The Third Law states that the entropy of a pure crystal at absolute zero is zero. As explained above, entropy is sometimes called "waste energy," i.e., energy that is unable to do work, and since there is no heat energy whatsoever at absolute zero, there can be no waste energy. Entropy is also a measure of the disorder in a system, and while a perfect crystal is by definition perfectly ordered, any positive value of temperature means there is motion within the crystal, which causes disorder. For these reasons, there can be no physical system with lower entropy, so entropy always has a positive value.

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Processes in TD

Here is a brief listing of a few kinds of processes, which we will encounter in TD:

Isothermal process → the process takes place at constant temperature T=C (e.g. freezing of water to ice at –10C)

Isobaric → constant pressure P=C (e.g. heating of water in open air→ under atmospheric pressure)

Isentropic process s=C

Isochoric → constant volume v=C (e.g. heating of gas in a sealed metal container)

Reversible process → the system is close to equilibrium at all times (and infinitesimal alteration of the conditions can restore the universe (system + surrounding) to the original state.

Cyclic process → the final and initial state are the same. However, q and w need not be zero. (VCC)

Adiabatic process delta H is zero during the process (no heat is added/removed to/from the system) Q=0

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