Ethanol is the main ingredient in alcoholic beverages. Ordinary vodka costs 40% of it. In everyday life it is called alcohol. Although in fact this term characterizes a huge class of organic substances. The boiling point of alcohol at normal pressure is 78.3 degrees Celsius. This only applies to undiluted ethanol. The boiling point of an alcohol solution is usually slightly lower. In this article, we will understand what ethanol is. We will also discuss its physical and chemical properties, features of production and application. We will not bypass the main question as to what is the boiling point of alcohol.

General information

Ethanol is one of the most famous alcohols. The composition of its molecule includes such elements as carbon, hydrogen and oxygen. The chemical formula of ethanol is C 2 H 6 O. It is a colorless liquid with a specific alcoholic odor. It is lighter than water. The boiling point of alcohol is 78.39 degrees Celsius. But this is at normal pressure. The boiling point of rectified alcohol is 78.15 degrees Celsius. It contains 4.43% water. The boiling point of ethyl alcohol is lower the more dilute it is.

Application in everyday life and industry

Ethyl alcohol is an excellent solvent. It is produced by fermenting sugar with yeast. In many villages of post-Soviet countries, it is still made at home. The resulting alcoholic drink is called moonshine. Ethyl alcohol is the oldest recreational drug used by man. It can cause alcohol intoxication if consumed in large quantities.

Ethanol is a volatile flammable substance. It is used in households and industry as an antiseptic, solvent, fuel, and active liquid in non-mercury thermometers (it freezes at -114 degrees Celsius).

The boiling point of alcohol against pressure

When the physical properties of substances are indicated in reference books, it must be understood that all these measurements were made under so-called normal conditions. As pressure increases, the boiling point of ethanol decreases. Today you can find many tables that provide reference data on this issue. At 780 mmHg, ethanol boils at 78.91 degrees Celsius, at 770 - 78.53ºC, at 760 - 78.15ºC, at 750 - 77.77ºC, at 740 - 77.39ºC, at 720 - 76.63ºC .

Boiling point of methyl alcohol

CH 3 OH was originally produced as a by-product of the destructive distillation of wood. To date, it is obtained directly from carbon dioxide and hydrogen. It smells very similar to ethanol. However, methanol is highly toxic and can lead to human death. The boiling point of alcohol is 64.7 degrees Celsius. It is used as an antifreeze and solvent. It is also used for the production of biodiesel fuel.

Manufacturing history

The fermentation of sugar to produce ethanol is one of the earliest biotechnologies in the service of humanity. The intoxicating effect of drinks based on it has been known since ancient times. People have always liked the state of altered consciousness that it causes. Even 9,000 years ago, the Chinese knew alcoholic beverages. Distillation as a process was well known to the Arabs and Greeks, but they had enough wine. Alchemists learned to produce alcohol from it only in the 12th century. Synthetically, ethanol was first produced only in 1825 by Michael Faraday.

Chemistry and medicine

Ethanol is mainly used as a raw material for the production of other substances and as a solvent. It is one of the components of many household chemicals that are used daily in everyday life. Ethanol is found in windshield wipers and antifreeze. In medicine, it is used as the simplest antiseptic. It disinfects well and dries up wounds. It is also used to make all kinds of tinctures and extracts. In addition, it cools and warms well. In the absence of other medicines, it was used as an anesthetic.

Society and culture

A study published in 2002 found that 41% of deaths in car accidents are due to drunk driving. The higher the driver's blood alcohol content, the greater the risk. The use of alcoholic beverages has a long history. Many studies have been devoted to this social phenomenon. The process of drinking alcoholic beverages and intoxication are described in many works of art. The famous New Year's film "The Irony of Fate, or Enjoy Your Bath!" is devoted just to the consequences of alcohol abuse, albeit in a comedic form. Many creative people have used alcohol as a necessary element in generating new ideas or as an easy way to overcome stress. Moderate drinking is acceptable and even desirable in most modern cultures. Drinking alcohol is a tradition at many festive occasions. The exception is Islam. According to the rules of this religion, the use of any alcoholic beverages is a terrible sin.

Alcoholism and its consequences

Excessive drinking is a disease. It is characterized by physical and mental dependence on vodka or other strong drinks, it is a kind of substance abuse. Alcoholics lose control over how much they drink. They need more and more to enjoy themselves. It is believed that improving the well-being of the population leads only to an increase in the consumption of alcoholic beverages. For the first time, the Swedish doctor M. Huss took up the study of chronic alcoholism in 1849. He singled out a number of pathological changes that appear in a person with the systematic use of alcohol. Now scientists draw a clear line between drunkenness and alcoholism. The second is a disease with which the person himself is not able to cope. It goes through several stages in its development. At each new stage, there is a gradual increase in dependence. The patient needs an increasing dose. Gradually, chronic alcohol intoxication leads to somatic disorders. The initial signs of physical and mental dependence include loss of control over use and the appearance of binges. Persons with severe alcoholism are distinguished by malfunctions in the work of internal organs and mental disorders.

Treatment and prevention

Drugs are required to fight alcohol addiction. First, medicines are needed to eliminate malfunctions in the body. Secondly, medicines that are not compatible with alcohol are mandatory. It is brought to the attention of the patient that binge drinking during treatment can lead to his death. In addition, psychologists must work with patients. Their task is to consolidate the effect of treatment and form a negative image of drunkenness. Also mandatory is the social rehabilitation of former alcoholics. It is important to help a person find his place in society, to return the family. Happy people don't get drunk. Therefore, the treatment of alcoholism is more dependent on the skills of a psychologist.

Boiling- This is an intense transition of liquid to vapor, occurring with the formation of vapor bubbles throughout the entire volume of the liquid at a certain temperature.

During boiling, the temperature of the liquid and vapor above it does not change. It remains unchanged until all the liquid boils away. This is because all the energy supplied to the liquid is spent on turning it into vapor.

The temperature at which a liquid boils is called boiling point.

The boiling point depends on the pressure exerted on the free surface of the liquid. This is due to the dependence of saturated vapor pressure on temperature. A vapor bubble grows as long as the pressure of the saturated vapor inside it slightly exceeds the pressure in the liquid, which is the sum of the external pressure and the hydrostatic pressure of the liquid column.

The greater the external pressure, the more boiling temperature.

Everyone knows that water boils at 100 ºC. But we should not forget that this is true only at normal atmospheric pressure (about 101 kPa). With an increase in pressure, the boiling point of water increases. So, for example, in pressure cookers, food is cooked under a pressure of about 200 kPa. The boiling point of water reaches 120°C. In water of this temperature, the cooking process is much faster than in ordinary boiling water. This explains the name "pressure cooker".

Conversely, by reducing the external pressure, we thereby lower the boiling point. For example, in mountainous regions (at an altitude of 3 km, where the pressure is 70 kPa), water boils at a temperature of 90 ° C. Therefore, the inhabitants of these areas, using such boiling water, require much more time for cooking than the inhabitants of the plains. And to cook in this boiling water, for example, a chicken egg is generally impossible, since at a temperature below 100 ° C the protein does not coagulate.

Each liquid has its own boiling point, which depends on the saturation vapor pressure. The higher the saturated vapor pressure, the lower the boiling point of the corresponding liquid, since at lower temperatures the saturated vapor pressure becomes equal to atmospheric pressure. For example, at a boiling point of 100 ° C, the pressure of saturated water vapor is 101,325 Pa (760 mm Hg), and vapor pressure is only 117 Pa (0.88 mm Hg). Mercury boils at 357°C at normal pressure.

The heat of vaporization.

Heat of vaporization (heat of vaporization)- the amount of heat that must be reported to the substance (at constant pressure and constant temperature) for the complete transformation of a liquid substance into vapor.

The amount of heat required for vaporization (or released during condensation). To calculate the amount of heat Q, necessary for the transformation into vapor of a liquid of any mass, taken at the boiling point, you need the specific heat of vaporization r mind-knife to the mass m:

When steam condenses, the same amount of heat is released.

The task consists of two stages - to establish the dependence of atmospheric pressure on altitude and the dependence of boiling point on pressure. Let's start with the latter, as the more interesting one.

Boiling is a phase transition of the first kind (water changes its state of aggregation from liquid to gaseous).
The phase transition of the first kind is described by the Clapeyron equation:
,
Where
- specific heat of the phase transition, which is numerically equal to the amount of heat reported to the unit mass of the substance for the implementation of the phase transition,
- phase transition temperature,
- change in specific volume during the transition

Clausius simplified Clapeyron's equation for the cases of evaporation and sublimation by assuming that

1. Steam obeys the ideal gas law
2. The specific volume of liquid is much less than the specific volume of vapor

From point one it follows that the state of the vapor can be described by the Mendeleev-Clapeyron equation
,
and from point two - that the specific volume of the liquid can be neglected.

Thus, the Clapeyron equation takes the form
,
where the specific volume can be expressed in terms of
,
and finally

separating the variables, we get

Having integrated the left side from to and the right side from to , i.e. from one point to another point lying on the liquid-vapor equilibrium line, we obtain the equation

called the Clausius-Clapeyron equation.

Actually, this is the desired dependence of the boiling point on pressure.

Let's do a couple more changes.
,
Here
- molar mass of water, 18 g/mol

Universal gas constant, 8.31 J/(mol × K)

Specific heat of vaporization of water 2.3 × 10 6 J/kg

Now it remains to establish the dependence of atmospheric pressure on altitude. Here we will use the barometric formula (we don’t have another one anyway):

or
,
Here
- molar mass of air, 29 g/mol
- universal gas constant, 8.31 J/(mol×K)
- acceleration of gravity, 9.81 m/(s×s)
- air temperature

The values ​​related to air will be marked with the index v, those related to water - h
Equating and getting rid of the exponent, we get

Well, the final formula

In fact, the actual air pressure does not follow the barometric formula, since with large elevation changes, the air temperature cannot be considered constant. In addition, the acceleration of free fall depends on the geographical latitude, and atmospheric pressure also depends on the concentration of water vapor. That is, according to this formula, we will get an approximate value. Therefore, below I have included another calculator that uses a formula to calculate the boiling point depending on the air pressure in millimeters of mercury.

Boiling temperature versus altitude calculator.

States of matter

Iron vapor and solid air

Isn't it a strange combination of words? However, this is not nonsense at all: both iron vapor and solid air exist in nature, but not under ordinary conditions.

What conditions are we talking about? The state of matter is determined by two circumstances: temperature and pressure.

Our life takes place in relatively little changing conditions. Air pressure fluctuates within a few percent around one atmosphere; air temperature, say, in the Moscow area lies in the range from -30 to + 30 ° C; in the absolute temperature scale, in which the lowest possible temperature (-273 ° C) is taken as zero; this interval will look less impressive: 240-300 K, which is also only ±10% of the average value.

It is quite natural that we are accustomed to these ordinary conditions, and therefore, when we say simple truths like: "iron is a solid, air is a gas," etc., we forget to add: "under normal conditions."

If iron is heated, it first melts and then evaporates. If the air is cooled, it will first turn into a liquid, and then solidify.

Even if the reader has never met with iron vapor and solid air, he will probably easily believe that any substance, by changing the temperature, can be obtained in solid, liquid, and gaseous states, or, as they say, in solid , liquid or gaseous phases.

It is easy to believe in this because one substance, without which life on Earth would be impossible, everyone observed both in the form of a gas, and as a liquid, and in the form of a solid body. We are, of course, talking about water.

What are the conditions under which a substance changes from one state to another?

Boiling

If we lower the thermometer into the water that is poured into the kettle, turn on the electric stove and monitor the mercury of the thermometer, we will see the following: almost immediately the level of mercury will creep up. It's already 90, 95, finally 100°C. The water boils, and at the same time the rise of mercury stops. The water has been boiling for many minutes, but the level of mercury does not change. Until all the water boils away, the temperature will not change (Fig. 4.1).

Rice. 4.1

Where does the heat go if the temperature of the water does not change? The answer is obvious. The process of turning water into steam requires energy.

Let's compare the energy of a gram of water and a gram of steam formed from it. Vapor molecules are farther apart than water molecules. It is clear that because of this, the potential energy of water will differ from the potential energy of steam.

The potential energy of attracted particles decreases as they approach each other. Therefore, the energy of steam is greater than the energy of water, and the transformation of water into steam requires energy. This excess of energy is communicated by an electric stove to boiling water in a kettle.

The energy needed to turn water into steam; called the heat of vaporization. It takes 539 calories to turn 1 g of water into steam (this is the figure for a temperature of 100°C).

If 539 cal goes to 1 g, then 18 * 539 \u003d 9700 cal will be spent on 1 mole of water. This amount of heat must be expended to break intermolecular bonds.

You can compare this figure with the amount of work required to break intramolecular bonds. In order to split 1 mole of water vapor into atoms, about 220,000 calories are required, that is, 25 times more energy. This directly proves the weakness of the forces that bind molecules to each other, compared with the forces that pull atoms together into a molecule.

Boiling temperature versus pressure

The boiling point of water is 100°C; one might think that this is an inherent property of water, that water, wherever and under what conditions it is, will always boil at 100 ° C.

But this is not so, and the inhabitants of high-mountain villages are well aware of this.

Near the top of Elbrus there is a house for tourists and a scientific station. Beginners sometimes wonder "how difficult it is to boil an egg in boiling water" or "why boiling water does not burn." Under these conditions, they are told that water boils at the top of Elbrus already at 82°C.

What is the matter here? What physical factor interferes with the phenomenon of boiling? What is the significance of altitude?

This physical factor is the pressure acting on the surface of the liquid. You do not need to climb to the top of the mountain to check the validity of what has been said.

By placing heated water under the bell and pumping air in or out of it, one can be convinced that the boiling point rises with increasing pressure and falls with decreasing pressure.

Water boils at 100°C only at a certain pressure - 760 mm Hg. Art. (or 1 atm).

The boiling point versus pressure curve is shown in fig. 4.2. At the top of Elbrus, the pressure is 0.5 atm, and this pressure corresponds to a boiling point of 82 ° C.

Rice. 4.2

But water boiling at 10-15 mm Hg. Art., you can freshen up in hot weather. At this pressure, the boiling point will drop to 10-15°C.

You can even get "boiling water", which has the temperature of freezing water. To do this, you will have to reduce the pressure to 4.6 mm Hg. Art.

An interesting picture can be observed if you place an open vessel with water under the bell and pump out the air. Pumping will make the water boil, but boiling requires heat. There is nowhere to take it from, and the water will have to give up its energy. The temperature of the boiling water will begin to drop, but as the pumping continues, so will the pressure. Therefore, the boiling will not stop, the water will continue to cool and eventually freeze.

Such boiling of cold water occurs not only when air is pumped out. For example, when a ship's propeller rotates, the pressure in a layer of water rapidly moving near a metal surface drops sharply and the water in this layer boils, i.e., numerous bubbles filled with steam appear in it. This phenomenon is called cavitation (from the Latin word cavitas - cavity).

By lowering the pressure, we lower the boiling point. What about increasing it? A graph like ours answers this question. A pressure of 15 atm can delay the boiling of water, it will only start at 200°C, and a pressure of 80 atm will make water boil only at 300°C.

So, a certain external pressure corresponds to a certain boiling point. But this statement can also be "turned over", saying this: each boiling point of water corresponds to its own specific pressure. This pressure is called vapor pressure.

The curve depicting the boiling point as a function of pressure is also the curve of vapor pressure as a function of temperature.

Figures plotted on a boiling point graph (or vapor pressure graph) show that vapor pressure changes very rapidly with temperature. At 0°C (i.e., 273 K), the vapor pressure is 4.6 mm Hg. Art., at 100 ° C (373 K) it is equal to 760 mm Hg. Art., i.e. increases by 165 times. When the temperature doubles (from 0 ° C, i.e. 273 K, to 273 ° C, i.e. 546 K), the vapor pressure increases from 4.6 mm Hg. Art. up to almost 60 atm, i.e., about 10,000 times.

Therefore, on the contrary, the boiling point changes rather slowly with pressure. When the pressure is doubled from 0.5 atm to 1 atm, the boiling point increases from 82°C (355 K) to 100°C (373 K) and when the pressure is doubled from 1 to 2 atm, from 100°C (373 K) to 120°C (393 K).

The same curve that we are now considering also controls the condensation (thickening) of steam into water.

Steam can be converted to water by either compression or cooling.

Both during boiling and during condensation, the point will not move off the curve until the conversion of steam to water or water to steam is complete. This can also be formulated as follows: under the conditions of our curve, and only under these conditions, the coexistence of liquid and vapor is possible. If at the same time no heat is added or taken away, then the quantities of vapor and liquid in a closed vessel will remain unchanged. Such vapor and liquid are said to be in equilibrium, and a vapor in equilibrium with its liquid is said to be saturated.

The curve of boiling and condensation, as we see, has another meaning: it is the equilibrium curve of liquid and vapor. The equilibrium curve divides the diagram field into two parts. To the left and upwards (toward higher temperatures and lower pressures) is the region of the steady state of steam. To the right and down - the region of the stable state of the liquid.

The vapor-liquid equilibrium curve, i.e., the dependence of the boiling point on pressure or, what is the same, vapor pressure on temperature, is approximately the same for all liquids. In some cases, the change may be somewhat more abrupt, in others - somewhat slower, but always the vapor pressure increases rapidly with increasing temperature.

We have used the words "gas" and "steam" many times. These two words are pretty much the same. We can say: water gas is the vapor of water, gas oxygen is the vapor of an oxygen liquid. Nevertheless, some habit has developed in the use of these two words. Since we are accustomed to a certain relatively small temperature range, we usually apply the word "gas" to those substances whose vapor pressure at ordinary temperatures is above atmospheric pressure. On the contrary, we speak of a vapor when, at room temperature and atmospheric pressure, the substance is more stable in the form of a liquid.

Evaporation

Boiling is a fast process, and in a short time there is no trace of boiling water, it turns into steam.

But there is another phenomenon of the transformation of water or other liquid into steam - this is evaporation. Evaporation occurs at any temperature, regardless of pressure, which under normal conditions is always close to 760 mm Hg. Art. Evaporation, unlike boiling, is a very slow process. The bottle of cologne we forgot to close will be empty in a few days; more time o a saucer with water will stand, but sooner or later it will turn out to be dry.

Air plays an important role in the evaporation process. By itself, it does not prevent water from evaporating. As soon as we open the surface of the liquid, water molecules will begin to move into the nearest layer of air.

The vapor density in this layer will increase rapidly; after a short time, the vapor pressure will become equal to the elasticity characteristic of the temperature of the medium. In this case, the vapor pressure will be exactly the same as in the absence of air.

The transition of vapor into air does not, of course, mean an increase in pressure. The total pressure in the space above the water surface does not increase, only the share in this pressure that is taken on by steam increases, and, accordingly, the proportion of air that is displaced by steam decreases.

Above the water there is steam mixed with air, above there are layers of air without steam. They will inevitably mix. Water vapor will continuously move to higher layers, and in its place, air will flow into the lower layer, which does not contain water molecules. Therefore, in the layer closest to the water, places will always be freed up for new water molecules. The water will continuously evaporate, maintaining the water vapor pressure at the surface equal to the elasticity, and the process will continue until the water has completely evaporated.

We started with the cologne and water example. It is well known that they evaporate at different rates. Ether evaporates exceptionally quickly, alcohol rather quickly, and water much more slowly. We will immediately understand what is the matter if we find in the reference book the values ​​of the vapor pressure of these liquids, say, at room temperature. Here are the numbers: ether - 437 mm Hg. Art., alcohol - 44.5 mm Hg. Art. and water - 17.5 mm Hg. Art.

The greater the elasticity, the more vapor in the adjacent layer of air and the faster the liquid evaporates. We know that vapor pressure increases with temperature. It is clear why the rate of evaporation increases with heating.

The rate of evaporation can also be influenced in another way. If we want to help evaporation, we must quickly remove the vapor from the liquid, i.e., speed up the mixing of air. That is why evaporation is greatly accelerated by blowing the liquid. Water, although it has a relatively small vapor pressure, will disappear rather quickly if the saucer is placed in the wind.

It is understandable, therefore, why a swimmer who comes out of the water feels cold in the wind. The wind accelerates the mixing of air with steam and, therefore, accelerates evaporation, and the heat for evaporation is forced to give up the human body.

A person's well-being depends on whether there is a lot or a little water vapor in the air. Both dry and humid air are unpleasant. Humidity is considered normal when it is 60%. This means that the density of water vapor is 60% of the density of saturated water vapor at the same temperature.

If moist air is cooled, then eventually the pressure of water vapor in it will be equal to the vapor pressure at this temperature. The steam will become saturated and, as the temperature drops further, it will begin to condense into water. Morning dew, moisturizing grass and leaves, appears just because of this phenomenon.

At 20°C, the density of saturated water vapor is about 0.00002 g/cm 3 . We will feel good if the air contains 60% of this number of water vapor - which means only a little more than one hundred thousandth of a gram in 1 cm 3.

Although this figure is small, it will lead to impressive amounts of steam for a room. It is easy to calculate that in a medium-sized room with an area of ​​12 m 2 and a height of 3 m, about a kilogram of water can "fit" in the form of saturated steam.

So, if you tightly close such a room and put an open barrel of water, then a liter of water will evaporate, no matter what the capacity of the barrel.

It is interesting to compare this result for water with the corresponding figures for mercury. At the same temperature of 20°C, the density of saturated mercury vapor is 10 -8 g/cm 3 .

In the room we have just discussed, no more than 1 g of mercury vapor will fit.

By the way, mercury vapor is very toxic, and 1 g of mercury vapor can seriously damage the health of any person. When working with mercury, care must be taken that even the smallest drop of mercury does not spill.

Critical temperature

How to turn gas into liquid? The boiling graph answers this question. You can turn a gas into a liquid by either decreasing the temperature or increasing the pressure.

In the 19th century, raising the pressure seemed easier than lowering the temperature. At the beginning of this century, the great English physicist Michael Farada managed to compress gases to the values ​​of vapor pressure and in this way turn many gases (chlorine, carbon dioxide, etc.) into liquid.

However, some gases - hydrogen, nitrogen, oxygen - did not lend themselves to liquefaction. No matter how much the pressure was increased, they did not turn into a liquid. One might have thought that oxygen and other gases could not be liquid. They were classified as true, or permanent, gases.

In fact, the failures were caused by a misunderstanding of one important circumstance.

Consider a liquid and a vapor in equilibrium and consider what happens to them as the boiling point rises and, of course, as the pressure rises accordingly. In other words, imagine that a point on the boiling graph moves up along the curve. It is clear that the liquid expands with increasing temperature and its density decreases. As for steam, an increase in the boiling point? of course, it contributes to its expansion, but, as we have already said, the saturation vapor pressure rises much faster than the boiling point. Therefore, the vapor density does not fall, but, on the contrary, increases rapidly with increasing boiling point.

Since the density of the liquid falls, and the density of the vapor increases, then, moving "up" along the boiling curve, we will inevitably reach a point at which the densities of the liquid and vapor become equal (Fig. 4.3).

Rice. 4.3

At this remarkable point, which is called the critical point, the boiling curve terminates. Since all differences between gas and liquid are due to the difference in density, at the critical point the properties of liquid and gas become the same. Each substance has its own critical temperature and its own critical pressure. Thus, for water, the critical point corresponds to a temperature of 374°C and a pressure of 218.5 atm.

If you compress a gas whose temperature is below the critical one, then the process of its compression will be depicted by an arrow crossing the boiling curve (Fig. 4.4). This means that at the moment of reaching a pressure equal to the vapor pressure (the point of intersection of the arrow with the boiling curve), the gas will begin to condense into a liquid. If our vessel were transparent, then at this moment we would see the beginning of the formation of a liquid layer at the bottom of the vessel. At constant pressure, the layer of liquid will grow until, finally, all the gas turns into a liquid. Further compression will require an increase in pressure.

Rice. 4.4

The situation is completely different when the gas is compressed, the temperature of which is higher than the critical one. The compression process can again be depicted as an arrow going from bottom to top. But now this arrow does not cross the boiling curve. This means that during compression, the vapor will not condense, but will only continuously condense.

At a temperature above the critical one, the existence of a liquid and a gas separated by an interface is impossible: When compressed to any density, a homogeneous substance will be under the piston, and it is difficult to say when it can be called a gas and when it can be called a liquid.

The presence of a critical point shows that there is no fundamental difference between the liquid and gaseous states. At first glance, it might seem that there is no such fundamental difference only in the case when we are talking about temperatures above the critical one. This, however, is not the case. The existence of a critical point indicates the possibility of the transformation of a liquid - a real liquid that can be poured into a glass - into a gaseous state without any semblance of boiling.

This transformation path is shown in Fig. 4.4. The known liquid is marked with a cross. If you lower the pressure a little (arrow down), it will boil, it will boil if you raise the temperature a little (arrow to the right). But we will do something completely different. We will compress the liquid very strongly, to a pressure above the critical one. The point representing the state of the liquid will go vertically upwards. Then we heat the liquid - this process is depicted by a horizontal line. Now, after we have found ourselves to the right of the Critical temperature, we will lower the pressure to the initial one. If we now reduce the temperature, then we can get the most real steam, which could be obtained from this liquid in a simpler and shorter way.

Thus, it is always possible, by varying the pressure and temperature to bypass the critical point, to obtain vapor by continuous transition from liquid or liquid from vapor. Such a continuous transition does not require boiling or condensation.

Early attempts to liquefy gases such as oxygen, nitrogen, hydrogen were therefore unsuccessful because the existence of a critical temperature was not known. These gases have very low critical temperatures: nitrogen has -147°C, oxygen has -119°C, hydrogen has -240°C, or 33 K. The record holder is helium, its critical temperature is 4.3 K. Turn these gases into liquid can only be done in one way - it is necessary to reduce their temperature below the specified one.

Getting low temperatures

A significant decrease in temperature can be achieved in various ways. But the idea of ​​all methods is the same: we must force the body that we want to cool down to expend its internal energy.

How to do it? One way is to make the liquid boil without supplying heat from outside. To do this, as we know, it is necessary to reduce the pressure - to reduce it to the value of vapor pressure. The heat expended for boiling will be borrowed from the liquid and the temperature of the liquid and vapor, and with it the vapor pressure will fall. Therefore, in order for the boiling not to stop and to happen faster, air must be continuously pumped out of the vessel with the liquid.

However, there is a limit to the temperature drop during this process: the vapor pressure eventually becomes completely insignificant, and even the strongest pumping pumps cannot create the required pressure.

In order to continue lowering the temperature, it is possible, by cooling the gas with the resulting liquid, to turn it into a liquid with a lower boiling point.

Now the pumping process can be repeated with the second substance and thus lower temperatures can be obtained. If necessary, such a "cascade" method for obtaining low temperatures can be extended.

This is exactly what they did at the end of the last century; the liquefaction of gases was carried out in stages: ethylene, oxygen, nitrogen, hydrogen, substances with boiling points of -103, -183, -196 and -253°C, were successively converted into liquid. Having liquid hydrogen, you can also get the lowest boiling liquid - helium (-269 ° C). The neighbor on the "left" helped to get the neighbor on the "right".

The cascade cooling method is almost a hundred years old. In 1877 liquid air was obtained by this method.

In 1884-1885. liquid hydrogen was produced for the first time. Finally, after another twenty years, the last fortress was taken: in 1908, Kamerling-Onnes in the city of Leiden in Holland turned helium into a liquid - a substance with the lowest critical temperature. The 70th anniversary of this important scientific achievement was recently celebrated.

For many years the Leiden Laboratory was the only "low-temperature" laboratory. Now in all countries there are dozens of such laboratories, not to mention plants that produce liquid air, nitrogen, oxygen and helium for technical purposes.

The cascade method for obtaining low temperatures is now rarely used. In technical installations, to lower the temperature, another method is used to lower the internal energy of the gas: the gas is forced to expand rapidly and perform work at the expense of internal energy.

If, for example, air compressed to several atmospheres is put into an expander, then when the work of moving the piston or rotating the turbine is performed, the air will cool so sharply that it will turn into a liquid. Carbon dioxide, if it is quickly released from the cylinder, cools so sharply that it turns into "ice" on the fly.

Liquid gases are widely used in engineering. Liquid oxygen is used in explosive technology as a component of the fuel mixture in jet engines.

Air liquefaction is used in engineering to separate the gases that make up air.

In various fields of technology, it is required to work at liquid air temperature. But for many physical studies, this temperature is not low enough. Indeed, if we translate degrees Celsius into an absolute scale, we will see that the temperature of liquid air is about 1/3 of room temperature. Much more interesting for physics are "hydrogen" temperatures, ie, temperatures of the order of 14-20 K, and especially "helium" temperatures. The lowest temperature obtained when liquid helium is pumped out is 0.7 K.

Physicists have managed to come much closer to absolute zero. At present, temperatures exceeding absolute zero by only a few thousandths of a degree have been obtained. However, these ultra-low temperatures are obtained in ways that are not similar to those that we have described above.

In recent years, low-temperature physics has given rise to a special branch of industry engaged in the production of apparatus that makes it possible to maintain large volumes at a temperature close to absolute zero; power cables have been developed whose busbars operate at a temperature of less than 10 K.

Supercooled vapor and superheated liquid

At the transition of the boiling point, the vapor must condense, turn into a liquid. However,; It turns out that if the vapor does not come into contact with the liquid, and if the vapor is very pure, then it is possible to obtain a supercooled or supersaturated vapor - a vapor that should have become a liquid long ago.

Supersaturated steam is very unstable. Sometimes a push or a grain of steam thrown into space is enough to start a belated condensation.

Experience shows that the condensation of vapor molecules is greatly facilitated by the introduction of small foreign particles into the vapor. In dusty air, supersaturation of water vapor does not occur. Can cause condensation with puffs of smoke. After all, smoke is made up of small solid particles. Getting into the steam, these particles collect molecules around themselves and become centers of condensation.

So, although unstable, steam can exist in the temperature range adapted for the "life" of the liquid.

Can a liquid `live' in the region of vapor under the same conditions? In other words, is it possible to superheat a liquid?

It turns out you can. To do this, it is necessary to ensure that the molecules of the liquid do not break away from its surface. The radical remedy is to eliminate the free surface, that is, to place the liquid in a vessel where it would be compressed on all sides by solid walls. In this way, it is possible to achieve overheating of the order of several degrees, i.e., to move the point depicting the state of liquids to the right of the boiling curve (Fig. 4.4).

Overheating is a shift of a liquid into a vapor region, so overheating of a liquid can be achieved both by supplying heat and by reducing pressure.

The last way you can achieve amazing results. Water or other liquid, carefully freed from dissolved gases (this is not easy to do), is placed in a vessel with a piston that reaches the surface of the liquid. The vessel and piston must be wetted by liquid. If you now pull the piston towards you, then the water adhered to the bottom of the piston will follow it. But the layer of water, clinging to the piston, will pull the next layer of water, this layer will pull the underlying one, as a result, the liquid will stretch.

In the end, the column of water will break (it is the column of water, and not the water, that will come off the piston), but this will happen when the force per unit area reaches tens of kilograms. In other words, a negative pressure of tens of atmospheres is created in the liquid.

Even at low positive pressures, the vapor state of matter is stable. A liquid can be brought to a negative pressure. You can't imagine a more striking example of "overheating".

Melting

There is no such solid body that would resist an increase in temperature as much as necessary. Sooner or later a solid piece turns into a liquid; right, in some cases we will not be able to get to the melting point - chemical decomposition can occur.

As the temperature rises, the molecules move faster and faster. Finally, there comes a moment when maintaining order "among strongly" swung "molecules becomes impossible. The solid melts. Tungsten has the highest melting point: 3380 ° C. Gold melts at 1063 ° C, iron at 1539 ° C. However, there are low-melting metals.Mercury, as is well known, melts already at a temperature of -39 ° C. Organic substances do not have high melting points. Naphthalene melts at 80 ° C, toluene - at -94.5 ° C.

It is not at all difficult to measure the melting point of a body, especially if it melts in the temperature range that is measured with an ordinary thermometer. It is not at all necessary to follow the melting body with your eyes. It is enough to look at the mercury column of the thermometer. Until melting has begun, the body temperature rises (Fig. 4.5). As soon as melting starts, the temperature rise stops and the temperature will remain unchanged until the melting process is complete.

Rice. 4.5

Like the transformation of a liquid into vapor, the transformation of a solid into a liquid requires heat. The heat required for this is called the latent heat of fusion. For example, melting one kilogram of ice requires 80 kcal.

Ice is one of the bodies with a high heat of fusion. Melting ice requires, for example, 10 times more energy than melting the same mass of lead. Of course, we are talking about the melting itself, we are not saying here that before the melting of lead begins, it must be heated to + 327 ° C. Due to the high heat of melting ice, the melting of snow slows down. Imagine that the heat of melting would be 10 times less. Then spring floods would bring unimaginable disasters every year.

So, the heat of melting of ice is great, but it is also small if compared with the specific heat of vaporization of 540 kcal/kg (seven times less). However, this difference is quite natural. When converting a liquid into vapor, we must tear the molecules one from the other, and when melting, we only have to destroy the order in the arrangement of the molecules, leaving them at almost the same distances. It is clear that less work is required in the second case.

The presence of a certain melting point is an important feature of crystalline substances. It is on this basis that they are easy to distinguish from other solids, called amorphous or glasses. Glasses are found among both inorganic and organic substances. Window panes are usually made from sodium and calcium silicates; often organic glass is placed on the desk (it is also called plexiglass).

Amorphous substances, in contrast to crystals, do not have a definite melting point. Glass does not melt, but softens. When heated, a piece of glass first becomes soft from hard, it can be easily bent or stretched; at a higher temperature, the piece begins to change its shape under the influence of its own gravity. As it heats up, the thick viscous mass of glass takes the shape of the vessel in which it lies. This mass is at first thick, like honey, then like sour cream, and, finally, it becomes almost as low-viscosity liquid as water. With all our desire, we cannot indicate here a specific temperature for the transition of a solid to a liquid. The reasons for this lie in the fundamental difference between the structure of glass and the structure of crystalline bodies. As mentioned above, atoms in amorphous bodies are arranged randomly. Glasses in structure resemble liquids. Even in solid glass, the molecules are arranged randomly. This means that an increase in the temperature of glass only increases the range of vibrations of its molecules, giving them gradually more and more freedom of movement. Therefore, the glass softens gradually and does not show a sharp "solid" - "liquid" transition, which is characteristic of the transition from the arrangement of molecules in a strict order to a random arrangement.

When it came to the boiling curve, we said that liquid and vapor can, albeit in an unstable state, live in foreign regions - vapor can be supercooled and transferred to the left of the boiling curve, liquid can be superheated and pulled to the right of this curve.

Are similar phenomena possible in the case of a crystal with a liquid? It turns out that the analogy here is incomplete.

If you heat the crystal, it will begin to melt at its melting point. The crystal cannot be overheated. On the contrary, by cooling the liquid, it is possible, if certain measures are taken, to “slip through” the melting point relatively easily. In some liquids, large subcoolings can be achieved. There are even liquids that are easy to supercool, but difficult to make crystallize. As such a liquid cools, it becomes more and more viscous and finally solidifies without crystallizing. Such is glass.

You can also recool water. Fog droplets may not freeze even in severe frosts. If a crystal of a substance, a seed, is thrown into a supercooled liquid, then crystallization will immediately begin.

Finally, in many cases delayed crystallization may be initiated by a shake or other random events. It is known, for example, that crystalline glycerol was first obtained during transportation by rail. Glasses after a long standing may begin to crystallize (devitrify, or "collapse", as they say in technology).

How to grow a crystal

Almost any substance can give crystals under certain conditions. Crystals can be obtained from a solution or from a melt of a given substance, as well as from its vapors (for example, black diamond-shaped crystals of iodine easily precipitate from its vapors at normal pressure without an intermediate transition to a liquid state).

Start dissolving table salt or sugar in the water. At room temperature (20°C), you will be able to dissolve only 70 g of salt in a faceted glass. Further additions of salt will not dissolve and will settle at the bottom in the form of sediment. A solution in which no further dissolution occurs is called saturated. .If you change the temperature, then the degree of solubility of the substance will also change. Everyone is well aware that hot water dissolves most substances much easier than cold water.

Imagine now - that you have prepared a saturated solution of, say, sugar at a temperature of 30 ° C and begin to cool it to 20 ° C. At 30°C, you were able to dissolve 223 g of sugar in 100 g of water, at 20°C, 205 g dissolves. Then, when cooled from 30 to 20°C, 18 g will be "extra" and, as they say, will fall out of solution. So, one of the possible ways to obtain crystals is to cool the saturated solution.

You can do it differently. Prepare a saturated salt solution and leave it in an open glass. After a while, you will find the appearance of crystals. Why did they form? Careful observation will show that simultaneously with the formation of crystals, another change occurred - the amount of water decreased. The water evaporated, and the "extra" substance appeared in the solution. So, another possible way for the formation of crystals is the evaporation of a solution.

How does crystals form from solution?

We said that the crystals "fall out" of the solution; Is it necessary to understand this in such a way that there was no crystal for a week, and in one moment it suddenly appeared at once? No, this is not the case: the crystals grow. It is not possible, of course, to detect the very initial moments of growth with the eye. At first, a few of the randomly moving molecules or atoms of the solute assemble in the approximate order needed to form the crystal lattice. Such a group of atoms or molecules is called a nucleus.

Experience shows that nuclei are more often formed in the presence of any extraneous minute dust particles in the solution. The fastest and easiest crystallization begins when a small seed crystal is placed in a saturated solution. In this case, the isolation of a solid from the solution will not consist in the formation of new crystals, but in the growth of the seed.

The growth of the embryo does not, of course, differ from the growth of the seed. The meaning of using a seed is that it "pulls" the released substance onto itself and thus prevents the simultaneous formation of a large number of nuclei. If many nuclei are formed, then they will interfere with each other during growth and will not allow us to obtain large crystals.

How are the portions of atoms or molecules released from the solution distributed on the surface of the nucleus?

Experience shows that the growth of a nucleus or a seed consists, as it were, in moving the faces parallel to themselves in a direction perpendicular to the face. In this case, the angles between the faces remain constant (we already know that the constancy of angles is the most important feature of a crystal, which follows from its lattice structure).

On fig. 4.6 the outlines of three crystals of the same substance that occur during their growth are given. Similar patterns can be observed under a microscope. In the case shown on the left, the number of faces is conserved during growth. The middle drawing gives an example of a new face appearing (upper right) and disappearing again.

Rice. 4.6

It is very important to note that the growth rate of the faces, i.e., the speed of their movement parallel to themselves, is not the same for different faces. In this case, exactly those faces that move the fastest, for example, the lower left face in the middle figure, "overgrow" (disappear). On the contrary, slowly growing faces are the widest, as they say, the most developed.

This is especially clear in the last figure. The shapeless fragment acquires the same shape as other crystals precisely because of the growth rate anisotropy. Well-defined facets develop at the expense of others most strongly and give the crystal a form characteristic of all samples of this substance.

Very beautiful transitional forms are observed when a ball is taken as a seed, and the solution is alternately slightly cooled and heated. When heated, the solution becomes unsaturated, and the seed is partially dissolved. Cooling leads to saturation of the solution and growth of the seed. But the molecules settle in a different way, as if giving preference to certain places. The substance is thus transferred from one place of the ball to another.

First, small circle-shaped faces appear on the surface of the ball. The circles gradually increase and, touching each other, merge along straight edges. The ball turns into a polyhedron. Then some faces overtake others, some of the faces overgrow, and the crystal acquires its characteristic shape (Fig. 4.7).

Rice. 4.7

When observing the growth of crystals, the main feature of growth is striking - the parallel movement of the faces. It turns out that the released substance builds up the face in layers: until one layer is completed, the next one does not begin to build.

On fig. 4.8 shows the "unfinished" packing of atoms. In which of the positions indicated by letters will the new atom be most firmly held, attached to the crystal? No doubt in A, since here he experiences the attraction of neighbors from three sides, while in B - from two, and in C - only from one side. Therefore, the column is first completed, then the entire plane, and only then the laying of a new plane begins.

Rice. 4.8

In a number of cases, crystals are formed from a molten mass - from a melt. In nature, this happens on an enormous scale: basalts, granites and many other rocks arose from fiery magma.

Let's start heating some crystalline substance, for example, rock salt. Up to 804°C, rock salt crystals will change little: they expand only slightly, and the substance remains solid. A temperature meter placed in a vessel with a substance shows a continuous increase in temperature when heated. At 804°C, we will immediately discover two new, interconnected phenomena: the substance will begin to melt, and the rise in temperature will stop. Until all matter turns into a liquid,; the temperature will not change; a further rise in temperature is already heating the liquid. All crystalline substances have a certain melting point. Ice melts at 0°C, iron melts at 1527°C, mercury melts at -39°C, etc.

As we already know, in each crystal the atoms or molecules of a substance form an ordered G packing and make small vibrations around their average positions. As the body heats up, the speed of the oscillating particles increases along with the amplitude of the oscillations. This increase in the speed of particles with increasing temperature is one of the basic laws of nature, which applies to matter in any state - solid, liquid or gaseous.

When a certain, sufficiently high temperature of the crystal is reached, the vibrations of its particles become so energetic that an accurate arrangement of the particles becomes impossible - the crystal melts. With the onset of melting, the heat supplied is no longer used to increase the particle velocity, but to destroy the crystal lattice. Therefore, the rise in temperature is suspended. Subsequent heating is an increase in the velocity of the liquid particles.

In the case of crystallization from a melt that interests us, the above phenomena are observed in the reverse order: as the liquid cools, its particles slow down their chaotic motion; when a certain, sufficiently low temperature is reached, the velocity of the particles is already so low that some of them, under the influence of attractive forces, begin to attach themselves to one another, forming crystalline nuclei. Until all the substance crystallizes, the temperature remains constant. This temperature is generally the same as the melting point.

If special measures are not taken, then crystallization from the melt will begin immediately in many places. Crystals will grow in the form of regular polyhedrons characteristic of them in exactly the same way as we described above. However, free growth does not last long: growing, the crystals collide with each other, growth stops at the points of contact, and the hardened body acquires a granular structure. Each grain is a separate crystal, which failed to take its correct form.

Depending on many conditions, and above all on the rate of cooling, a solid body may have more or less large grains: the slower the cooling, the larger the grains. The grain sizes of crystalline bodies range from a millionth of a centimeter to several millimeters. In most cases, the granular crystalline structure can be observed under a microscope. Solids usually have just such a fine-grained structure.

For technology, the process of solidification of metals is of great interest. The events that occur during casting and during the solidification of metal in molds have been studied by physicists in great detail.

For the most part, during solidification, tree-like single crystals grow, which are called dendrites. In other cases, the dendrites are oriented randomly, in other cases, they are parallel to each other.

On fig. 4.9 shows the stages of growth of one dendrite. With this behavior, a dendrite can overgrow before it meets another similar one. Then we will not find dendrites in the casting. Events can also develop differently: dendrites can meet and grow into each other (branches of one in the gaps between the branches of another) while they are still "young".

Rice. 4.9

In this way, castings may arise whose grains (shown in Fig. 2.22) have a very different structure. And the properties of metals significantly depend on the nature of this structure. It is possible to control the behavior of the metal during solidification by changing the cooling rate and the heat removal system.

Now let's talk about how to grow a large single crystal. It is clear that measures must be taken to ensure that the crystal grows from one place. And if several crystals have already begun to grow, then in any case it is necessary to make sure that the growth conditions are favorable for only one of them.

Here, for example, is how they proceed when growing crystals of low-melting metals. The metal is melted in a glass test tube with a drawn end. A test tube suspended by a thread inside a vertical cylindrical furnace is slowly lowered down. The drawn end gradually exits the furnace and cools. Crystallization begins. At first, several crystals form, but those that grow sideways rest against the wall of the test tube and their growth slows down. Only the crystal that grows along the axis of the test tube, i.e., deep into the melt, will be in favorable conditions. As the test tube is lowered, new portions of the melt, falling into the region of low temperatures, will "feed" this single crystal. Therefore, of all the crystals, he alone survives; as the tube is lowered, it continues to grow along its axis. In the end, all the molten metal solidifies in the form of a single crystal.

The same idea underlies the growth of refractory ruby ​​crystals. A fine powder of the substance is squirted through the flame. At the same time, the powders melt; tiny drops fall on a refractory support of a very small area, forming many crystals. As the drops fall further onto the stand, all the crystals grow, but again, only the one that is in the most favorable position for "receiving" the falling drops grows.

What are large crystals for?

Industry and science often need large single crystals. Of great importance for technology are crystals of Rochelle salt and quartz, which have the remarkable property of converting mechanical actions (for example, pressure) into electrical voltage.

The optical industry needs large crystals of calcite, rock salt, fluorite, etc.

The watch industry needs crystals of rubies, sapphires and some other precious stones. The fact is that individual moving parts of ordinary watches make up to 20,000 vibrations per hour. Such a high load places unusually high demands on the quality of the axle tips and bearings. Abrasion will be the smallest when a ruby ​​or sapphire serves as a bearing for the tip of an axle with a diameter of 0.07-0.15 mm. Artificial crystals of these substances are very durable and are very little abraded by steel. It is remarkable that artificial stones turn out to be better than the same natural stones.

However, the growth of single crystals of semiconductors - silicon and germanium - is of the greatest importance for industry.

The influence of pressure on the melting point

If the pressure is changed, the melting point will also change. We met with the same regularity when we talked about boiling. The more pressure; the higher the boiling point. As a rule, this is also true for melting. However, there are a small number of substances that behave anomalously: their melting point decreases with increasing pressure.

The fact is that the vast majority of solids are denser than their liquids. The exception to this dravil is precisely those substances whose melting point does not change quite normally with a change in pressure, for example, water. Ice is lighter than water, and the melting point of ice decreases as pressure increases.

Compression promotes the formation of a denser state. If a solid is denser than a liquid, then compression helps solidify and prevents melting. But if melting is hampered by compression, then this means that the substance remains solid, whereas earlier at this temperature it would have already melted, i.e., with increasing pressure, the melting point increases. In the anomalous case, the liquid is denser than the solid, and the pressure helps the formation of the liquid, i.e., lowers the melting point.

The effect of pressure on the melting point is much less than that of boiling. An increase in pressure by more than 100 kgf / cm 2 lowers the melting point of ice by 1°C.

Why do skates glide only on ice, but not on equally smooth parquet? Apparently, the only explanation is the formation of water, which lubricates the skate. To understand the contradiction that has arisen, we need to remember the following: blunt skates slide very poorly on ice. Skates need to be sharpened to cut ice. In this case, only the tip of the edge of the ridge presses on the ice. The pressure on the ice reaches tens of thousands of atmospheres, the ice still melts.

Evaporation of solids

When they say "a substance evaporates", they usually mean that a liquid evaporates. But solids can also evaporate. Sometimes the evaporation of solids is called sublimation.

The evaporating solid is, for example, naphthalene. Naphthalene melts at 80°C and evaporates at room temperature. It is this property of naphthalene that allows it to be used to exterminate moths.

A fur coat covered with naphthalene is saturated with naphthalene vapor and creates an atmosphere that moths cannot stand. Any smelling solid sublimes to a large extent. After all, the smell is created by molecules that have broken away from the substance and reached our nose. However, there are more frequent cases where the substance is sublimated to an insignificant degree, sometimes to a degree that cannot be detected even by very careful research. In principle, any solid substance (precisely any, even iron or copper) evaporates. If we do not detect sublimations, this only means that the density of the saturating vapor is very low.

It can be seen that a number of substances that have a pungent odor at room temperature lose it at low temperature.

The density of saturated vapor in equilibrium with a solid increases rapidly with increasing temperature. We illustrated this behavior with the curve for ice shown in Fig. 4.10. True, the ice does not smell ...

Rice. 4.10

In most cases, it is impossible to significantly increase the density of saturated vapor of a solid for a simple reason - the substance will melt earlier.

The ice also evaporates. This is well known to housewives who hang out wet laundry to dry in cold weather. The water first freezes, and then the ice evaporates, and the laundry turns out to be dry.

triple point

So, there are conditions under which vapor, liquid and crystal can exist in pairs in equilibrium. Can all three states be in equilibrium? Such a point on the pressure-temperature diagram exists, it is called triple. Where is she?

If you place water with floating ice in a closed vessel at zero degrees, then water (and "ice") vapors will begin to flow into the free space. At a vapor pressure of 4.6 mm Hg. Art. Evaporation will stop and saturation will begin. Now the three phases - ice, water and steam - will be in equilibrium. This is the triple point.

The relationship between the various states is clearly and clearly shown by the diagram for water shown in fig. 4.11.

Rice. 4.11

Such a diagram can be constructed for any body.

The curves in the figure are familiar to us - these are equilibrium curves between ice and steam, ice and water, water and steam. As usual, pressure is plotted vertically, and temperature is plotted horizontally.

The three curves intersect at the triple point and divide the diagram into three areas - the living spaces of ice, water and water vapor.

The state diagram is a concise reference. Its purpose is to answer the question of what state of the body is stable at such and such a pressure and such and such a temperature.

If water or steam is placed in the conditions of the "left region", they will become ice. If a liquid or a solid body is introduced into the "lower region", then steam will be obtained. In the "right region" the vapor will condense and the ice will melt.

The diagram of the existence of phases allows you to immediately answer what happens to the substance when heated or when compressed. Heating at a constant pressure is shown as a horizontal line in the diagram. A dot moves along this line from left to right, representing the state of the body.

The figure shows two such lines, one of them is heating at normal pressure. The line lies above the triple point. Therefore, it will cross first the melting curve, and then, outside the drawing, the evaporation curve. Ice at normal pressure will melt at 0°C, and the resulting water will boil at 100°C.

The situation will be different for ice heated at very low pressure, say just below 5 mm Hg. Art. The heating process is represented by a line below the triple point. The melting and boiling curves do not intersect with this line. At such a slight pressure, heating will lead to a direct transition of ice into steam.

On fig. 4.12, the same diagram shows what an interesting phenomenon will occur when water vapor is compressed in the state marked with a cross in the figure. The steam will first turn into ice and then melt. The figure allows you to immediately tell at what pressure the growth of the crystal will begin and when the melting will occur.

Rice. 4.12

State diagrams of all substances are similar to each other. Large, from an everyday point of view, differences arise due to the fact that the location of the triple point on the diagram can be very different for different substances.

After all, we exist near "normal conditions", that is, primarily at a pressure close to one atmosphere. How the triple point of matter is located in relation to the line of normal pressure is very important for us.

If the pressure at the triple point is less than atmospheric, then for us, living in "normal" conditions, the substance is melting. When the temperature rises, it first turns into a liquid, and then boils.

In the opposite case - when the pressure at the triple point is higher than atmospheric - we will not see liquid when heated, the solid will directly turn into vapor. This is how "dry ice" behaves, which is very convenient for ice cream sellers. Blocks of ice cream can be shifted with pieces of "dry ice" and not be afraid that the ice cream will become wet. "Dry ice" is solid carbon dioxide CO 2 . The triple point of this substance lies at 73 atm. Therefore, when solid CO 2 is heated, the point representing its state moves horizontally, crossing only the evaporation curve of the solid (just like for ordinary ice at a pressure of about 5 mm Hg).

We have already told the reader how one degree of temperature is determined on the Kelvin scale, or, as the SI system now requires, one kelvin. However, it was about the principle of determining the temperature. Not all metrology institutes have ideal gas thermometers. Therefore, the temperature scale is built with the help of equilibrium points fixed by nature between different states of matter.

The triple point of water plays a special role in this. The degree Kelvin is now defined as 273.16th of the thermodynamic temperature of the triple point of water. The triple point of oxygen is taken equal to 54.361 K. The solidification temperature of gold is set to 1337.58 K. Using these reference points, any thermometer can be accurately calibrated.

The same atoms, but ... different crystals

The matte black soft graphite we write with and the brilliant, transparent, hard, glass-cutting diamond are built from the same carbon atoms. Why are the properties of these two identical substances so different?

Recall the lattice of layered graphite, each atom of which has three nearest neighbors, and the lattice of diamond, whose atom has four nearest neighbors. This example clearly shows that the properties of crystals are determined by the mutual arrangement of atoms. Graphite is used to make refractory crucibles that can withstand temperatures up to two to three thousand degrees, and diamond burns at temperatures above 700 ° C; the density of diamond is 3.5, and that of graphite is 2.3; graphite conducts electricity, diamond does not, etc.

It is not only carbon that has this feature of producing different crystals. Almost every chemical element, and not only an element, but any chemical substance, can exist in several varieties. Six varieties of ice, nine varieties of sulfur, four varieties of iron are known.

When discussing the state diagram, we did not talk about different types of crystals and drew a single area of ​​a solid body. And this area for very many substances is divided into sections, each of which corresponds to a certain "grade" of a solid body or, as they say, a certain solid phase (a certain crystalline modification).

Each crystalline phase has its own region of stable state, limited by a certain range of pressures and temperatures. The laws of transformation of one crystalline variety into another are the same as the laws of melting and evaporation.

For each pressure, you can specify the temperature at which both types of crystals will peacefully coexist. If the temperature is increased, a crystal of one kind will turn into a crystal of the second kind. If the temperature is lowered, the reverse transformation will occur.

In order for red sulfur to turn yellow at normal pressure, a temperature below 110 ° C is needed. Above this temperature, up to the melting point, the arrangement of atoms characteristic of red sulfur is stable. The temperature drops, the vibrations of the atoms decrease, and, starting from 110 ° C, nature finds a more convenient arrangement of atoms. There is a transformation of one crystal into another.

No one came up with names for six different ices. So they say: ice one, ice two, ...., ice seven. How about seven, if there are only six varieties? The fact is that ice four was not detected during repeated experiments.

If water is compressed at a temperature of about zero, then at a pressure of about 2000 atm ice five is formed, and at a pressure of about 6000 atm ice six is ​​formed.

Ice two and ice three are stable at temperatures below zero degrees.

Ice seven - hot ice; it occurs when hot water is compressed to pressures of about 20,000 atm.

All ice, except ordinary ice, is heavier than water. Ice produced under normal conditions behaves anomalously; on the contrary, ice obtained under conditions different from the norm behaves normally.

We say that each crystalline modification is characterized by a certain area of ​​existence. But if so, how do graphite and diamond exist under the same conditions?

Such "lawlessness" in the world of crystals is very common. The ability to live in "foreign" conditions for crystals is almost the rule. If in order to transfer a vapor or a liquid to other areas of existence, one has to resort to various tricks, then a crystal, on the contrary, can almost never be forced to remain within the boundaries assigned to it by nature.

Overheating and supercooling of crystals are explained by the difficulty of converting one order into another under conditions of extreme crowding. Yellow sulfur should turn red at 95.5°C. With more or less rapid heating, we will "skip" this transformation point and bring the temperature up to the melting point of sulfur 113°C.

The true transformation temperature is easiest to detect when the crystals come into contact. If they are closely placed one on top of the other and kept at 96°C, then the yellow will be eaten by the red, and at 95°C the yellow will absorb the red. In contrast to the "crystal-liquid" transition, the "crystal-crystal" transformations are usually delayed both during supercooling and overheating.

In some cases, we are dealing with such states of matter, which would be supposed to live at completely different temperatures.

White tin should turn gray when the temperature drops to +13°C. We usually deal with white tin and know that nothing is done with it in winter. It perfectly withstands hypothermia of 20-30 degrees. However, in severe winter conditions, white tin turns into gray. Ignorance of this fact was one of the circumstances that ruined Scott's expedition to the South Pole (1912). The liquid fuel taken by the expedition was in vessels brazed with tin. In great colds, white tin turned into a gray powder - the vessels were unsoldered; and the fuel spilled out. No wonder the appearance of gray spots on white tin is called tin plague.

Just as in the case of sulfur, white tin can be turned into gray at a temperature just below 13 ° C; if only a tiny grain of the gray variety falls on a pewter object.

The existence of several varieties of the same substance and delays in their mutual transformations are of great importance for technology.

At room temperature, iron atoms form a body-centered cubic lattice in which the atoms occupy positions at the vertices and in the center of the cube. Each atom has 8 neighbors. At high temperatures, iron atoms form a denser "packing" - each atom has 12 neighbors. Iron with 8 neighbors is soft, iron with 12 neighbors is hard. It turns out that it is possible to obtain iron of the second type at room temperature. This method - hardening - is widely used in metallurgy.

Hardening is carried out very simply - a metal object is red-hot, and then thrown into water or oil. Cooling occurs so rapidly that the transformation of the structure, which is stable at high temperature, does not have time to occur. Thus, a high-temperature structure will exist indefinitely under conditions unusual for it: recrystallization into a stable structure proceeds so slowly that it is practically imperceptible.

Speaking about the hardening of iron, we were not entirely accurate. Steel is tempered, i.e. iron containing fractions of a percent of carbon. The presence of very small carbon impurities delays the transformation of hard iron into soft and allows hardening. As for completely pure iron, it is not possible to harden it - the transformation of the structure has time to occur even with the most abrupt cooling.

Depending on the type of state diagram, by changing the pressure or temperature, certain transformations are achieved.

Many crystal-to-crystal transformations are observed with a change in pressure alone. In this way, black phosphorus was obtained.

Rice. 4.13

It was possible to turn graphite into diamond only by using both high temperature and high pressure at the same time. On fig. 4.13 shows the state diagram of carbon. At pressures below ten thousand atmospheres and at temperatures below 4000 K, graphite is a stable modification. Thus, the diamond lives in "foreign" conditions, so it can be easily turned into graphite. But the inverse problem is of practical interest. It is not possible to carry out the transformation of graphite into diamond only by increasing the pressure. The phase transformation in the solid state apparently proceeds too slowly. The appearance of the state diagram suggests the correct solution: increase the pressure and heat at the same time. Then we get (right corner of the diagram) molten carbon. Cooling it at high pressure, we must get into the area of ​​the diamond.

The practical possibility of such a process was proved in 1955, and at present the problem is considered to be technically solved.

Amazing Liquid

If you lower the body temperature, then sooner or later it will harden and acquire a crystalline structure. It does not matter at what pressure the cooling occurs. This circumstance seems quite natural and understandable from the point of view of the laws of physics, with which we have already become acquainted. Indeed, by lowering the temperature, we reduce the intensity of thermal motion. When the movement of molecules becomes so weak that it no longer interferes with the forces of interaction between them, the molecules line up in a neat order - they form a crystal. Further cooling will take away from the molecules all the energy of their movement, and at absolute zero the substance must exist in the form of resting molecules arranged in a regular lattice.

Experience shows that all substances behave in this way. All, except for one and only: such a "freak" is helium.

We have already given the reader some information about helium. Helium holds the record for its critical temperature. No substance has a critical temperature lower than 4.3 K. However, this record in itself does not mean anything surprising. Another thing is striking: by cooling helium below the critical temperature, reaching almost absolute zero, we will not get solid helium. Helium remains liquid even at absolute zero.

The behavior of helium is completely inexplicable from the point of view of the laws of motion we have outlined and is one of the signs of the limited validity of such laws of nature, which seemed to be universal.

If the body is liquid, then its atoms are in motion. But after all, having cooled the body to absolute zero, we took away all the energy of movement from it. We have to admit that helium has such an energy of motion that cannot be taken away. This conclusion is incompatible with the mechanics we have been dealing with so far. According to this mechanics we have studied, the movement of a body can always be slowed down to a complete stop by taking away all its kinetic energy; in the same way, it is possible to stop the movement of molecules by taking away their energy when they collide with the walls of a cooled vessel. For helium, such mechanics is clearly not suitable.

The "strange" behavior of helium is an indication of a fact of great importance. We first met with the impossibility of applying in the world of atoms the basic laws of mechanics, established by direct study of the motion of visible bodies, laws that seemed to be the unshakable foundation of physics.

The fact that helium "refuses" to crystallize at absolute zero cannot be reconciled in any way with the mechanics we have studied so far. The contradiction with which we met for the first time - the disobedience of the world of atoms to the laws of mechanics - is only the first link in the chain of even sharper and sharper contradictions in physics.

These contradictions lead to the need to revise the foundations of the mechanics of the atomic world. This revision is very profound and leads to a change in our entire understanding of nature.

The need for a radical revision of the mechanics of the atomic world does not mean that we should put an end to the laws of mechanics we have studied. It would be unfair to force the reader to learn unnecessary things. The old mechanics is completely valid in the world of large bodies. Already this is enough to treat the relevant chapters of physics with full respect. However, it is also important that a number of laws of the "old" mechanics pass into the "new" mechanics. This includes, in particular, the law of conservation of energy.

The presence of "irremovable" energy at absolute zero is not a special property of helium. Turns out; "zero" energy is present in all substances.

Only in helium this energy is enough to prevent the atoms from forming the correct crystal lattice.

It is not necessary to think that helium cannot be in a crystalline state. For the crystallization of helium, it is only necessary to increase the pressure to about 25 atm. Cooling carried out at a higher pressure will lead to the formation of solid crystalline helium with quite ordinary properties. Helium forms a face-centered cubic lattice.

On fig. 4.14 shows a diagram of the state of helium. It differs sharply from the diagrams of all other substances in the absence of a triple point. The melting and boiling curves do not intersect.

Rice. 4.14

And this unique state diagram has one more feature: there are two different helium liquids. What is their difference - you will learn a little later.

Above all liquids, as a result of their evaporation, an equilibrium is established between liquid and vapor, and, consequently, a certain vapor pressure. The magnitude of this pressure depends on the nature of the liquid and on the temperature. With an increase in temperature, the kinetic energy of the molecules in the liquid increases, an increasing number of them are able to pass into the gas phase and, consequently, the vapor pressure above the liquid increases (Figure 4).

Figure 4 - Water vapor pressure curve

The temperature at which the vapor pressure becomes equal to the external pressure is called boiling point. The point of intersection (Figure 4) of the horizontal line corresponding to a pressure of 760 mm Hg. Art., and the vapor pressure curve corresponds to the boiling point at normal pressure. Any liquid that does not decompose when heated to a temperature at which the vapor pressure becomes 760 mm Hg. Art., has its own characteristic boiling point at normal atmospheric pressure. Figure 4 also shows that at a pressure of 200 mm Hg. Art. water would boil at about 66°C. This dependence of the boiling point on pressure is used in laboratory practice and industry for distillation without decomposition of substances boiling at high temperatures (vacuum distillation). In a number of reference and teaching aids, nomograms are given that make it possible to relate the boiling points at atmospheric pressure and in vacuum, i.e., to determine the maximum residual pressure that must be in the distillation plant so that the substance is distilled below its decomposition temperature (see. for example, /3, p. 32/).

Other modifications of distillation serve the same purpose (purification of high-boiling substances). For example, steam distillation makes it possible to distill a high-boiling substance at atmospheric pressure, but the vapor pressure above the liquid surface, which is equal to atmospheric pressure, is the sum of the partial pressures of the substance itself and water vapor. Water vapor in this method is blown (sparged) through the thickness of the substance in the distillation cube.

In most cases, the determination of the boiling point is carried out during the distillation of a substance during its purification. If necessary, the determination of the boiling point of a small amount of liquid can be used Sivolobov's micromethod(Figure 6).

To carry it out, you can use the standard device for determining the melting point described above (Figure 5). A drop of liquid is placed into a thin-walled glass tube (6) sealed at one end (diameter ~ 3 mm). A capillary (4), sealed from the upper end, is lowered into the tube, the tube is attached to the thermometer with an elastic band (5) and heated in the device until bubbles begin to emerge from the capillary in a continuous stream. Note the temperature at which continuous bubbling began. It corresponds to the boiling point of the liquid. Be sure to record the barometric pressure. By the value of the boiling point, a substance can be identified and its purity can be determined.