7

SECTION 2 HEAT
2.1 HEAT AS ENERGY Heat is a form of energy, also called thermal energy, which can be obtained from electrical, light, chemical, and nuclear energy, as well as mechanical work. Heat is given the symbol Q, and is measured in joules, J. Heat is defined as the thermal energy transferred due to atomic collisions, from a region of high temperature to a region of low temperature. Generally, the concept of heat is only used in relation to heat transfer. When heat has been transferred to a body it is no longer called heat, but internal energy. A body cannot store heat, but its internal energy can increase. There are a number of possible effects of heat transfer to a body: the body's temperature may change; the body may undergo expansion, possibly resulting in a pressure change; or the body may undergo a change of state. 2.2 INTERNAL ENERGY Internal energy (symbol U, measured in J) is related to the kinetic and potential energy of molecules inside a body. The average kinetic energy of molecules in a body is proportional to the absolute temperature (K). The internal energy of a body can be increased or decreased by transferring heat or by transferring work. This leads to the First law of thermodynamics: Change in internal energy of a Body = heat inflow + work done on Body, or: U = Q + W Note, for heat inflow, Q > 0. For heat loss, Q < 0. The internal energy of a body will increase if heat is absorbed, or if work (i.e. a force acting through a distance) is done on the body.

8 2.3 TEMPERATURE Temperature and heat are totally different. Temperature is the property of an object which determines which way net heat flow will occur, if the object is placed in contact with another object.
Q Q

T1

T2

In the above diagram, object 1 is at T1 , and object 2 is at T2, where T1 < T2. As a result, a greater quantity of heat, Q2 > Q1,will flow from object 2 to object 1. THE ZERO'TH LAW OF THERMODYNAMICS

When two systems (A and B) are the same temperature as a third (C), it follows that all three are at the same temperature, and are in thermal equilibrium. The First Law of Thermodynamics was defined before the above statement was made, but because this statement is so fundamental to the understanding of thermodynamics, it became known as the Zero'th Law. 2.4 TEMPERATURE MEASUREMENTS Different properties are used to measure changes in temperature. The instrument used to measure the change is generally called a thermometer, while the property used is called a thermometric property. Some examples are given below:

9 Thermometric property
Change resistance in

Thermometer Type

Measured Quantity
electric current produced

electrical resistance thermometer

Expansion of liquid Expansion of solid Expansion of gas

mercury in glass Bimetallic strip constant volume gas thermom. constant pressure gas thermom.

expansion of alcohol in glass tube bending of strip pressure increases with temp. volume increases with temp.

The basic principle of all these thermometers is the same: Change in property temperature change TEMPERATURE SCALES Water is a convenient substance on which to base a temperature scale. Two fixed points are used: melting point, at which water changes to ice, and boiling point, at which water changes to steam, both at standard atmospheric pressure Patm = 101300 Pa. Anders Celsius used these two points when he developed the Celsius scale. The freezing point of water was set at 0C, while the boiling point of water was set at 100C. From now on, the Greek letter theta, , will be used in equations to represent a temperature in C. The Fahrenheit scale is used in America. The freezing point of water is 32F, while the boiling point of water is 212F. The Celsius scale () and the Fahrenheit scale (TF) are related as follows: 5 TF = 32+ 9 or = 9 ( TF 32) 5 The Absolute, Thermodynamic, or Kelvin temperature scale is based on the Celsius scale. If the pressure of a constant volume of gas is plotted as a function of temperature, a straight line is obtained. If this line is extended backwards, it will cross the x (temperature) axis at the same point: -273.16 K. The same thing happens when the volume of a gas at constant pressure is plotted as a function of temperature.
P V

-273.16C 0C 100C 200C T (C) 0K 273.16 K 473.16K

-273.16C 0C 100C 200C T (C) 0K 273.16 K 473.16K

10 The temperature at which the pressure or volume goes to zero, which we approximate to -273C, is called absolute zero. At this temperature, the gas is so cold that the atoms in the gas have absolutely no kinetic energy, i.e. the atoms in the gas do not move at all. Since the pressure of a gas in a container is due to the large number of atoms striking the container walls, atoms with zero kinetic energy exert zero pressure. In the second graph, the gas pressure stays constant, as the gas volume varies with temperature. To keep the pressure constant as the temperature nears absolute zero, the volume of the container must decrease, so that there will be enough atoms striking the walls, even as their kinetic energy nears zero. The Kelvin scale (T) is based on the Celsius scale (), so that a change of 1 K is the same as a change of 1C, even though 1C 1 K. T = + 273 e.g. 538 K = 538 - 273 = 265C. -116,4C = -116,4 + 273 = 156,6 K 2.5 THE GAS LAWS The word gas comes from a Flemish translation of the Greek word chaos. At sea level, every square centimeter of your face, and any other exposed surface is being bombarded by 3 x 1023 gas molecules every second, each moving at roughly 450 m.s-1 = 1620 km/h. Gas molecules absorb all this energy from the suns radiation. Gas molecules also tend to collide with each other 6 x 109 times every second, and have an average mean free path of 8 x 10-8 m. Because a gas expands to fill the container that confines it, gases do not undergo a simple temperature dependent volume change. In gases, the pressure (symbol P, units Pascals 1 Pa = 1 N.m-2), mass (m, units kg), volume (symbol V, units m3) and temperature (symbol T, units K) are all inter-related. To study the effect of variation of one quantity (e.g. pressure) on another quantity (e.g. volume) we need to keep the other quantities fixed. SOME OBSERVABLE PHYSICAL PROPERTIES OF GASES [1] [2] [3] [4] [5] Fill all available volume and take shape of the container. Are infinitely expandable. Are very compressible. Flow rapidly. Expand and contract with changes in temperature.

11 [6] [7] Exert greater pressure in closed container when the temperature rises. Have a low density.

KINETIC-MOLECULAR THEORY OF GASES Based on the concept of an ideal gasa gas composed of molecules that occupy neglible volume and exert no forces on each other. [1] Gases are made up of molecules that are relatively far apart; in comparison with their own volume, the spaces between them are large. Molecules are in constant random motion and the collisions with surfaces results in pressure. The average speed and average kinetic energy of the molecules are proportional to the temperature. At the same temperature all molecules of the gas have the same average kinetic energy. Collisions between gas molecules and the sides of the container are perfectly elastic.

[2]

[3]

[4]

[5]

BOYLES LAW
At constant temperature, the volume of a given mass of gas is inversely proportional to the pressure exerted upon the gas. Mathematically we can write

PV = constant
Example A sample of an ideal gas at 930 Pa and 25o C occupied a volume of 17.3 m3. This gas was transferred to a 3.7 m3 container without a temperature change. What was the pressure of the gas under the new conditions?

12

COMBINED GAS LAW

PV PV2 1 1 = 2 T T2 1
This equation holds for a fixed mass of gas.

PROBLEM SOLVING STRATEGY [1] Study the problem and be sure you understand it. a) What is known? b) What is unknown? [2] Decide how to solve the problem. a) What is the connection between the known and the unknown? c) What is necessary to make the connection? [3] [4] Set up the problem and solve it. Check the result, ie., does your answer make sense?

STANDARD TEMPERATURE AND PRESSURE Standard temperature is defined as 273 K, while standard pressure is set to the atmospheric pressure at sea level, 101300 Pa = 101,3 kPa Since volume of gas depends so much on pressure and temperature, values are often quoted at STP. 1 mole of an ideal gas at STP occupies 22,4 dm3.

13 Easy Conversion: 1 dm3 = (1 dm)3 = (10-1 m)3 = 10-3 m3 e.g. 1 Calculate the volume occupied by a given mass of nitrogen gas at 250 kPa pressure and 25C, if at standard atmospheric pressure (101,3 kPa) and at 25C this gas occupies 310 m3.

e.g. 2 A gas has a volume of 245 cm3 at 35C and 120 kPa. Calculate the volume of this gas at STP.

DALTON'S LAW OF PARTIAL PRESSURES When a number of different gases fill a container, the total pressure is equal to the sum of the pressures that each gas in the mixture would exert if it alone filled the container. P = P1 + P2 + P3 + .....

THE IDEAL GAS LAW The ideal gas law is given by the following equation. It applies to an imaginary gas whose pressure or volume decrease to 0 as its temperature decreases to 0.

PV = nRT
where the molar gas constant R = 8,314 J.mol-1.K-1 is approximately constant for all gases at normal temperatures. For very high pressures or very low temperatures, the ideal gas law fails. VALIDITY OF THE IDEAL GAS LAW The ideal gas law is set up to describe a special kind of gas whose volume will decrease to zero as its temperature decreases to zero. A typical gas would liquefy, before this happens. If we plot an isotherm (a line showing the relationship between two variables, at a constant temperature) of pressure as a function of volume, for a typical gas, such as CO2 , at some temperature greater than or equal to 31.1C, then the graph is almost an hyperbola, showing the close agreement with the ideal gas law relationship. However, if we plot pressure as a function of volume for some

14 temperature below 31.1C, we will see that decreasing the volume of this gas initially has the effect of increasing the pressure of the gas. Then, at some point, the gas starts to liquefy, and the pressure remains constant. Eventually, the entire gas has liquefied, and now, for any further decrease in volume, the pressure in the liquid increases very rapidly.

The temperature 31.1C is called the critical temperature for CO2. Above this temperature, CO2 behaves like an ideal gas, but below this temperature, it tends to liquefy for high pressures. When CO2 is at a temperature below the critical temperature of 31.1C, we say it is a vapor. Vapors can be condensed via compression - gases cannot. As the volume of the CO2 vapor decreases, the vapor becomes saturated - no more molecules can remain in the vapor state at that specific P, T and V. As the volume decreases further, the pressure no longer increases, as the vapor begins to liquefy. As the volume continues to decrease, the entire vapor will liquefy, and then the pressure of the liquid CO2 will continue to increase.

DEVIATIONS FROM THE IDEAL GAS LAW

We firstly note that real gases exhibit different characteristics from ideal gases. Real gases [1] [2] occupy volume. forces exist between molecules.
PV

Real gas

Ideal gas

Real gas molecules have a finite volume. Thus compressing a real gas at high pressure results in the molecules being pushed closer. This results in

15 increased collisions thus resulting in a pressure increase. Furthermore, the molecules themselves occupy volume thus the product PV is greater for a real gas than an ideal gas. Refer to the above graph.

16

Temperature behaviour of real and ideal gases

V Ideal gas

Real gas

temperature

CONCEPTUAL QUESTIONS [1] [2] Why is best to use helium gas in a gas thermometer as opposed to using oxygen? An inflated rubber balloon filled with air is immersed in a flask of liquid nitrogen that is at 77 K. Describe what happens to the balloon, assuming that it remains flexible while being cooled. Two cylinders are at the same temperature each contain the same kind and quantity of gas. If the volume of cylinder A is three times greater than the volume of B, what can you say about the relative pressures in the cylinders?

[3]

17 2.6 VAPORS If a liquid is placed in a closed container, some of the liquid will evaporate, forming a vapor over the liquid, exerting a small amount of pressure on the liquid and container walls. Over time, enough liquid will evaporate to saturate the air above the liquid - no more liquid will be able to evaporate without some of the vapor condensing. Thus, the molecules enter and leave the liquid state at the same rate. At this point, the vapor pressure is at the saturation vapor pressure (S.V.P.). Reducing the volume of (i.e. increasing the pressure on) a saturated vapor does not increase it's pressure - it merely makes some of the vapor condense to liquid. Similarly if the volume of a saturated vapor is increased, the pressure does not change, and more liquid evaporates. The S.V.P. of a liquid varies with temperature: TEMPERATURE 0C S.V.P (Pa) 613 5C 866 10C 1226 50C 12329 100C 101300 140C 361214

VARIATION OF S.V.P. WITH TEMPERATURE FOR WATER. BOILING A liquid boils when its S.V.P. is the same as atmospheric pressure. That is why water boils at 100C in Durban, (sea level P = 1 atm = 101300 Pa), and at lower temperatures in Johannesburg, where the atmospheric pressure is lower. At very high altitudes, such as near the top of Mount Everest, you cant boil an egg, because water boils at such a low temperature, that the protein in the egg does not reach a high enough temperature to coagulate. A pressure cooker works on this principle: water is boiled under increased pressure, which causes it to boil at temperatures greater than 100C, so cooking the food faster.

18 BOILING POINT OF A SOLUTION The boiling point of a liquid containing dissolved substances is higher than the boiling point of the pure liquid at the same atmospheric pressure. The temperature of the steam is the same temperature as for saturated steam produced by the pure liquid (at atmospheric pressure). Dissolving substances must therefore lower the S.V.P. of the solution (since the liquid boils when the S.V.P is the same as the atmospheric pressure). This is because dissolved substances hinder the escape of the molecules of the liquid.

LIQUID MOLECULES NEED MORE KINETIC ENERGY TO BREAK BONDS. Also, the reduction of the S.V.P. does not depend on the nature of the dissolved substance, but on the number of dissolved particles in relation to the total number of particles (liquid + solute molecules). KINETIC THEORY OF SATURATION Consider a container filled with a mixture of vapor and liquid. The lid of the container is a piston, with which the volume can be increased or decreased. When the piston is stationary, at constant temperature, a dynamic equilibrium exists between the vapor and the liquid (i.e. for every liquid molecule that enters the vapor state, a vapor molecule enters the liquid Vapor state). If the temperature is increased, more liquid evaporates, until another dynamic Liquid equilibrium is established. If the temperature is decreased, more vapor condenses, until dynamic equilibrium is established. If the volume of the vapor is reduced (at constant temperature), the density of the vapor molecules increases, which causes the pressure to increase, as more molecules collide with the walls per unit area. As the pressure increases, some vapor molecules enter the liquid state, however, the vapor eventually reaches saturation. At this point, a further decrease in volume causes condensation of the vapor, with no increase in pressure. It is possible to liquefy all the vapor by decreasing the volume of the container. Piston

19 TUTORIAL QUESTIONS [1] A container having a volume of 1.00 m3 contains hydrogen gas at a pressure of 200 atm. How many spheres can the container fill if each filled sphere has a diameter of 20 cm at an absolute pressure of 2atm? A room at 25o C and 100 kPa pressure has dimensions 10 m x 20 m x 30 m. How many molecules of air fill the room? A car tyre is pumped up using air at 10oC and normal atmospheric pressure. During the process, the air is compressed to 30 % of its original volume and the temperature is raised to 50o C. a) What is the tyre pressure? b) After driving the car at high speed, the temperature inside the tyre increases to 80o C and the interior volume of the tyre increases by 2%. Cal. the pressure inside the tyre. [4] A weather balloon is designed to expand to maximum radius of 20 m when in flight at its working altitude, where the air pressure is 0.03 atm and the temperature is 200 K. If the balloon is filled at atmospheric pressure and 300 K, what is the radius at lift-off? A vertical cylinder of cross-sectional area A is fitted with a tight-fitting, frictionless piston of mass m (see figure below) a) If there are n mol of an ideal gas in the cylinder at a temperature of T, determine the height h at which the piston is in equilibrium under its own weight.

[2]

[3]

[5]