Thermodynamics and Heat Transfer (ABE 2) Pure Substance > In thermodynamic systems, primary properties are necessary to define the state of a system. > Problem: to discover the thermodynamic properties necessary to define the state of the system which are known as the primary properties. The other thermodynamic properties will then be functionally related to the primary properties (independent variables). Example. > An ideal gas requires only two properties to define the state of the system. Any two of pressure, volume or temperature may be used. Phase > is any homogeneous part of a system which is physically | distinct and is separated from other parts of the system by distinct bounding surfaces Three (3) Phases of pure substances > Solid a > Liquid oe > Gas or Vapor Three (3) Phases of Water: ice, liquid water and water vapor > Aliquid solution constitutes a single phase no matter if it is homogeneous. > Ex. solution of sugar in water ( assuming that sugar is dissolved in water) > Even if solid or liquid is composed of several substances as long as solution is homogeneous then the substance is said to be a single phase ‘ When more than one phase is present, the phases are ‘separated from each other by the phase boundaries. In each phase the substance may exist at various pressures and temperatures or, to use the thermodynamic term, in various states State > may be identified or described by certain properties i.e. temperature, pressure, density _| Property > Any quantity that depends on the state of the system and is, independent of the path (the prior history) by which the system arrived at the given state Thermodynamic | Two (2) general classes properties > Intensive Property-> independer tof the uantity of matter “ (mass) t tem ex. pressure, temperature and density extensive | , Properties per unit mass: specific volume | > Extensive property> value varies directly with mass ex. mass and total volume¢ In general, an extensive property when divided by the mass of the system becomes an intensive property anc ieee Thermal equilibrium same temperature throughout the entire system Mechanical equilibrium->no tendency for the pressure at any point to change with time as long as the system is isolated from the surroundings Pure substance > one that is chemically homogeneous and invariable in chemical composition > it may exist in more than one phase but the chemical ‘composition is the same > ex. mixture of liquid water and water vapor (steam), mixture of ice and liquid water, air (mixture of mainly oxygen and nitrogen has only one phase but two components) > (liquid air + gaseous air) is no longer a pure substance because liquid air has higher fraction of nitrogen than gaseous air Two (2) phases of pure substance can coexist in equilibrium at a given temperature only if the pressure is a particular value which corresponds to that temperature. These corresponding values of pressure and temperature are called saturation pressure and saturation temperature : There is only one saturation temperature for a given saturation pressure and vice versa. Saturation condition condition under which two or more phases of a pure substance can exist together in equilibrium Phase diagram > is a pressure-temperature diagram showing more than one of the saturation lines (liquid- vapor, liquid-solid, solid-vapor or other) of a pure substance > a phase diagram for water (a substance which contracts on freezing) is shown > any point on a saturation line of a phase diagram tepresents conditions of pressure and temperature under , Which two phases are existing in equilibritT ~ cyvcaok AT agai TT superneated al acted L Pr onsont (Ane cate Tact & Toate onpreiea @ T= owen ae Some Jem fac > Fearn Tele i of water Ne be a2 Pa Temperature-Pressure diagram for water _ ‘saturation lines: solid-liquid, solid-vapor and liquid-vapor lines > all points not on a saturation line represent conditions under which only one phase of the pure substance can exist > points between the solid-liquid and liquid-vapor lines represent liquid states, and this region is called liquid region. > points to the left of the solid-vapor and solid-liquid lines represent solid states, and this region is called solid region > points to the right of the solid-vapor and liquid-vapor lines represent vapor states, and the region is now called vapor region. Subcooled liquid or compressed liquid> liquid whose temperature is lower than its saturation temperature at the same pressure actual pressure of liquid is higher than its saturation pressure at the same actual temperature all points in the liquid region and not on the liquid-vapor saturation line represent states of subcooled liquids Superheated-vapor~ vapor at a temperature higher than its saturation temperature at the same pressure Triple point (point b)> the intersection oft the vaporization line (line bd), fusion line (line bc), and subliniation line (line ab) on a pT diagram represents the conditions under which three phases can coexist in equilibrium Critical point end of the liquid-vapor line (point d) > at pressures or temperatures higher than the critical point, there is no distinction whether the substance is liquid nor vapor and the specific volume of liquid and vapor are equal Pressure-volume diagram of water (see attached diagram) % Line ab - saturated solid line> a series of saturation points at different temperatures | |> a point to the left of this line is at a higher pressure than the ‘saturation pressure at the same temperature » Line be — solid-liquid line or fusion line->when solid is slowly turning into liquid Ex. ice when exposed to the sun melt while at constant temperature of 0°C Heat of fusion> heat involved after complete change from solid to liquid All points to the right of line ab and to the left of line gh ->mixture of solid and vapor which happens during the process of sublimation solid is directly changed into vapor without passing the liquid phase happens at a relatively low pressure such as for carbon dioxide (dry ice) > Line ce — saturated liquid line->series of saturation points at different temperatures. >to the left of this line and to the right of the solid-liquid line is the subcooled liquid > Line df — liquid vapor line->when liquid turned into vapor at unchanging temperature Ex. liquid water when heated at constant pressure will vaporize at 100°C Heat of vaporization>heat involved in the vaporization process Liquid-vapor region >area enclosed by line def Point e critical point Line eh — saturated vapor line >series of saturation points at different temperatures >to the right of this line is called superheated vapor region where temperature of vapor is higher than its saturation temperature at the same pressure Ex. ice at a temperature lower than 0°C when heated will increase its temperature to its melting temperature-- 0°C further addition of heat will result to melting of ice while the temperature remains constant water at 0°C when heated will increase its temperature to 100°C only at this point that liquid will change into vapor until it becomes saturated vapor/ vy edd ab 2 pala ee sown, b ¥ Necite ped Figure 2. pv diagram for water x rie nek = a0 lose anges — Ge Mcp AT @ Du gomt Veh Tea acw ead Iie ens > @amby ane Figure 3. shows a more detailed picture of processes and changed of skates of water in three dimensions using pressure. (p), temperature (t), and specific volume (v). b1gure / i sou Figure 3. pvt diagram for water etree : eeduly ainjeseduiaj-yue suo twyaowld ayihd ~ aqeys ajduy 4odea pue A anion oe ae pinb)) pue pljos d aunssalgt BuNndsad| Criheal Point et * { / \. i Io : \/ Triple line os | € = Pd & Solid v @ Sold + Liquid = Liquid @ |iquid + Vapor @ Vapor . Pat a nota