TEMPERATURE AND HEAT

CONCEPT

Temperature, heat, and related concepts belong to the world of physics rather than chemistry; yet it would be impossible for the chemist to work without an understanding of these properties. Thermometers, of course, measure temperature according to one or both of two well-known scales based on the freezing and boiling points of water, though scientists prefer a scale based on the virtual freezing point of all matter. Also related to temperature are specific heat capacity, or the amount of energy required to change the temperature of a substance, and also calorimetry, the measurement of changes in heat as a result of physical or chemical changes. Although these concepts do not originate from chemistry but from physics, they are no less useful to the chemist.

HOW IT WORKS

Energy

The area of physics known as thermodynamics, discussed briefly below in terms of thermodynamics laws, is the study of the relationships between heat, work, and energy. Work is defined as the exertion of force over a given distance to displace or move an object, and energy is the ability to accomplish work. Energy appears in numerous manifestations, including thermal energy, or the energy associated with heat.
Another type of energy—one of particular interest to chemists—is chemical energy, related to the forces that attract atoms to one another in chemical bonds. Hydrogen and oxygen atoms in water, for instance, are joined by chemical bonding, and when those bonds are broken, the forces joining the atoms are released in the form of chemical energy. Another example of chemical energy release is combustion, whereby chemical bonds in fuel, as well as in oxygen molecules, are broken and new chemical bonds are formed. The total energy in the newly formed chemical bonds is less than the energy of the original bonds, but the energy that makes up the difference is not lost; it has simply been released.
Energy, in fact, is never lost: a fundamental law of the universe is the conservation of energy, which states that in a system isolated from all other outside factors, the total amount of energy remains the same, though transformations of energy from one form to another take place. When a fire burns, then, some chemical energy is turned into thermal energy. Similar transformations occur between these and other manifestations of energy, including electrical and magnetic (sometimes these two are combined as electromagnetic energy), sound, and nuclear energy. If a chemical reaction makes a noise, for instance, some of the energy in the substances being mixed has been dissipated to make that sound. The overall energy that existed before the reaction will be the same as before; however, the energy will not necessarily be in the same place as before.
Note that chemical and other forms of energy are described as “manifestations,” rather than “types,” of energy. In fact, all of these can be described in terms of two basic types of energy: kinetic energy, or the energy associated with movement, and potential energy, or the energy associated with position. The two are inversely related: thus, if a spring is pulled back to its maximum point of tension, its potential energy is also at a maximum, while its kinetic energy is zero. Once it is released and begins springing through the air to return to the position it maintained before it was stretched, it begins gaining kinetic energy and losing potential energy.


Heat

Thermal energy is actually a form of kinetic energy generated by the movement of particles at the atomic or molecular level: the greater the movement of these particles, the greater the thermal energy. When people use the word “heat” in ordinary language, what they are really referring to is “the quality of hotness”—that is, the thermal energy internal to a system. In scientific terms, however, heat is internal thermal energy that flows from one body of matter to another— or, more specifically, from a system at a higher temperature to one at a lower temperature.
Two systems at the same temperature are said to be in a state of thermal equilibrium. When this state exists, there is no exchange of heat. Though in everyday terms people speak of “heat” as an expression of relative warmth or coldness, in scientific terms, heat exists only in transfer between two systems. Furthermore, there can never be a transfer of “cold”; although coldness is a recognizable sensory experience in human life, in scientific terms, cold is simply the absence of heat.
If you grasp a snowball in your hand, the hand of course gets cold. The mind perceives this as a transfer of cold from the snowball, but in fact exactly the opposite has happened: heat has moved from your hand to the snow, and if enough heat enters the snowball, it will melt. At the same time, the departure of heat from your hand results in a loss of internal energy near the surface of the hand, experienced as a sensation of coldness.

Understanding Temperature

Just as heat does not mean the same thing in scientific terms as it does in ordinary language, so “temperature” requires a definition that sets it apart from its everyday meaning. Temperature may be defined as a measure of the average internal energy in a system. Two systems in a state of thermal equilibrium have the same temperature; on the other hand, differences in temperature determine the direction of internal energy flow between two systems where heat is being transferred.
This can be illustrated through an experience familiar to everyone: having one’s temperature taken with a thermometer. If one has a fever, the mouth will be warmer than the thermometer, and therefore heat will be transferred to the thermometer from the mouth. The thermometer, discussed in more depth later in this essay, measures the temperature difference between itself and any object with which it is in contact.

Temperature and Thermodynamics

One might pour a kettle of boiling water into a cold bathtub to heat it up; or one might put an ice cube in a hot cup of coffee “to cool it down.” In everyday experience, these seem like two very different events, but from the standpoint of thermodynamics, they are exactly the same. In both cases, a body of high temperature is placed in contact with a body of low temperature, and in both cases, heat passes from the high-temperature body to the low-temperature body.
The boiling water warms the tub of cool water, and due to the high ratio of cool water to boiling water in the bathtub, the boiling water
Because of water's high specific heat capacity, cities located next to large bodies of water tend to stay warmer in the winter and cooler in the summer. During the early summer months, for instance, Chicago's lakefront stays cooler than areas further inland. This is because the lake is cooled from the winter's cold temperatures and snow runoff.
Because of water’s high specific heat capacity, cities located next to large bodies of water tend to stay warmer in the winter and cooler in the summer. During the early summer months, for instance, Chicago’s lakefront stays cooler than areas further inland. This is because the lake is cooled from the winter’s cold temperatures and snow runoff.
expends all its energy raising the temperature in the bathtub as a whole. The greater the ratio of very hot water to cool water, of course, the warmer the bathtub will be in the end. But even after the bath water is heated, it will continue to lose heat, assuming the air in the room is not warmer than the water in the tub—a safe assumption. If the water in the tub is warmer than the air, it will immediately begin transferring thermal energy to the lower-temperature air until their temperatures are equalized.
As for the coffee and the ice cube, what happens is opposite to the explanation ordinarily given. The ice does not “cool down” the coffee: the coffee warms up, and presumably melts, the ice. However, it expends at least some of its thermal energy in doing so, and, as a result, the coffee becomes cooler than it was.

The Laws of Thermodynamics

These situations illustrate the second of the three laws of thermodynamics. Not only do these laws help to clarify the relationship between heat, temperature, and energy, but they also set limits on what can be accomplished in the world. Hence British writer and scientist C. P. Snow (1905-1980) once described the thermodynamics laws as a set of rules governing an impossible game.
The first law of thermodynamics is essentially the same as the conservation of energy: because the amount of energy in a system remains constant, it is impossible to perform work that results in an energy output greater than the energy input. It could be said that the conservation of energy shows that “the glass is half full”: energy is never lost. By contrast, the first law of thermodynamics shows that “the glass is half empty”: no system can ever produce more energy than was put into it. Snow therefore summed up the first law as stating that the game is impossible to win.
The second law of thermodynamics begins from the fact that the natural flow of heat is always from an area of higher temperature to an area of lower temperature—just as was shown in the bathtub and coffee cup examples above. Consequently, it is impossible for any system to take heat from a source and perform an equivalent amount of work: some of the heat will always be lost. In other words, no system can ever be perfectly efficient: there will always be a degree of breakdown, evidence of a natural tendency called entropy.
Snow summed up the second law of thermodynamics, sometimes called “the law of entropy,” thus: not only is it impossible to win, it is impossible to break even. In effect, the second law compounds the “bad news” delivered by the first with some even worse news. Though it is true that energy is never lost, the energy available for work output will never be as great as the energy put into a system.
The third law of thermodynamics states that at the temperature of absolute zero—a phenomenon discussed later in this essay—entropy also approaches zero. This might seem to counteract the second law, but in fact the third states in effect that absolute zero is impossible to reach. The French physicist and engineer Sadi Carnot (1796-1832) had shown that a perfectly efficient engine is one whose lowest temperature was absolute zero; but the second law of thermodynamics shows that a perfectly efficient engine (or any other perfect system) cannot exist. Hence, as Snow observed, not only is it impossible to win or break even; it is impossible to get out of the game.

REAL-LIFE APPLICATIONS

Evolution of the Thermometer

A thermometer is a device that gauges temperature by measuring a temperature-dependent property, such as the expansion of a liquid in a sealed tube. The Greco-Roman physician Galen (c. 129-c. 199) was among the first thinkers to envision a scale for measuring temperature, but development of a practical temperature-measuring device—the thermoscope—did not occur until the sixteenth century.
The great physicist Galileo Galilei (15641642) may have invented the thermoscope; certainly he constructed one. Galileo’s thermoscope consisted of a long glass tube planted in a container of liquid. Prior to inserting the tube into the liquid—which was usually colored water, though Galileo’s thermoscope used wine—as much air as possible was removed from the tube. This created a vacuum (an area devoid ofmatter, including air), and as a result of pressure differences between the liquid and the interior of the thermoscope tube, some of the liquid went into the tube.
But the liquid was not the thermometric medium—that is, the substance whose temperature-dependent property changes were measured by the thermoscope. (Mercury, for instance, is the thermometric medium in many thermometers today; however, due to the toxic quality of mercury, an effort is underway to remove mercury thermometers from U.S. schools.) Instead, the air was the medium whose changes the thermoscope measured: when it was warm, the air expanded, pushing down on the liquid; and when the air cooled, it contracted, allowing the liquid to rise.

Early Thermometers: The Search For a Temperature Scale

The first true thermometer, built by Ferdinand II, Grand Duke of Tuscany (16101670) in 1641, used alcohol sealed in glass. The latter was marked with a temperature scale containing 50 units, but did not designate a value for zero. In 1664, English physicist Robert Hooke (1635-1703) created a thermometer with a scale divided into units equal to about 1/500 of the volume of the thermometric medium. For the zero point, Hooke chose the temperature at which water freezes, thus establishing a standard still used today in the Fahrenheit and Celsius scales.
Olaus Roemer (1644-1710), a Danish astronomer, introduced another important standard. Roemer’s thermometer, built in 1702, was based not on one but two fixed points, which he designated as the temperature of snow or crushed ice on the one hand, and the boiling point of water on the other. As with Hooke’s use of the freezing point, Roemer’s idea of designating the freezing and boiling points of water as the two parameters for temperature measurements has remained in use ever since.

Temperature Scales

The Fahrenheit Scale

Not only did he develop the Fahrenheit scale, oldest of the temperature scales still used in Western nations today, but in 1714, German physicist Daniel Fahrenheit (1686-1736) built the first thermometer to contain mercury as a thermo-metric medium. Alcohol has a low boiling point, whereas mercury remains fluid at a wide range of temperatures. In addition, it expands and contracts at a very constant rate, and tends not to stick to glass. Furthermore, its silvery color makes a mercury thermometer easy to read.
Fahrenheit also conceived the idea of using “degrees” to measure temperature. It is no mistake that the same word refers to portions of a circle, or that exactly 180 degrees—half the number of degrees in a circle—separate the freezing and boiling points for water on Fahrenheit’s thermometer. Ancient astronomers first divided a circle into 360 degrees, as a close approximation of the ratio between days and years, because 360 has a large quantity of divisors. So, too, does 180—a total of 16 whole-number divisors other than 1 and itself.
Though today it might seem obvious that 0 should denote the freezing point of water, and 180 its boiling point, such an idea was far from obvious in the early eighteenth century. Fahrenheit considered a 0-to-180 scale, but also a 180-to-360 one, yet in the end he chose neither—or rather, he chose not to equate the freezing point of water with zero on his scale. For zero, he chose the coldest possible temperature he could create in his laboratory, using what he described as “a mixture of sal ammoniac or sea salt, ice, and water.” Salt lowers the melting point of ice (which is why it is used in the northern United States to melt snow and ice from the streets on cold winter days), and thus the mixture of salt and ice produced an extremely cold liquid water whose temperature he equated to zero.
On the Fahrenheit scale, the ordinary freezing point of water is 32°, and the boiling point exactly 180° above it, at 212°. Just a few years after Fahrenheit introduced his scale, in 1730, a French naturalist and physicist named Rene Antoine Ferchault de Reaumur (1683-1757) presented a scale for which 0° represented the freezing point of water and 80° the boiling point. Although the Reaumur scale never caught on to the same extent as Fahrenheit’s, it did include one valuable addition: the specification that temperature values be determined at standard sea-level atmospheric pressure.

The Celsius Scale

With its 32° freezing point and its 212° boiling point, the Fahrenheit system lacks the neat orderliness of a decimal or base-10 scale. Thus when France adopted the metric system in 1799, it chose as its temperature scale not the Fahrenheit but the Celsius scale. The latter was created in 1742 by Swedish astronomer Anders Celsius (1701-1744).
Like Fahrenheit, Celsius chose the freezing and boiling points of water as his two reference points, but he determined to set them 100, rather than 180, degrees apart. The Celsius scale is sometimes called the centigrade scale, because it is divided into 100 degrees, cent being a Latin root meaning “hundred.” Interestingly, Celsius planned to equate 0° with the boiling point, and 100° with the freezing point; only in 1750 did fellow Swedish physicist Martin Stromer change the orientation of the Celsius scale. In accordance with the innovation offered by Reaumur, Celsius’s scale was based not simply on the boiling and freezing points of water, but specifically on those points at normal sea-level atmospheric pressure.
In SI, a scientific system of measurement that incorporates units from the metric system along with additional standards used only by scientists, the Celsius scale has been redefined in terms of the triple point of water. (Triple point is the temperature and pressure at which a substance is at once a solid, liquid, and vapor.) According to the SI definition, the triple point of water—which occurs at a pressure considerably below normal atmospheric pressure—is exactly 0.01°C.

The Kelvin Scale

French physicist and chemist J. A. C. Charles (1746-1823), who is credited with the gas law that bears his name (see below), discovered that at 0°C, the volume of gas at constant pressure drops by 1/273 for every Celsius degree drop in temperature. This suggested that the gas would simply disappear if cooled to -273°C, which of course made no sense.
The man who solved the quandary raised by Charles’s discovery was William Thompson, Lord Kelvin (1824-1907), who, in 1848, put forward the suggestion that it was the motion of molecules, and not volume, that would become zero at -273°C. He went on to establish what came to be known as the Kelvin scale. Sometimes known as the absolute temperature scale, the Kelvin scale is based not on the freezing point of water, but on absolute zero—the temperature at which molecular motion comes to a virtual stop. This is -273.15°C (-459.67°F), which, in the Kelvin scale, is designated as 0K. (Kelvin measures do not use the term or symbol for “degree.”)
Though scientists normally use metric units, they prefer the Kelvin scale to Celsius because the absolute temperature scale is directly related to average molecular translational energy, based on the relative motion of molecules. Thus if the Kelvin temperature of an object is doubled, this means its average molecular translational energy has doubled as well. The same cannot be said if the temperature were doubled from, say, 10°C to 20°C, or from 40°C to 80°F, since neither the Celsius nor the Fahrenheit scale is based on absolute zero.

Conversions between scales

The Kelvin scale is closely related to the Celsius scale, in that a difference of one degree measures the same amount of temperature in both. Therefore, Celsius temperatures can be converted to Kelvins by adding 273.15. Conversion between Celsius and Fahrenheit figures, on the other hand, is a bit trickier.
To convert a temperature from Celsius to Fahrenheit, multiply by 9/5 and add 32. It is important to perform the steps in that order, because reversing them will produce a wrong figure. Thus, 100°C multiplied by 9/5 or 1.8 equals 180, which, when added to 32 equals 212°F. Obviously, this is correct, since 100°C and 212°F each represent the boiling point of water. But if one adds 32 to 100°, then multiplies it by 9/5, the result is 237.6°F—an incorrect answer.
For converting Fahrenheit temperatures to Celsius, there are also two steps involving multiplication and subtraction, but the order is reversed. Here, the subtraction step is performed before the multiplication step: thus 32 is subtracted from the Fahrenheit temperature, then the result is multiplied by 5/9. Beginning with 212°F, when 32 is subtracted, this equals 180. Multiplied by 5/9, the result is 100°C—the correct answer.
One reason the conversion formulae use simple fractions instead of decimal fractions (what most people simply call “decimals”) is that 5/9 is a repeating decimal fraction (0.55555…. )
Furthermore, the symmetry of5/9 and 9/5 makes memorization easy. One way to remember the formula is that Fahrenheit is multiplied by a fraction—since 5/9 is a real fraction, whereas 9/5 is actually a mixed number, or a whole number plus a fraction.

Modern Thermometers

Mercury Thermometers

For a thermometer, it is important that the glass tube be kept sealed; changes in atmospheric pressure contribute to inaccurate readings, because they influence the movement of the thermometric medium. It is also important to have a reliable thermometric medium, and, for this reason, water—so useful in many other contexts—was quickly discarded as an option.
Water has a number of unusual properties: it does not expand uniformly with a rise in temperature, or contract uniformly with a lowered temperature. Rather, it reaches its maximum density at 39.2°F (4°C), and is less dense both above and below that temperature. Therefore alcohol, which responds in a much more uniform fashion to changes in temperature, soon took the place of water, and is still used in many thermometers today. But for the reasons mentioned earlier, mercury is generally considered preferable to alcohol as a thermometric medium.
In a typical mercury thermometer, mercury is placed in a long, narrow sealed tube called a capillary. The capillary is inscribed with figures for a calibrated scale, usually in such a way as to allow easy conversions between Fahrenheit and Celsius. A thermometer is calibrated by measuring the difference in height between mercury at the freezing point of water, and mercury at the boiling point of water. The interval between these two points is then divided into equal increments—180, as we have seen, for the Fahrenheit scale, and 100 for the Celsius scale.


Volume Gas Thermometers

Whereas most liquids and solids expand at an irregular rate, gases tend to follow a fairly regular pattern of expansion in response to increases in temperature. The predictable behavior of gases in these situations has led to the development of the volume gas thermometer, a highly reliable instrument against which other thermometers—including those containing mercury—are often calibrated.
In a volume gas thermometer, an empty container is attached to a glass tube containing mercury. As gas is released into the empty container; this causes the column of mercury to move upward. The difference between the earlier position of the mercury and its position after the introduction of the gas shows the difference between normal atmospheric pressure and the pressure of the gas in the container. It is then possible to use the changes in the volume of the gas as a measure of temperature.

Electric Thermometers

All matter displays a certain resistance to electric current, a resistance that changes with temperature; because of this, it is possible to obtain temperature measurements using an electric thermometer. A resistance thermometer is equipped with a fine wire wrapped around an insulator: when a change in temperature occurs, the resistance in the wire changes as well. This allows much quicker temperature readings than those offered by a thermometer containing a traditional thermometric medium.
Resistance thermometers are highly reliable, but expensive, and primarily are used for very precise measurements. More practical for everyday use is a thermistor, which also uses the principle of electric resistance, but is much simpler and less expensive. Thermistors are used for providing measurements of the internal temperature of food, for instance, and for measuring human body temperature.
Another electric temperature-measurement device is a thermocouple. When wires of two different materials are connected, this creates a small level of voltage that varies as a function of temperature. A typical thermocouple uses two junctions: a reference junction, kept at some constant temperature, and a measurement junction. The measurement junction is applied to the item whose temperature is to be measured, and any temperature difference between it and the reference junction registers as a voltage change, measured with a meter connected to the system.

Other Types of Thermometer

A pyrometer also uses electromagnetic properties, but of a very different kind. Rather than responding to changes in current or voltage, the pyrometer is gauged to respond to visible and infrared radiation. As with the thermocouple, a pyrometer has both a reference element and a measurement element, which compares light readings between the reference filament and the object whose temperature is being measured.
Still other thermometers, such as those in an oven that register the oven’s internal temperature, are based on the expansion of metals with heat. In fact, there are a wide variety of thermometers, each suited to a specific purpose. A pyrometer, for instance, is good for measuring the temperature of a object with which the thermometer itself is not in physical contact.

Measuring Heat

The measurement of temperature by degrees in the Fahrenheit or Celsius scales is a part of daily life, but measurements of heat are not as familiar to the average person. Because heat is a form of energy, and energy is the ability to perform work, heat is therefore measured by the same units as work. The principal SI unit of work or energy is the joule (J). A joule is equal to 1 newton-meter (N • m)—in other words, the amount of energy required to accelerate a mass of 1 kilogram at the rate of 1 meter per second squared across a distance of 1 meter.
The joule’s equivalent in the English system is the foot-pound: 1 foot-pound is equal to 1.356 J, and 1 joule is equal to 0.7376 ft • lbs. In the British system, Btu, or British thermal unit, is another measure of energy, though it is primarily used for machines. Due to the cumbersome nature of the English system, contrasted with the convenience of the decimal units in the SI system, these English units of measure are not used by chemists or other scientists for heat measurement.

Specific Heat Capacity

Specific heat capacity (sometimes called specific heat) is the amount of heat that must be added to, or removed from, a unit of mass for a given substance to change its temperature by 1°C. Typically, specific heat capacity is measured in units of J/g • °C (joules per gram-degree Celsius).
The specific heat capacity of water is measured by the calorie, which, along with the joule, is an important SI measure of heat. Often another unit, the kilocalorie—which, as its name suggests—is 1,000 calories—is used. This is one of the few confusing aspects of SI, which is much simpler than the English system. The dietary Calorie (capital C) with which most people are familiar is not the same as a calorie (lowercase c)—rather, a dietary Calorie is the same as a kilo-calorie.

Comparing specific heat capacities

The higher the specific heat capacity, the more resistant the substance is to changes in temperature. Many metals, in fact, have a low specific heat capacity, making them easy to heat up and cool down. This contributes to the tendency of metals to expand when heated, and thus affects their malleability. On the other hand, water has a high specific heat capacity, as discussed below; indeed, if it did not, life on Earth would hardly be possible.
One of the many unique properties of water is its very high specific heat capacity, which is easily derived from the value of a kilocalorie: it is 4.184, the same number of joules required to equal a calorie. Few substances even come close to this figure. At the low end of the spectrum are lead, gold, and mercury, with specific heat capacities of 0.13, 0.13, and 0.14 respectively. Aluminum has a specific heat capacity of 0.89, and ethyl alcohol of 2.43. The value for concrete, one of the highest for any substance other than water, is 2.9.
As high as the specific heat capacity of concrete is, that of water is more than 40% higher. On the other hand, water in its vapor state (steam) has a much lower specific heat capacity—2.01. The same is true for solid water, or ice, with a specific heat capacity of2.03. Nonetheless, water in its most familiar form has an astoundingly high specific heat capacity, and this has several effects in the real world.

Effects of water’s high specific heat capacity

For instance, water is much slower to freeze in the winter than most substances. Furthermore, due to other unusual aspects of water—primarily the fact that it actually becomes less dense as a solid—the top of a lake or other body of water freezes first. Because ice is a poor medium for the conduction of heat (a consequence of its specific heat capacity), the ice at the top forms a layer that protects the still-liquid water below it from losing heat. As a result, the water below the ice layer does not freeze, and the animal and plant life in the lake is preserved.
Conversely, when the weather is hot, water is slow to experience a rise in temperature. For this reason, a lake or swimming pool makes a good place to cool off on a sizzling summer day. Given the high specific heat capacity of water, combined with the fact that much of Earth’s surface is composed of water, the planet is far less susceptible than other bodies in the Solar System to variations in temperature.
The same is true of another significant natural feature, one made mostly of water: the human body. A healthy human temperature is 98.6°F (37°C), and, even in cases of extremely high fever, an adult’s temperature rarely climbs by more than 5°F (2.7°C). The specific heat capacity of the human body, though it is of course lower than that of water itself (since it is not entirely made of water), is nonetheless quite high: 3.47.

Calorimetry

The measurement of heat gain or loss as a result of physical or chemical change is called calorime-try (pronounced kal-or-IM-uh-tree). Like the word “calorie,” the term is derived from a Latin root word meaning “heat.” The foundations of calorimetry go back to the mid-nineteenth century, but the field owes much to the work of scientists about 75 years prior to that time.
In 1780, French chemist Antoine Lavoisier (1743-1794) and French astronomer and mathematician Pierre Simon Laplace (1749-1827) had used a rudimentary ice calorimeter for measuring heat in the formations of compounds. Around the same time, Scottish chemist Joseph Black (1728-1799) became the first scientist to make a clear distinction between heat and temperature.
By the mid-1800s, a number of thinkers had come to the realization that—contrary to prevailing theories of the day—heat was a form of energy, not a type of material substance. (The belief that heat was a material substance, called “phlogiston,” and that phlogiston was the part of a substance that burned in combustion, had originated in the seventeenth century. Lavoisier was the first scientist to successfully challenge the phlogiston theory.) Among these were American-British physicist Benjamin Thompson, Count Rumford (1753-1814) and English chemist James Joule (1818-1889)—for whom, of course, the joule is named.
Calorimetry as a scientific field of study actually had its beginnings with the work of French chemist Pierre-Eugene Marcelin Berthelot (1827-1907). During the mid-1860s, Berthelot became intrigued with the idea of measuring heat, and, by 1880, he had constructed the first real calorimeter.

Calorimeters

Essential to calorimetry is the calorimeter, which can be any device for accurately measuring the temperature of a substance before and after a change occurs. A calorimeter can be as simple as a styrofoam cup. Its quality as an insulator, which makes styrofoam ideal both for holding in the warmth of coffee and protecting the human hand from scalding, also makes styrofoam an excellent material for calorimetric testing. With a styrofoam calorimeter, the temperature of the substance inside the cup is measured, a reaction is allowed to take place, and afterward, the temperature is measured a second time.
The most common type of calorimeter used is the bomb calorimeter, designed to measure the heat of combustion. Typically, a bomb calorimeter consists of a large container filled with water, into which is placed a smaller container, the combustion crucible. The crucible is made of metal, with thick walls into which is cut an opening to allow the introduction of oxygen. In addition, the combustion crucible is designed to be connected to a source of electricity.
In conducting a calorimetric test using a bomb calorimeter, the substance or object to be studied is placed inside the combustion crucible and ignited. The resulting reaction usually occurs so quickly that it resembles the explosion of a bomb—hence the name “bomb calorimeter” Once the “bomb” goes off, the resulting transfer of heat creates a temperature change in the water, which can be readily gauged with a thermometer.
To study heat changes at temperatures higher than the boiling point of water, physicists use substances with higher boiling points. For experiments involving extremely large temperature ranges, an aneroid (without liquid) calorimeter may be used. In this case, the lining of the combustion crucible must be of a metal, such as copper, with a high coefficient or factor of thermal conductivity—that is, the ability to conduct heat from molecule to molecule.

Temperature in Chemistry

The Gas Laws

A collection of statements regarding the behavior of gases, the gas laws are so important to chemistry that a separate essay is devoted to them elsewhere. Several of the gas laws relate temperature to pressure and volume for gases. Indeed, gases respond to changes in temperature with dramatic changes in volume; hence the term “volume,” when used in reference to a gas, is meaningless unless pressure and temperature are specified as well.
Among the gas laws, Boyle’s law holds that in conditions of constant temperature, an inverse relationship exists between the volume and pressure of a gas: the greater the pressure, the less the volume, and vice versa. Even more relevant to the subject of thermal expansion is Charles’s law, which states that when pressure is kept constant, there is a direct relationship between volume and absolute temperature.

Chemical equilibrium and changes in temperature

Just as two systems that exchange no heat are said to be in a state of thermal equilibrium, chemical equilibrium describes a dynamic state in which the concentration of reactants and products remains constant. Though the concentrations of reactants and products do not change, note that chemical equilibrium is a dynamic state—in other words, there is still considerable molecular activity, but no net change.
Calculations involving chemical equilibrium make use of a figure called the equilibrium constant (K). According to Le Chatelier’s principle, named after French chemist Henri Le Chatelier (1850-1936), whenever a stress or change is imposed on a chemical system in equilibrium, the system will adjust the amounts of the various substances in such a way as to reduce the impact of that stress. An example of a stress is a change in temperature, which changes the equilibrium equation by shifting K (itself dependant on temperature).
Using Le Chatelier’s law, it is possible to determine whether K will change in the direction of the forward or reverse reaction. In an exothermic reaction (a reaction that produces heat), K will shift to the left, or in the direction of the forward reaction. On the other hand, in an endothermic reaction (a reaction that absorbs heat), K will shift to the right, or in the direction of the reverse reaction.

Temperature and reaction rates

Another important function of temperature in chemical processes is its function of speeding up chemical reactions. An increase in the concentration of reacting molecules, naturally, leads to a sped-up reaction, because there are simply more molecules colliding with one another. But it is also possible to speed up the reaction without changing the concentration.
By definition, wherever a temperature increase is involved, there is always an increase in average molecular translational energy. When temperatures are high, more molecules are colliding, and the collisions that occur are more energetic. The likelihood is therefore increased that any particular collision will result in the energy necessary to break chemical bonds, and thus bring about the rearrangements in molecules needed for a reaction.

KEY TERMS

Absolute zero: The temperature, defined as 0K on the Kelvin scale, at which the motion of molecules in a solid virtually ceases. The third law of thermodynamics establishes the impossibility of actually reaching absolute zero.
Calorie: A measure of specific heat capacity in the SI or metric system, equal to the heat that must be added to or removed from 1 gram of water to change its temperature by 1°C. The dietary Calorie (capital C), with which most people are familiar, is the same as the kilocalorie.
Calorimetry: The measurement of heat gain or loss as a result of physical or chemical change.
Celsius scale: The metric scale of temperature, sometimes known as the centigrade scale, created in 1742 by Swedish astronomer Anders Celsius (17011744). The Celsius scale establishes the freezing and boiling points of water at 0° and 100° respectively. To convert a temperature from the Celsius to the Fahrenheit scale, multiply by 9/5 and add 32. Though the worldwide scientific community uses the metric or SI system for most measurements, scientists prefer the related Kelvin scale of absolute temperature.
Conservation of energy: A law of physics which holds that within a system isolated from all other outside factors, the total amount of energy remains the same, though transformations of energy from one form to another take place. The first law of thermodynamics is the same as the conservation of energy.
Energy: The ability to accomplish work—that is, the exertion of force over a given distance to displace or move an object.
Entropy: The tendency of natural systems toward breakdown, and specifically the tendency for the energy in a system to be dissipated. Entropy is closely related to the second law of thermodynamics.
Fahrenheit scale: The oldest of the temperature scales still in use, created in 1714 by German physicist Daniel Fahrenheit (1686-1736). The Fahrenheit scale establishes the freezing and boiling points of water at 32° and 212° respectively. To convert a temperature from the Fahrenheit to the Celsius scale, subtract 32 and multiply by 5/9.
First law of thermodynamics:A law which states the amount of energy in a system remains constant, and therefore it is impossible to perform work that results in an energy output greater than the energy input. This is the same as the conservation of energy.
Heat: Internal thermal energy that flows from one body of matter to another.
Joule: The principal unit of energy— and thus of heat—in the SI or metric system, corresponding to 1 newton-meter (N • m). A joule (J) is equal to 0.7376 footpounds in the English system.
Kelvin scale: Established by William Thompson, Lord Kelvin (18241907), the Kelvin scale measures temperature in relation to absolute zero, or 0K. (Units in the Kelvin system, known as Kelvins, do not include the word or symbol for degree.) The Kelvin scale, which is the system usually favored by scientists, is directly related to the Celsius scale; hence Celsius temperatures can be converted to Kelvins by adding 273.15.
Kilocalorie: A measure of specific heat capacity in the SI or metric system, equal to the heat that must be added to or removed from 1 kilogram of water to change its temperature by 1°C. As its name suggests, a kilocalorie is 1,000 calories. The dietary Calorie (capital C) with which most people are familiar is the same as the kilocalorie.
Kinetic energy: The energy that an object possesses by virtue of its motion.
Molecular translational energy: The kinetic energy in a system produced by the movement of molecules in relation to one another. Thermal energy is a manifestation of molecular translational energy.
Second law of thermodynamics: A law of thermodynamics which states that no system can simply take heat from a source and perform an equivalent amount of work. This is a result of the fact that the natural flow of heat is always from a high-temperature reservoir to a low-temperature reservoir. In the course of such a transfer, some of the heat will always be lost—an example of entropy. The second law is sometimes referred to as “the law of entropy.”
Specific heat capacity: The amount of heat that must be added to, or removed from, a unit of mass of a given substance to change its temperature by 1°C. It is typically measured in J/g • °C (joules per gram-degree Celsius). A calorie is the specific heat capacity of 1 gram of water.
System: In chemistry and other sciences, the term “system” usually refers to any set of interactions isolated from the rest of the universe. Anything outside of the system, including all factors and forces irrelevant to a discussion of that system, is known as the environment.
Thermal energy: Heat energy resulting from internal kinetic energy.
Thermal equilibrium: A situation in which two systems have the same temperature. As a result, there is no exchange of heat between them.
Thermodynamics: The study of the relationships between heat, work, and energy.
Thermometer: A device that gauges temperature by measuring a temperature-dependent property, such as the expansion of a liquid in a sealed tube, or resistance to electric current.
Thermometric medium: A substance whose physical properties change with temperature. A mercury or alcohol thermometer measures such changes.
Third law of thermodynamics:A law of thermodynamics stating that at the temperature of absolute zero, entropy also approaches zero. Zero entropy contradicts the second law of thermodynamics, meaning that absolute zero is therefore impossible to reach.

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