TERMODINAMIKA

Thermodynamic Systems and Their Surroundings

Thermodynamics is the branch of physics that is built upon the fundamental laws that heat and work obey.

Thermodynamics
In thermodynamics the collection of objects upon which attention is being focused is called the system, while everything else in the environment is called the surroundings. The system and its surroundings are separated by walls of some kind. Walls that permit heat to flow through them, such as those of the engine block, are called diathermal walls. Perfectly insulating walls that do not permit heat to flow between the system and its surroundings are called adiabatic walls.

State of a System
To understand what the laws of thermodynamics have to say about the relationship between heat and work, it is necessary to describe the physical condition or state of a system. The state of the system would be specified by giving values for the pressure, volume, temperature, and mass of the hot air.

The Zeroth Law of Thermodynamics

(a) Systems A and B are surrounded by adiabatic walls and register the same temperature on the thermometer. (b) When A is put into thermal contact with B through diathermal walls, no net flow of heat occurs between the systems.

The Zeroth Law of Thermodynamics

Two systems individually in thermal equilibrium with a third system are in thermal equilibrium with each other.

The Zeroth Law of Thermodynamics

Temperature is the indicator of thermal equilibrium in the sense that there is no net flow of heat between two systems in thermal contact that have the same temperature. There can be no flow of heat within a system in thermal equilibrium.

The First Law of Thermodynamics

The First Law of Thermodynamics

The internal energy of a system changes from an initial value Ui to a final value of Uf due to heat Q and work W: DU = Uf - Ui = Q W Q is positive when the system gains heat and negative when it loses heat. W is positive when work is done by the system and negative when work is done on the system.

The Internal Energy

The internal energy depends only on the state of a system, not on the method by which the system arrives at a given state.

EXAMPLE : An Ideal Gas

The temperature of three moles of a monatomic ideal gas is reduced from Ti = 540 K to Tf = 350 K by two different methods. In the first method 5500 J of heat flows into the gas, while in the second, 1500 J of heat flows into it. In each case find (a) the change in the internal energy and (b) the work done by the gas.

Solution

Since the internal energy of a monatomic ideal gas is U = (3/2) nRT and since the number of moles n is fixed, only a change in temperature T can alter the internal energy. Since the change in T is the same in both methods, the change in U is also the same. From the given temperatures, the change DU in internal energy can be determined. Then, the first law of thermodynamics can be used with DU and the given heat values to calculate the work.

Solution
(a) Using Equation U = (3/2) nRT for the internal energy of a monatomic ideal gas, we find for each method of adding heat that (b) Since DU is now known and the heat is given in each method, DU = Q W can be used to determine the work:

Thermal Processes
A system can interact with its surroundings in many ways, and the heat and work that come into play always obey the first law of thermodynamics. thermal process is assumed to be quasistatic, which means that it occurs slowly enough that a uniform pressure and temperature exist throughout all regions of the system at all times.

An Isobaric Process
The substance in the chamber is expanding isobarically because the pressure is held constant by the external atmosphere and the weight of the piston and the block. An isobaric process is one that occurs at constant pressure.

An Isobaric Process

The Figure shows a substance (solid, liquid, or gas) contained in a chamber fitted with a frictionless piston. The pressure P experienced by the substance is always the same and is determined by the external atmosphere and the weight of the piston and the block resting on it. Heating the substance makes it expand and do work W in lifting the piston and block through the displacement s.

An Isobaric Process

The work can be calculated from W = Fs, where F is the magnitude of the force and s is the magnitude of the displacement. The force is generated by the pressure P acting on the bottom surface of the piston (area = A), according to F = PA. With this substitution for F, the work becomes W = (PA)s. But the product A s is the change in volume of the material, DV = Vf - Vi, where Vf and Vi are the final and initial volumes, respectively.

An Isobaric Process
Thus, the expression for the work is Isobaric process W = PDV = P(Vf Vi ) A positive value for the work done by a system when it expands isobarically (Vf exceeds Vi). That Equation also applies to an isobaric compression (Vf less than Vi). Then, the work is negative, since work must be done on the system to compress it.

An Isobaric Process
For an isobaric process, a pressure-versus-volume plot is a horizontal straight line, and the work done [W = P(Vf2 Vi2)] is the colored rectangular area under the graph.

An Isochoric Process
a) The substance in the chamber is being heated isochorically because the rigid chamber keeps the volume constant. (b) The pressurevolume plot for an isochoric process is a vertical straight line. The area under the graph is zero, indicating that no work is done. an isochoric process, one that occurs at constant volume.

An Isochoric Process
Figure a illustrates an isochoric process in which a substance (solid, liquid, or gas) is heated. The substance would expand if it could, but the rigid container keeps the volume constant, so the pressurevolume plot shown in Figure b is a vertical straight line Because the volume is constant, the pressure inside rises, and the substance exerts more and more force on the walls.

An Isochoric Process
While enormous forces can be generated in the closed container, no work is done, since the walls do not move. Consistent with zero work being done, the area under the vertical straight line in Figure b is zero. Since no work is done, the first law of thermodynamics indicates that the heat in an isochoric process serves only to change the internal energy: DU = Q - W = Q.

An Isothermal Process
The colored area gives the work done by the gas for the process from X to Y.

A third important thermal process is an isothermal process, one that takes place at constant temperature.

The Adiabatic Process

Last, there is the adiabatic process, one that occurs without the transfer of heat. Since there is no heat transfer, Q equals zero, and the first law indicates that DU = Q - W = -W. Thus, when work is done by a system adiabatically, the internal energy of the system decreases by exactly the amount of the work done.

The Adiabatic Process

Thus, when work is done by a system adiabatically, the internal energy of the system decreases by exactly the amount of the work done. When work is done on a system adiabatically, the internal energy increases correspondingly.

Thermal Processes That Utilize an Ideal Gas

Isothermal Expansion or Compression

(a) The ideal gas in the cylinder is expanding isothermally at temperature T. The force holding the piston in place is reduced slowly, so the expansion occurs quasi-statically. (b) The work done by the gas is given by the colored area.

Isothermal Expansion or Compression

When a system performs work isothermally, the temperature remains constant. In Figure a, for instance, a metal cylinder contains n moles of an ideal gas, and the large mass of hot water maintains the cylinder and gas at a constant Kelvin temperature T. The piston is held in place initially so the volume of the gas is Vi.

Isothermal Expansion or Compression

As the external force applied to the piston is reduced quasi-statically, the gas expands to the final volume Vf . Figure b gives a plot of pressure (P = nRT / V) versus volume for the process. The solid red line in the graph is called an isotherm (meaning constant temperature) because it represents the relation between pressure and volume when the temperature is held constant.

Isothermal Expansion or Compression

The work W done by the gas is not given by W = PDV = P(Vf - Vi) because the pressure is not constant. Nevertheless, the work is equal to the area under the graph. The techniques of integral calculus lead to the following result for W:

V f W nRT ln Vi

Isothermal Expansion or Compression

Where does the energy for this work originate? Since the internal energy of any ideal gas is proportional to the Kelvin temperature (U= (3/2) nRT for a monatomic ideal gas, for example), the internal energy remains constant throughout an isothermal process, and the change in internal energy is zero.

Isothermal Expansion or Compression

The first law of thermodynamics becomes DU = 0 = Q - W. In other words, Q = W, and the energy for the work originates in the hot water.

Adiabatic Expansion or Compression

a) The ideal gas in the cylinder is expanding adiabatically. The force holding the piston in place is reduced slowly, so the expansion occurs quasi-statically. (b) A plot of pressure versus volume yields the adiabatic curve shown in red, which intersects the isotherms (blue) at the initial temperature Ti and the final temperature Tf . The work done by the gas is given by the colored area.

Adiabatic Expansion or Compression

When a system performs work adiabatically, no heat flows into or out of the system. Figure a shows an arrangement in which n moles of an ideal gas do work under adiabatic conditions, expanding quasistatically from an initial volume Vi to a final volume Vf. The arrangement is similar to that in Figure for isothermal expansion.

Adiabatic Expansion or Compression

However, a different amount of work is done here, because the cylinder is now surrounded by insulating material that prevents the flow of heat, so Q = 0. According to the first law of thermodynamics, the change in internal energy is DU = Q - W = -W. Since the internal energy of an ideal monatomic gas is U= (3/2)nRT , it follows that DU = (3/2)nR(Tf Ti) , where Ti and Tf are the initial and final Kelvin temperatures. With this substitution, the relation DU = -W becomes

Adiabatic Expansion or Compression

When an ideal gas expands adiabatically, it does positive work, so W is positive. Therefore, the term Ti - Tf is also positive, and the final temperature of the gas must be less than the initial temperature. The internal energy of the gas is reduced to provide the necessary energy to do the work, and because the internal energy is proportional to the Kelvin temperature, the temperature decreases.

Adiabatic Expansion or Compression

Figure b shows a plot of pressure versus volume for the adiabatic process. The adiabatic curve (red) intersects the isotherms (blue) at the higher initial temperature [Ti = PiVi/(nR)] and the lower final temperature [Tf = PfVf/(nR)]. The colored area under the adiabatic curve represents the work done.

Adiabatic Expansion or Compression

The equation that gives the adiabatic curve (red) between the initial pressure and volume (Pi, Vi) and the final pressure and volume (Pf, Vf) in Figure b can be derived using integral calculus. The result is

where the exponent g is the ratio of the specific heat capacities at constant pressure and constant volume, g = cP/cV.

THE SECOND LAW OF THERMODYNAMICS

THE SECOND LAW OF THERMODYNAMICS: THE HEAT FLOW STATEMENT

Heat flows spontaneously from a substance at a higher temperature to a substance at a lower temperature and does not flow spontaneously in the reverse direction

It is important to realize that the second law of thermodynamics deals with a different aspect of nature than does the first law of thermodynamics. The second law is a statement about the natural tendency of heat to flow from hot to cold, whereas the first law deals with energy conservation and focuses on both heat and work.

A heat engine is any device that uses heat to perform work. It has three essential features:
Heat is supplied to the engine at a relatively high temperature from a place called the hot reservoir. Part of the input heat is used to perform work by the working substance of the engine, which is the material within the engine that actually does the work (e.g., the gasolineair mixture in an automobile engine). 3 The remainder of the input heat is rejected at a . temperature lower than the input temperature to a place called the cold reservoir 1 . 2 .

This schematic representation of a heat engine shows the input heat (magnitude = QH) that originates from the hot reservoir, the work (magnitude = W) that the engine does, and the heat (magnitude = QC ) that the engine rejects to the cold reservoir.

To be highly efficient, a heat engine must produce a relatively large amount of work from as little input heat as possible. Thus, the efficiency e of a heat engine is defined as the ratio of the work W done by the engine to the input heat QH:

If the input heat were converted entirely into work, the engine would have an efficiency of 1.00, since W = QH; such an engine would be 100% efficient.

What is it that allows a heat engine to operate with maximum efficiency? The French engineer Sadi Carnot (17961832) proposed that a heat engine has maximum efficiency when the processes within the engine are reversible. A reversible process is one in which both the system and its environment can be returned to exactly the states they were in before the process occurred.

In a reversible process, both the system and its environment can be returned to their initial states. A process that involves an energy-dissipating mechanism, such as friction, cannot be reversible because the energy wasted due to friction would alter the system or the environment or both.

CARNOT'S PRINCIPLE: AN ALTERNATIVE STATEMENT OF THE SECOND LAW OF THERMODYNAMICS

No irreversible engine operating between two reservoirs at constant temperatures can have a greater efficiency than a reversible engine operating between the same temperatures. Furthermore, all reversible engines operating between the same temperatures have the same efficiency.

Natural Limits on the Efficiency of a Heat Engine

Consider a hypothetical engine that receives 1000 J of heat as input from a hot reservoir and delivers 1000 J of work, rejecting no heat to a cold reservoir whose temperature is above 0 K. Decide whether this engine violates the first or the second law of thermodynamics, or both.

The first law of thermodynamics is an expression of energy conservation. From the point of view of energy conservation, nothing is wrong with an engine that converts 1000 J of heat into 1000 J of work.

Energy has been neither created nor destroyed; it has only been transformed from one form (heat) to another (work).

This engine does, however, violate the second law of thermodynamics. Since all of the input heat is converted into work, the efficiency of the engine is 1, or 100%.

Since we know that TC is above 0 K, it is clear that the ratio TC/TH is greater than zero, so the maximum possible efficiency is less than 1, or less than 100%.

A Heat Pump
An ideal or Carnot heat pump is used to heat a house to a temperature of TH = 294 K (21 C). How much work must be done by the pump to deliver QH = 3350 J of heat into the house when the outdoor temperature TC is (a) 273 K (0 C) and (b) 252 K (-21 C)?

Reasoning
The conservation of energy (QH = W + QC) applies to the heat pump. Thus, the work can be determined from W = QH - QC, provided we can obtain a value for QC, the heat taken by the pump from the outside. To determine QC, we use the fact that the pump is a Carnot heat pump and operates reversibly. Therefore, the relation QC/QH = TC/TH applies. Solving it for QC, we obtain QC = QH(TC/TH). Using this result, we find that

Solution
(a) At an indoor temperature of TH = 294 K and an outdoor temperature of TC = 273 K, the work needed is

(b) This solution is identical to that in part (a), except that it is now cooler outside, so TC = 252 K. The necessary work is , which is more than in part (a).

ENTROPY
To introduce the idea of entropy we recall the relation QC/QH = TC/TH that applies to a Carnot engine. This equation can be rearranged as QC/TC = QH/TH, which focuses attention on the heat Q divided by the Kelvin temperature T. The quantity Q/T is called the change in the entropy DS:

the SI unit for entropy is a joule per kelvin (J/K).

THE SECOND LAW OF THERMODYNAMICS STATED IN TERMS OF ENTROPY

The total entropy of the universe does not change when a reversible process occurs (DSuniverse = 0 ) and increases when an irreversible process occurs (DSuniverse 0 ).

The Entropy of the Universe Increases

This Figure shows 1200 J of heat flowing spontaneously through a copper rod from a hot reservoir at 650 K to a cold reservoir at 350 K. Determine the amount by which this irreversible process changes the entropy of the universe, assuming that no other changes occur.

Reasoning

The hot-to-cold heat flow is irreversible, so the relation DS = (Q/T)R is applied to a hypothetical process whereby the 1200 J of heat is taken reversibly from the hot reservoir and added reversibly to the cold reservoir.

Solution

The total entropy change of the universe is the algebraic sum of the entropy changes for each reservoir:

Order to Disorder

Find the change in entropy that results when a 2.3-kg block of ice melts slowly (reversibly) at 273 K (0 C).

Reasoning & Solution

Since the phase change occurs reversibly at a constant temperature, the change in entropy can be found by using, DS = (Q/T)R, where Q is the heat absorbed by the melting ice. This heat can be determined by using the relation Q = mLf, where m is the mass and Lf = 3.35 105 J/kg is the latent heat of fusion of water.

THE THIRD LAW OF THERMODYNAMICS It is not possible to lower the temperature of any system to absolute zero in a finite number of steps.