Thermodynamics

The Ideal Gas Law Assumptions The particles of a gas (atoms or molecules) obey Newton’s laws. Particles in the gas move with a range of speeds The volume of the individual gas particles is negligible compared to the volume of the gas. The collisions between the particles and the walls of the container and between the particles themselves are elastic (no kinetic energy lost) There are no forces between the particles (except when colliding). This means that the particles only have kinetic energy (no potential) The duration of a collision is small compared to the time between collisions. The temperature is directly proportional to the average kinetic energy of the gas particles. One mole of an ideal gas contains 6.02x10 23 particles and occupies 22.4dm 3 (L) at Standard Temperature Pressure. (STP T=0ºC and P=1.01x10 5 Pa.)

Pressure – A reminder Pressure is defined as the normal (perpendiculr) force per unit area P = F/A It is measured in Pascals, Pa (N.m -2 )

Ideal Gas Law Equation P = Pressure (N/m 2 = Pa) V = Volume n = # of moles R = Universal Gas Constant (8.31Jmol -1 K -1 ) T = Temperature (K) simulation

Graphical relationships between pressure, volume and temperature. Constant Temperature V P T P Constant Volume T V Constant Pressure

Combined Gas Law

Example 1: The internal volume of a gas cylinder is 3.0x10 -2 m 3. An ideal gas is pumped into the cylinder until the pressure is 15MPa at a temperature of 25ºC. a)Determine the number of moles of the gas in the cylinder b)Determine the number of gas atoms in the cylinder? c)Determine the average volume occupied by one atom of the gas. d)Estimate the average separation of the gas atoms.

Example 2: A sample of gas is contained in a vessel at 20ºC at a pressure P. What temperature does the gas need to be heated to in order for the pressure of the gas to be doubled if the volume remains constant?

Work done by a gas on a piston. ΔxΔx ΔVΔV A Gas

The First Law of Thermodynamics The study of processes in which thermal energy is transferred as heat and work. Applies to engines that convert thermal energy to mechanical energy. Macroscopic view of pressure, volume, temperature and internal energy in determining the state of a system.

System Engine (piston) Q=Thermal Energy (Heat) WORK ΔU = The change in internal Energy, which is an increase in temperature of the System. System Engine (piston) ΔU ↑

First Law of Thermodynamics Q = Heat added to system (+) or removed from system (-) W = Work done by system (+) or Work done on system (-). Work is done when there is a change in volume. ΔU = increase in internal energy (+) or decrease in internal energy (-). ΔU represents a temperature change. All quantities are measured in joules. Statement of conservation of ENERGY

Specific Processes and their corresponding PV graphs Isobaric Process – Pressure remains constant and work is done by (+ΔV) or on the system (- ΔV). Isochoric (isovolumetric) Process - Volume remains constant. No work is done, so there must be a change in internal energy. Isothermal Process – Temperature is constant and the pressure and volume vary inversely. Adiabatic Process – No thermal energy is added or removed from the system. (Q=0)

ProcessDefinitionPV diagram isobaricconstant pressure W=PΔV isochoricconstant volume W = 0 isothermalconstant temperature W = ? adiabatic no heat added or taken away (ΔU = W) P V P V W P V P V

Heat Engine P V D C B A D B C A simulation

Net work is done by the gas Cycle is clockwise Net work is done on the gas Cycle is counter- clockwise. Heat Engine Heat Pump or Refrigerator

Efficiency Q h = Input Heat (Joules) Q c = Exhaust Heat (Joules)

Maximum Efficiency – Carnot Cycle T h = Maximum temperature in Kelvin T c = Minimum temperature in Kelvin Maximum Efficiency