Unit 10

10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9

Laws of Thermodynamics and Thermal Processes

Temperature scale Thermodynamic temperature and absolute zero Gas Laws Kinetic theory The internal energy of an ideal gas Important terms used in thermodynamics The zeroth law of thermodynamics The first law of thermodynamics Thermal Processes

10.10 Specific heats for an ideal gas 10.11 The second law of thermodynamics 10.12 The third law of thermodynamics

10.1 Temperature scale

The Fahrenheit scale goes from 32 to 212 (a total of 180 divisions). The Celsius scale goes from 0 to 100 (a total of 100 divisions). Fahrenheit F Boiling of water Freezing of water
o o o o o o

Celsius C 100 0
o o

212 32
o

Now, we have 100 C correspond to 180 F , that is, 1C corresponds to 180/100 F , or 1C corresponds to (9/5) F . Here, we have a formula to relate C and F 9 TF = 32 + TC . 5 Example Two thermometers, one marked in Fahrenheit the other in Celsius, are placed in a bath. At what temperature will both thermometers read the same?
o o o o

Answer: The same reading will occur at T, where T = 5 9 (T 32) gives T = 40 .

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10.2 Thermodynamic temperature and absolute zero

Pressure versus temperature for a gas at constant volume As the gas is cooled, its atoms lose some of their thermal energy; they travel more slowly and collide with the chamber walls less frequently and less forcefully, As a result, the pressure in the chamber drops. A plot of pressure versus temperature is
o shown below. All gases show straight lines of the same intercept at 273.15 C, but

different gases have different slopes.

273.15

T ( C)

Volume versus temperature for a gas at constant pressure As the temperature of a gas is lowered, its atoms are less energetic. To keep the pressure constant, the volume must decrease, which will make it easier for atoms to strike the chamber walls frequently, thereby sustaining the pressure. All gases shrink toward zero volume at T = 273.15 C. V
o

273.15

T ( C)

 The 273.15 C is referred as the absolute zero temperature. An absolute temperature is given a SI unit, Kelvin K, in which 0 K
o o corresponds to 273.15 C; and has the same size as Celsius; therefore 0 C

corresponds to 273.15 K. In general, the temperature in Kelvin relates the Celsius degree by the relation T = TC + 273.15.

10.3 Gas Laws

Boyles law Keeping the temperature constant, the volume of a gas varies inversely with the pressure, which is equivalent to saying that pressure times volume is constant. V 1 P or PV = constant

Charless law When the pressure is kept constant, the volume of a given amount of any gas varies directly with the temperature (in Kelvin). V T or V T Gay-Lussacs law = constant

When the volume is kept constant, the absolute pressure of a given amount of any gas varies directly with the temperature (in Kelvin). PT T The ideal gas law or P = constant

As the pressure increases with the number of moles of gas molecules linearly, we have P n , where n is the number of moles of gas molecules. From the Boyles law and the Gay-Lussacs law, we have P 1 and P T respectively. Summing up the V

PV relations, we conclude that P nT , i.e. = n constant . The proportional V T constant is nearly the same for all gases at low pressures and is referred as the universal gas constant R, where R = 8.31451 J/(mol K). The ideal gas law is given by PV = n RT .

The Avogadros number NA = 6.022 10 rewritten as

23

is the number of molecules per mole, and

so nNA equals N molecules present in a sample of gas. Now, the ideal gas law can be PV = n RT = N R )T = N k T , B RT = N (N NA A where kB is the Boltzmanns constant and kB = 1.38066 10
23

J/K.

10.6

Important terms used in thermodynamics

Heat: Heat is the energy transferred between objects because of a temperature difference Thermal equilibrium: Objects that are in thermal contact, but have no heat exchange between them, are said to be in thermal equilibrium. Temperature: Temperature is the quantity that determines whether or not two objects will be in thermal equilibrium.

10.7 The zeroth law of thermodynamics

If object A is in thermal equilibrium with object C, and object B is separately in thermal equilibrium with object C, then objects A and B will be in thermal equilibrium if they are placed in thermal contact.

10.8 The first law of thermodynamics

The change in a systems internal energy, U, is related to the heat Q and the work W as follows: U = Q + W , where W = PdV . Q is positive Q is negative W is positive W is negative System gains heat System loses heat Work done on system Work done by system

It is noted that if work is done on an insulated system (i.e. Q = 0) its internal energy increases. The work done W has a positive value when the external world does work on the system (e.g. compression), and it has a negative value when work is done by the system (e.g. expansion). U = U f U i = W On the other hand, if the system does work, and / or heat is removed, its internal energy decreases.

10.9 Thermal Processes

All processes discussed in this section are assumed to be quasi-static, which means the processes occur so slowly that at any given time the system and its surroundings are essentially in equilibrium. Thus, in a quasi-static process, the pressure and temperature are always uniform throughout the system. If friction or dissipative forces are neglected, the process is considered to be reversible. For a reversible process, it must be possible to return both the system and its surroundings to exactly the same states they were in before the process began. (a) Isothermal processes Constant-temperature heat bath

Piston Piston

Consider the following reversible processes at constant temperature, the piston moves down without friction. Applying the first law of thermodynamics, U = Q + W , and making use the property of ideal gas which has its internal energy depends only on the temperature, we have U = 0 and Q = W , since the process is carried out at constant temperature. The work done, W, is positive as work is done on the system. Hence we have a negative Q, that is, heat is given out by the system to the external world. The reversed process in the figure below performs the same idea, but this time the work W is negative, as work is done by the system. Since U = 0 again, the heat Q is then positive or we conclude that heat is gained by the system from the external world.

Constant-temperature heat bath

Piston Piston

(b) Adiabatic processes A process is said to be adiabatic if there are no heat flows into or out of the system. We can have such process if the system is well insulated. The figure below is an adiabatic compression, the gas heats up and its pressure increases. Similarly, for an adiabatic expansion, the gas cools down and the pressure decrease. Example When a rod that fits snugly into a cylinder is pushed downward rapidly, the temperature of the gas increases before there is time for heat to flow out of the system. Thus, the process is essentially adiabatic. As a result, the temperature of the gas can increase enough to ignite bits of paper in the cylinder. In a diesel engine the same principle is used to ignite an air-gasoline mixture. Example An amount of gas is compressed from volume A isothermally and the PV plot is obtained as shown in curve (ii). If the same gas is compressed adiabatically, which curve would show the correct curve? Curve (i) or curve (iii)?

Answer: In an adiabatic compression, no heat change occurs in the process. According to the first law of thermodynamics, U = Q + W = W , U is positive as W is positive during compression. The increasing temperature gives an increasing pressure for a

given volume of gas. Hence, curve (iii) is the correct curve.

10.11 The second law of thermodynamics

When objects of different temperatures are brought into thermal contact, the spontaneous flow of heat that results is always from the high temperature object to the low temperature object. Spontaneous heat flow never proceeds in the reverse direction. The second law of thermodynamics is more restrictive than the first law; it says that of all processes that conserve energy, only those that proceed in a certain direction actually occur. In a sense, the second law enforces a certain directionality on the behavior of nature.

10.12 The third law of thermodynamics

The third law of thermodynamics states that there is no temperature lower than absolute zero, and that absolute zero is unattainable. It is possible to cool an object to temperatures arbitrarily close to absolute zero experiments have reached
-8 temperatures as low as 2.010 K but no object can ever be cooled to precisely 0 K.

To cool an object, you can place it in thermal contact with an object that is colder. Heat transfer will occur, with your object ending up cooler and the other object ending up warmer. In particular, suppose you had a collection of objects at 0 K to use for cooling. You put your object in contact with one of the 0-K objects and your object cools, while the 0-K object warms slightly. You continue this process, each time throwing away the warmed up 0-K object and using a new one. Each time you cool your object it gets closer to 0 K, without ever actually getting there.