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Thermodynamics, science of the relationship between heat, work, temperature, and energy. In broad terms, thermodynamics deals with the transfer of energy from one place to another and from one form to another. The key concept is that heat is a form of energy corresponding to a definite amount of mechanical work. Heat was not formally recognized as a form of energy until about 1798, when Count Rumford (Sir Benjamin Thompson), a British military engineer, noticed that limitless amounts of heat could be generated in the boring of cannon barrels and that the amount of heat generated is proportional to the work done in turning a blunt boring tool. Rumford’s observation of the proportionality between heat generated and work done lies at the foundation of thermodynamics. Another pioneer was the French military engineer Sadi Carnot, who introduced the concept of the heat-engine cycle and the principle of reversibility in 1824. Carnot’s work concerned the limitations on the maximum amount of work that can be obtained from a steam engine operating with a high-temperature heat transfer as its driving force. Later that century, these ideas were developed by Rudolf Clausius, a German mathematician and physicist, into the first and second laws of thermodynamics, respectively.

The most important laws of thermodynamics are:

  The zeroth law of thermodynamics. When two systems are each in thermal equilibrium with a third system, the first two systems are in thermal equilibrium with each other. This property makes it meaningful to use thermometers as the “third system” and to define a temperature scale.  The first law of thermodynamics, or the law of conservation of energy. The change in a system’s internal  energy is equal to the difference between heat added to the system from its surroundings and work done by the system on its surroundings. The second law of thermodynamics. Heat does not flow spontaneously from a colder region to a hotter  region, or, equivalently, heat at a given temperature cannot be converted entirely into work. Consequently, the entropy of a closed system, or heat energy per unit temperature, increases over time toward some maximum value. Thus, all closed systems tend toward an equilibrium state in which entropy is at a maximum and no energy is available to do useful work. This asymmetry between forward and backward processes gives rise to what is known as the “arrow of time.” The third law of thermodynamics. The entropy of a perfect crystal of an element in its most stable form tends to zero as the temperature approaches absolute zero. This allows an absolute scale for entropy to be established that, from a statistical point of view, determines the degree of randomness or disorder in a system.

Although thermodynamics developed rapidly during the 19th century in response to the need to optimize the performance of steam engines, the sweeping generality of the laws of thermodynamics makes them applicable to all physical and biological systems. In particular, the laws of thermodynamics give a complete description of all changes in the energy state of any system and its ability to perform useful work on its surroundings.

This article covers classical thermodynamics, which does not involve the consideration of individual atoms or molecules. Such concerns are the focus of the branch of thermodynamics known as statistical thermodynamics, or statistical mechanics, which expresses macroscopic thermodynamic properties in terms of the behaviour of individual particles and their interactions. It has its roots in the latter part of the 19th century, when atomic and molecular theories of matter began to be generally accepted.

Thermodynamics is the field of physicsthat deals with the relationship between heat and other properties (such as pressure, density, temperature, etc.) in a substance.

Specifically, thermodynamics focuses largely on how a heat transfer is related to various energy changes within a physical system undergoing a thermodynamic process. Such processes usually result in work being done by the system and are guided by the laws of thermodynamics.

BASIC CONCEPTS OF HEAT TRANSFER

Broadly speaking, the heat of a material is understood as a representation of the energy contained within the particles of that material. This is known as the kinetic theory of gases, though the concept applies in varying degrees to solids and liquids as well. The heat from the motion of these particles can transfer into nearby particles, and therefore into other parts of the material or other materials, through a variety of means:

  Thermal Contact is when two substances can affect each other's temperature.  Thermal Equilibrium is when two substances in thermal contact no longer transfer heat.  Thermal Expansion takes place when a substance expands in volume as it gains heat. Thermal  contraction also exists. Conduction is when heat flows through a heated solid.  Convection is when heated particles transfer heat to another substance, such as cooking  something in boiling water.  Radiation is when heat is transferred through electromagnetic waves, such as from the sun. Insulation is when a low-conducting material is used to prevent heat transfer.

THERMODYNAMIC PROCESSES

A system undergoes a thermodynamic process when there is some sort of energetic change within the system, generally associated with changes in pressure, volume, internal energy (i.e. temperature), or any sort of heat transfer.

There are several specific types of thermodynamic processes that have special properties:

  Adiabatic process - a process with no heat transfer into or out of the system.  Isochoric process - a process with no change in volume, in which case the system does no work.  Isobaric process - a process with no change in pressure.  Isothermal process - a process with no change in temperature.

STATES OF MATTER

A state of matter is a description of the type of physical structure that a material substance manifests, with properties that describe how the material holds together (or doesn't). There are five states of matter, though only the first three of them are usually included in the way we think about states of matter:

  gas  liquid  solid   superfluid (such as a Bose-Einstein Condensate)

Many substances can transition between the gas, liquid, and solid phases of matter, while only a few rare substances are known to be able to enter a superfluid state. Plasma is a distinct state of matter, such as lightning

  condensation - gas to liquid  freezing - liquid to solid  melting - solid to liquid  sublimation - solid to gas

vaporization - liquid or solid to gas

HEAT CAPACITY

The heat capacity, C, of an object is the ratio of change in heat (energy change, ΔQ, where the Greek symbol Delta, Δ, denotes a change in the quantity) to change in temperature (ΔT).

C = ΔQ / ΔT

The heat capacity of a substance indicates the ease with which a substance heats up. A good thermal conductor would have a low heat capacity, indicating that a small amount of energy causes a large temperature change. A good thermal insulator would have a large heat capacity, indicating that much energy transfer is needed for a temperature change.

There are various ideal gas equations which relate temperature (T 1 ), pressure (P 1 ), and volume (V 1 ). These values after a thermodynamic change is indicated by (T 2 ), (P 2 ), and (V 2 ). For a given amount of a substance, n (measured in moles), the following relationships hold:

Boyle's Law (T is constant):

P 1 V 1 = P 2 V 2

Charles/Gay-Lussac Law (P is constant):

V 1 /T 1 = V 2 /T 2

Ideal Gas Law:

P 1 V 1 /T 1 = P 2 V 2 /T 2 = nR

R is the ideal gas constant, R = 8.3145 J/mol*K.

For a given amount of matter, therefore, nR is constant, which gives the Ideal Gas Law.

LAWS OF THERMODYNAMICS

  Zeroeth Law of Thermodynamics - Two systems each in thermal equilibrium with a third system  are in thermal equilibrium to each other. First Law of Thermodynamics - The change in the energy of a system is the amount of energy  added to the system minus the energy spent doing work. Second Law of Thermodynamics - It is impossible for a process to have as its sole result the  transfer of heat from a cooler body to a hotter one. Third Law of Thermodynamics - It is impossible to reduce any system to absolute zero in a finite series of operations. This means that a perfectly efficient heat engine cannot be created.

THE SECOND LAW & ENTROPY

The Second Law of Thermodynamics can be restated to talk about entropy, which is a quantitative measurement of the disorder in a system. The change in heat divided by the absolute temperature is the entropy change of the process. Defined this way, the Second Law can be restated as:

In any closed system, the entropy of the system will either remain constant or increase.

By "closed system" it means that every part of the process is included when calculating the entropy of the system.

In some ways, treating thermodynamics as a distinct discipline of physics is misleading. Thermodynamics touches on virtually every field of physics, from astrophysics to biophysics, because they all deal in some fashion with the change of energy in a system. Without the ability of a system to use energy within the system to do work the heart of thermodynamics there would be nothing for physicists to study.

That having been said, there are some fields use thermodynamics in passing as they go about studying other phenomena, while there are a wide range of fields which focus heavily on the thermodynamics situations involved. Here are some of the sub-fields of thermodynamics:

  Cryophysics / Cryogenics / Low Temperature Physics - the study of physical properties in low temperature situations, far below temperatures experienced on even the coldest regions of the Earth. An example of this is the study of superfluids.  Fluid Dynamics / Fluid Mechanics - the study of the physical properties of "fluids,"  specifically defined in this case to be liquids and gases. High Pressure Physics - the study of physics in extremely high pressure systems, generally  related to fluid dynamics. Meteorology / Weather Physics - the physics of the weather, pressure systems in the  atmosphere, etc. Plasma Physics - the study of matter in the plasma state.

Transitions between solid, liquid, and gaseous phases typically involve large amounts of energy compared to the specific heat. If heat w plateaus in the temperature vs time graph. The graph below presumes that the pressure is one standard atmosphere.

 R Nave
 The data for the vaporization phase change presumes that the pressure is one standard atmosphere. R Nave Why is the Potential Energy Negative?
In discussing the energy of the phase changes in water, we found that the potential energy is treated as a negative
quantity. An analogy with a mechanical system with gravitational potential energy and kinetic energy might be
helpful in understanding the logic of a negative energy quantity. You are always free to choose the zero of
potential energy, and it seems logical to choose the zero of potential energy such that a free molecule at rest has
zero energy. A bound particle at rest then has negative potential energy.
Index
Phase
change
concepts
Water phase changes
Go Back
HyperPhysics***** Thermodynamics
R Nave
 It is known that 100 calories of energy must be added to raise the temperature of one gram of water from 0° to 100°C. Part of that ener The sizes of the blocks which represent the kinetic energy of the molecules at 0°C and 100°C provide a visual illustration of the meani temperatures. But the kinetic temperature is inherently the absolute temperature, so that the ratio of the heights of the blocks is 373K/2 R Nave

Some energy details related to heating water

In the process of heating water from from 0 to 100 C, 100 calories of energy must be added. Part of that energy increases the kinetic energy of the molecules, and some adds to the potential energy. To assess the amount added to kinetic energy, the molecular speeds at the two temperatures may be evaluated with the Boltzmann speed distribution. f heating water from from 0 to 100 C, 100 calories of energy must be added. Part of that energy increases the kinetic energy of the molecules, and some adds to the potential energy . To assess the amount added to kinetic energy, the molecular speeds at the two temperatures may be evaluated with the Boltzmann speed distribution . The net gain in kinetic energy is then 16.7 calories/gram when the water is heated from 0 to 100 C. The remainder of the energy goes into weakening the attractive forces between the water molecules. This weakening of the intermolecular forces manifests itself in the reduction of the surface tension of water as it is heated. In the process of vaporization of water, a large amount of energy must be added to overcome the remaining cohesive forces between the molecules and an additional amount of energy goes into PdV work to expand the gas from its very small liquid volume to the volume occupied by the resulting vapor. If the heat of vaporization of water at 100°C is 539 calories, then subtracting the 41 calorie work component suggests that the actual binding energy of the water molecules at 100°C is 539-41=498 calories. Why is the heat of vaporization more at body temperature? An interesting feature of the process o f cooling the human body by evaporation is that the heat extracted by the evaporation of a gram of perspiration from the human skin at body temperature (37°C) is quoted in physiology books as 580 calories/gm " id="pdf-obj-8-15" src="pdf-obj-8-15.jpg">

The net gain in kinetic energy is then 16.7 calories/gram when the water is heated from 0 to 100 C. The remainder of the energy goes into weakening the attractive forces between the water molecules. This weakening of the intermolecular forces manifests itself in the reduction of the surface tension of water as it is heated.

In the process of vaporization of water, a large amount of energy must be added to overcome the remaining cohesive forces between the molecules and an additional amount of energy goes into PdV work to expand the gas from its very small liquid volume to the volume occupied by the resulting vapor. f heating water from from 0 to 100 C, 100 calories of energy must be added. Part of that energy increases the kinetic energy of the molecules, and some adds to the potential energy . To assess the amount added to kinetic energy, the molecular speeds at the two temperatures may be evaluated with the Boltzmann speed distribution . The net gain in kinetic energy is then 16.7 calories/gram when the water is heated from 0 to 100 C. The remainder of the energy goes into weakening the attractive forces between the water molecules. This weakening of the intermolecular forces manifests itself in the reduction of the surface tension of water as it is heated. In the process of vaporization of water, a large amount of energy must be added to overcome the remaining cohesive forces between the molecules and an additional amount of energy goes into PdV work to expand the gas from its very small liquid volume to the volume occupied by the resulting vapor. If the heat of vaporization of water at 100°C is 539 calories, then subtracting the 41 calorie work component suggests that the actual binding energy of the water molecules at 100°C is 539-41=498 calories. Why is the heat of vaporization more at body temperature? An interesting feature of the process o f cooling the human body by evaporation is that the heat extracted by the evaporation of a gram of perspiration from the human skin at body temperature (37°C) is quoted in physiology books as 580 calories/gm " id="pdf-obj-8-25" src="pdf-obj-8-25.jpg">

If the heat of vaporization of water at 100°C is 539 calories, then subtracting the 41 calorie work component suggests that the actual binding energy of the water molecules at 100°C is 539-41=498 calories.

Why is the heat of vaporization more at body temperature?

An interesting feature of the process of cooling the human body by evaporation is that the heat extracted by the evaporation

of a gram of perspiration from the human skin at body temperature (37°C) is quoted in physiology books as 580 calories/gm

rather than the nominal 540 calories/gm at the normal boiling point. The question is, why is it larger at body temperature?

The main part of the answer is that the binding energy of the water molecules is greater at that lower temperature, and it therefore takes more energy to break them apart into the gaseous state. The change in the heat of vaporization can be roughly calculated using what we know from the specific heat of water, 1 calorie/gm °C. It takes 37 calories to heat a gram of water from 0°C to 37°C, but the change in the kinetic energy is much less than that: specific heat of water, 1 calorie/gm °C. It takes 37 calories to heat a gram of water from 0°C to 37°C, but the change in the kinetic energy is much less than that: It was shown above that the kinetic energy of the water molecules only increases by 61.7 - 45 = 16.7 calories/gm when the water is heated from zero to 100°C but we know it takes 100 calories to do that heating. Therefore the contribution to weakening the water bonds is 83.3 calories/gm. Using the result for water at 37°C it is evident that 52.4 calories of additional energy must be supplied at 37°C to vaporize the water. There is one additional element in modeling the heat of vaporization at body temperature - the PdV work required to expand the water into its gaseous form is slightly less at 37°C. By analogy with the work calculation above, that work is found to be 34.2 calories/gm, 6.8 calories/gm less than at 100°C. This model then suggests a heat of vaporization at 37°C: Body temperature heat of vaporization = 539 cal/gm + 52.4 cal/gm - 6.8 cal/gm = 585 cal/gm. So this simple model agrees fairly well with the quoted 580 cal/gm. " id="pdf-obj-9-9" src="pdf-obj-9-9.jpg">

It was shown above that the kinetic energy of the water molecules only increases by 61.7 - 45 = 16.7 calories/gm when the water is heated from zero to 100°C but we know it takes 100 calories to do that heating. Therefore the contribution to weakening the water bonds is 83.3 calories/gm. Using the result for water at 37°C it is evident that 52.4 calories of additional energy must be supplied at 37°C to vaporize the water.

There is one additional element in modeling the heat of vaporization at body temperature - the PdV work required to expand the water into its gaseous form is slightly less at 37°C. By analogy with the work calculation above, that work is found to be 34.2 calories/gm, 6.8 calories/gm less than at 100°C.

This model then suggests a heat of vaporization at 37°C:

Body temperature heat of vaporization = 539 cal/gm + 52.4 cal/gm - 6.8 cal/gm = 585 cal/gm.

So this simple model agrees fairly well with the quoted 580 cal/gm.

# Changes of Phase (or State) # The term 'change of phase' means the same thing as the term 'change of state'.

## There are four states, or phases, of matter: Solid
Liquid
Gas
Plasma

# When a substance changes from one state, or phase,

of matter to another we say that it has undergone a change of state, or we say that it has undergone a change of phase. For example, ice melts and becomes water; water evaporates and becomes water vapor.

These changes of phase always occur with a change of heat. Heat, which is energy, either comes into the material during a change of phase or heat comes out of the material during this change. However, although the heat content of the material changes, the temperature does not. # Here are the five changes of phase. They are diagrammed

in the opening animation and listed below.

 Description of Phase Change Term for Phase Change Solid to liquid Melting Liquid to solid Freezing Liquid to gas Vaporization, which includes boiling and evaporation Gas to liquid Condensation Solid to gas Sublimation

Heat Movement During Phase Change

Heat goes into the solid as it melts.

Temperature Change During Phase Change

None

Heat leaves the liquid as it freezes.

Heat goes into the liquid as it vaporizes.

Heat leaves the gas as it condenses.

None

None

None

Heat goes into the solid as it sublimates.

None # So, how could there be a change in heat during a state change without a change in

temperature? During a change in state the heat energy is used to change

the bonding between the molecules. In the case of melting, added energy is used to break the bonds between the molecules. In the case of freezing, energy is subtracted as the molecules bond to one another. These energy exchanges are not changes in kinetic energy. They are changes in bonding energy between the molecules.

If heat is coming into a substance during a phase change, then this energy is used to break the bonds between the molecules of the substance. The example we will use here is ice melting into water. Immediately after the molecular bonds in the ice are broken the molecules are moving (vibrating) at the same average speed as before, so their average kinetic energy remains the same, and, thus, their Kelvin temperature remains the same. # Below is a picture of solid ice melting into

liquid water. The molecule of ice and the molecule of water (the black balls) are

moving with the same rate of vibration in this diagram. This is meant to show that they have the same average speed and thus the same average kinetic energy (since they have the same mass) and thus the same Kelvin temperature. The motions are, though, greatly exaggerated. Actually, the motions of the molecules should be considered tiny vibrations. At the moment of melting the average kinetic energy o molecules does not change.

The heat is used to break the bonds between the ice molecules as they turn into a liquid phase.

Since the average kinetic energy of the molecules doe change at the moment of melting, the temperature of t molecules does not change.

Since both the ice and the water molecules have the sa average kinetic energy at the time of melting, the temperatures of both are the same.

Click this button to see the computer code for this animation.

# In the ice the molecules are strongly bonded to one another, thus forming a rigid solid.When heat is

added to the ice these bonds are broken and the ice melts. The molecules afterward bond to one another with less strength and a different geometry, and water is formed.

Now, before the melting, the molecules were actually moving when in the solid state. They were vibrating back and forth. They had an average kinetic energy. So they had a Kelvin temperature proportional to this average kinetic energy.

After the melting the water molecules are still vibrating. And they have the same average kinetic energy as they had before the melting. So, the water is at the same temperature at the moment after the melting that the ice was at the moment before the melting.

# Heat came into the situation, but it was not used to change the kinetic energy of the

molecules. It was used to change the bonding between the molecules. Breaking the bonds between the molecules of the ice requires energy, and this energy is the added heat.

In a similar way heat enters a liquid to change the molecular bonding when the liquid boils or evaporates into a gas, and heat enters a solid to change the molecular bonding when it sublimates into a gas.

In an inverse way heat leaves a gas to change the molecular bonding when the gas condenses into a liquid, and heat leaves a liquid to change the molecular bonding when it freezes into a solid.

# In none of these changes of state is the heat (energy) that is input or output used to change

the speed of the molecules. The average speed of the molecules is the same before and after a phase change, and so is the average kinetic energy.

Heat (energy) is transferred into the ice. The heat is used to break the bonds between molecules, not to increase the average kinetic energy of the molecules. # Introduction

Since the bonds among the ice molecules have been broken, water is formed. The water molecules, at this moment, have the same average kinetic energy as they did when they were ice. Since the ice and water molecules both have the same average kinetic energy, they are at the same Kelvin temperature.

# Systems and surroundings

### ecosystem) is called the system, while everything that's not included in the system we’ve defined is called the surroundings. # The First Law of Thermodynamics

### The first law of thermodynamics thinks big: it deals with the total amount of energy in the universe, and in particular, it states that this total amount does not change. Put another way, the First Law of Thermodynamics states that energy cannot be created or destroyed. It can only change form or be transferred from one object to another. ### Image of sun (light energy) being converted to sugars in a leaf (chemical energy).

Image credit: OpenStax Biology. Credit “Ice cream," modification of work by D. Sharon Pruitt; credit "Kids on bikes," modification of work by Michelle Riggen-Ransom, and credit “Leaf”: modification of work by Cory Zanker.

# Entropy in biological systems

### sources is simply transformed into heat. Some of the heat keeps your body warm, but much of it dissipates into the surrounding environment. 