Thermodynamics

Some Definitions 1. A closed system contains a fixed mass of gas. The boundaries may be fixed or movable. Energy may be exchanged with the environment, but no mass enters or leaves. eg. Heat a piston which lifts a weightwork is done. 2. When one or more properties of a system change, a change of state has occurred. eg. Removing the weight on the piston decreases pressure and increases the volume of the gas. 3. A process is the path of successive states which the system undergoes (top graph on the left). 4. A cycle is the process which returns the system to its initial state (bottom graph on the left). eg. The circulation of steam in a power plant. 5. Pressure: In thermodynamic problems, we consider the absolute pressure. Gauge Atmospheric Absolute = + Pressure Pressure Pressure

Some Basic Laws 1. Zeroth Law

2. The Ideal Gas Law: The relationship seen in a low-density gas of volume , temperature , and pressure is (constant ) (constant ) { 1 (constant )

The Laws of Thermodynamics (adapted from Walker) 1. Zeroth Law: 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. eg. This is how thermometers work. 2. First Law: = + , , and are all forms of energy and they are measured in Joules (J). is the net heat added to the system. is the change in internal energy of the closed system. is the work done by the system.

Question: When you go running, you do 5.0 105 J of work, and you give off 4.0 105 J of heat. Calculate the change in internal energy, . = 4.0 105 J Heat out = +5.0 105 J Work done by the system = + = = (4.0 105 J) (+5.0 105 J) = . J Thermal Processes A reversible process occurs when the system is able to return to its original state, before the process began (ie. same , , ). For this ideal process, the system must be frictionless. Certain real processes approximate reversible processes: 1. Constant Pressure (Isobaric):

The piston moves outwards and increases the volume of the gas from i to f. The gas exerts a force on the piston, = 0 , where 0 is a constant. Since i = i and f = f, = (f i ) = 0 (f i ) = 0 f 0 i = 0 f 0 i = 0

Question 1: A gas expands from 0.60 m3 to 1.0 m3 at a constant pressure of 200 kPa. How much work does the gas do? (1 Pa (Pascal) = 1 Nm2 S.I. unit) = 0 = (200 kPa 1000 Pa ) (1.0 m3 0.60 m3 ) 1 kPa

= J = (This is the same as the area under the vs. graph, right) Question 2: A gas expands from 0.30 m3 to 0.50 m3 as the pressure increases linearly from 110 kPa to 200 kPa (heat added to system; temperature increases). Find the work done by the gas. (Note: this is NOT isobaric) = Area under vs. graph 1 = (1 + 2 ) 2 1 1000 Pa = (110 kPa + 200 kPa) ( ) (0.50 m3 0.30 m3 ) 2 1 kPa = J = J 2. Constant Volume (Isovolumetric or Isochoric): Since = 0, = 0. Thus, = . This means that heat flows into the system and the temperature increases.

Question: Find the total work done for the 3-part process.

1000 Pa Work done at (1) = (120 kPa) ( ) (0.40 m3 0.25 m3 ) = 18 000 J 1 kPa ;Work done at (2) = 0 J 1 1000 Pa Work done at (3) = (120 kPa + 180 kPa) ( ) (0.54 m3 0.40 m3 ) = 21 000 J 2 1 kPa Total work done = 18 000 J + 0 J + 21 000 J = J = kJ 3. Constant Temperature (Isothermal): For an ideal gas, the pressure varies with volume as shown on the - graph. = or =

During an isothermal process, we move along an isotherm, a line of constant temperature. Since =

for an ideal gas, we can show that the work done to go from volume i to volume f in an isothermal process is
f 1 = = = i i i f f

= [ln ]f = (ln f ln i ) i f f = ln ( ) or ln ( ) i i f = ln ( ) i or f = ln ( ) i

Note: The isothermal process happens when the volume is changed very slowly.

Question: A cylinder holds 0.50 mol of an ideal gas at 310 K. The gas expands isothermally from 0.31 m3 to 0.45 m3. What is the work done by the gas? What is the heat gained by the gas? = (0.50 mol)(8.315 J/mol K)(310 K) ln ( = + 0.45 m3 ) = J 0.31 m3

Since the temperature remains constant, = 0 = = J (heat is added to the system)

4. Adiabatic Process (no heat in or out): In an adiabatic process, the change of temperature happens in a very short time and there is no chance for heat to enter or exit the system: = + = 0 =

Question: When a gas is compressed adiabatically, the amount of work done on it is 640 J. a) Calculate the change in internal energy of the gas. = 640 J = = (640 J) = + b) If we had a mole of gas, what is its change in temperature? 3 = 2 = or 3 2

2 2(640 J) = = . 3 3(1 mol)(8.315 J/mol K) Second Law of Thermodynamics

Heat moves from hot to cold, not vice versa (unless additional energy or work is provided). Heat engines cannot be 100% efficient Entropy (disorder) of a closed system remains constant or increases. Heat Engines

Example - Graph for a Heat Engine

Thermal Efficiency Efficiency = Useful out H L = = Total in H H L H

Efficiency = 1

For an ideal engine (a.k.a. Carnot engine), the maximum efficiency possible is Carnot Efficiency = 1 L H