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Pure substances

A pure substance is a substance of constant chemical composition throughout its mass. It is an one component system, but it may exist in one or more phases. One of the important features of pure substance is that its state can be represented as a point on a plane diagram and state changes can be recognized by curves.

A pure substance is one that has homogeneous and invariable chemical composition i.e. the substance retains its chemical composition even during a change of phase. Examples are: Water, nitrogen, helium, carbon dioxide etc. A pure substance does not have to be of a single chemical element or compound. However, a mixture of various chemical elements or compounds also qualifies as a pure substance as long as the mixture is homogeneous. A mixture of two or more phases of a pure substance is still a pure substance as long as the chemical composition of all phases is the same.

Equation of State
For a perfect gas the temperature has a definite value if the pressure and volume are fixed. This relation is known as equation of state. One such relation is PV = mRT or P v = RT.

Two property rule


It states that The state of a pure substance of given mass can be fixed by specifying two properties, provided that the system is in equilibrium and gravity, motion, electricity, magnetism and capillarity are without significant effects. This two property rule can be applied only to liquid and gaseous systems.

Energy and enthalpy of a pure substance


From first law of thermodynamics, we have, Q W = U. For a pure substance, H = U + pV.

Cv and Cp
It is the rate of change of internal energy with respect to temperature at constant volume. The characteristic of Cv are:

It is the rate of change of enthalpy with respect to temperature at constant pressure. The characteristic of Cp are:

It is a property i.e. function of state. It can be taken as constant over a range of temperature and pressure It can be specified in terms of U and T.

It is a property i.e. function of state. It is the heat transfer required to raise the temperature of unit mass of substance through one degree at constant pressure.

Types of Heating
Sensible heating: The temperature of the substance changes but the phase remains same. Example: - Sensible heating of solid, sensible heating of liquid and super heating. Latent heating: The heating process in which temperature remains constant but phase change takes place. Example: Melting process- solid to liquid, Vaporization process- liquid to vapour.

Basic definitions
Saturation Temperature: - The saturation temperature at a given pressure is the temperature at which evaporation or condensation takes place. Saturation Pressure: - For a given temperature the pressure at which evaporation takes place is called saturation pressure. Saturated liquid: -The pure substance existing completely in liquid state at saturation temperature and pressure is called or saturated liquid. Saturated vapor: - The pure substance existing completely in vapor state at saturation temperature and pressure is called saturated vapor.

Sub cooling liquid or Compressed liquid: - If the given pure substance is at a temperature less than saturation temperature at a given pressure it is called sub-cooled liquid also called as compressed liquid. Super heated Vapour: - If the vapour phase of the pure substance is at a temperature higher than saturation temperature for a given pressure it is called as superheated vapour. Degree of Superheat: - The difference between actual temperature of superheated steam and saturation temperature at a given pressure is called as degree of superheat.

P- V diagram for a pure substance


Consider a piston cylinder arrangement containing unit mass of ice at say 10C and 1 atm. If the ice is heated slowly at constant pressure, there is state change of ice into water as temperature is increased and it can be plotted on P-V coordinates.

1-2---The temperature of ice increases from 10C to 0C. The ice starts melting. The volume of ice also increases from V1 to V2. 2-3---At constant temperature of 0C, ice melts into water. At state 2, melting of ice begins and at state 3 melting ends. The volume decreases from V2 to V3. 3-4---Further addition of heat at same pressure increases the temperature of water from 0C to 100C. The volume of water increases because of thermal expansion. 4-5---The phase change from liquid to vapour occurs at constant temperature of 100C. The boiling of water starts at 4 and ends at 5 during which there is large increase in volume.

5-6 ---The vapour at state 5 is heated to superheated condition to state 6. Volume of vapour increases from V5 to V6. If the processes are reversed starting from 6, the following observations can be made while cooling. 6-5 Desuperheating process 5-4 Condensation at constant pressure (from vapour to liquid) 4-3 Sub cooling, sensible cooling of liquid. 3-2 - Freezing which is the process of converting liquid to solid. 2-1 - Sub- cooling or sensible cooling of solid phase.

In regime 1-2, water exists in solid phase, in 3-4 liquid phase and beyond 5 it exists in vapour state. During 2-3, ice absorbs latent heat of fusion and changes into liquid phase. For 4-5, water absorbs latent heat of evaporation and changes into vapour phase. The points 2, 3, 4 and 5 are known as saturated states. Saturated solid state: at state 2, solid changes into liquid at constant temperature and pressure. It also represents the end of solid phase

Saturated liquid state: at state 3 and 4, the substance (water) exists in liquid phase. Hence both points are called as saturated liquid states. Point 3 is called as saturated liquid state with respect to solidification and state 4 is known as saturated liquid state with respect to vaporization. Saturated vapour state: from point 5, saturated vapour state exist

The saturated solid line: it is the line which passes through all the saturated solid states 2. The saturated liquid lines: these are the lines passing through saturated liquid states 3 and 4. The line passing through all saturated liquid state with respect to solidification(3) is called as saturated liquid line with respect to solidification and, The line passing through all saturated liquid state with respect to vaporization(4) is called as saturated liquid line with respect to vaporization. The saturated vapour line: it is the line passing through saturated vapour states 5.

The saturated liquid line with respect to vaporization and the saturated vapor line meet a point called as critical point

The salient features of PV diagram

Solid region exists to the left of saturated solid line. Solid liquid mixture region exists between saturated solid line and saturated liquid line with respect to solidification. The compressed liquid region is present between two saturated liquid lines. Liquid vapour mixture exists between saturated liquid line with respect to vaporization and saturated vapour line. Vapour region exists to the right of saturated vapour line. Triple point is a point on PV diagram where all three phases exist in equilibrium. The substance cannot exist in liquid phase at a pressure below triple point.

If the substance at a pressure below triple point line, when it is heated, it is converted into vapour form directly from solid phase. This process is called as sublimation.

P T diagram for pure substance

This P T diagram is often called the phase diagram since all three phases are separated from each other by three lines. The sublimation line separates the solid and vapor regions. Vaporization line separate the liquid and vapor regions. The melting (or fusion) line separates the solid and liquid regions. These three lines meet at the triple point, where all three phases coexist in equilibrium.

P V T Surfaces

Any point on PVT surface represents an equilibrium state of the substance. Such a graphical representation of a pure substance is called as PVT surfaces (also called as thermodynamic surfaces)

In PVT Surfaces, pressure, specific volume and temperature are taken on mutually perpendicular axes and each possible equilibrium state is represented by a point on the surface. The regions having single phase are made curved. The regimes with two phases are drawn parallel to volume axis.

T-S Diagram for a pure substance


Consider the heating of 1 kg of ice at 50C to steam at 250C. The pressure being maintained at 1 atm. It is observed that the entropy of steam increases in different regimes of heating. Entropy increase of ice to saturated freezing temperature Entropy increase of ice as it melts into water. Entropy increase of water as it is heated from 0c to 100C. Entropy increase of water as it is vaporized at 100C absorbing latent heat of vaporization. Entropy increase of vapor as it is heated from 100C to 250C

H-S diagram (Mollier diagram) for a pure substance

The slope of an isobar on the h-s coordinates is equal to the absolute temperature. If the temperature remains constant the slope will remain constant. If the temperature increases the slope of the isobar will increase. Consider the heating of ice at 5OC to steam at 250C the pressure being maintained constant at 1 atm.

The slope of the isobar of 1 bar on the h-s coordinates first increases as the temperature of the ice increases from 5C to 0C. The slope then remains constant as ice melts to water at 0C. The slope of isobar again increases as the temperature of water rises from 0C to 100C. The slope again remains constant as water vaporizes at constant temperature. Finally the slope of the isobar continues to increase as the temperature of steam increases to 250C and beyond.

Here at a particular pressure hf is the specific enthalpy of saturated water and hg is specific enthalpy of saturated vapor and hfg(= hg - hf) is the latent heat of vaporization at that pressure. As the pressure increases hfg decreases and at the critical pressure hfg becomes zero.

Dryness fraction and various equations


Dryness fraction is defined as the ratio of mass of dry steam to total mass of steam. It is denoted by x and is also called as quality of steam. x = mg / (mg +mf ),where mg and mf are the masses of vapor and liquid respectively.

We have, m = mf + mg and V= Vf +Vg Therefore, mv = mf * vf + mg*vg ; v= (1-x) vf + x* vg. Similarly; s = (1-x) sf + x sg; h= (1-x) hf + x hg; u= (1-x) uf + x* ug. Same equations are written as: v = vf + x*vfg, h = hf + x*hfg, u = uf + x*ufg, s = sf + x*sfg

If the condition of the steam is superheated then we have degree of superheat, which is the difference between the superheated temperature to the saturation temperature for that particular pressure. super = Tsuper Tsaturation. The other properties are calculated as, vsup = vsat * Tsup / Tsat hsup = hg + Cp (Tsup-Tsat) ssup = sg + Cp log(Tsup/Tsat)

Clausius Clapeyron Equation


It enables us to determine the enthalpy change associated with a phase change (such as the enthalpy of vaporization hfg) from a knowledge of P, v, and T data alone.

Consider the third Maxwell relation, During a phase-change process, the pressure is the saturation pressure, which depends on the temperature only and is independent of the specific volume. That is, Psat = f(Tsat). It can be expressed as a total derivative (dP/dT )sat, which is the slope of the saturation curve on a P-T diagram at a specified saturation state. This slope is independent of the specific volume, and thus it can be treated as a constant during the integration of above equation between two saturation states at the same temperature.

For an isothermal liquidvapor phase-change process, for example, the integration yields,

It can be expressed in a general form as,

At low pressures vg >>vf

vg = RT/P.

Determination of dryness fraction


The quality or dryness fraction is defined as the ratio of mass of dry saturated vapor to the total mass of the mixture. Total mass of the mixture contains mass of saturated liquid and mass of saturated vapors.

Separating calorimeter

A known quantity of steam is passed through a separating calorimeter. The steam is made to change direction suddenly, the water being denser than the dry steam, it is separated out. The quantity of water, which is separated out, is measured at the separator. The dry steam coming out of the separator is sent through a condenser where it is condensed separately.

Let M = mass of dry steam condensed m = mass of suspended water separated in calorimeter in the same time.

Throttling Calorimeter

A sample of wet steam of mass m at pressure p1 is taken from the steam main through a perforated sampling tube. Then it is throttled by the partially opened valve to a pressure p2 measured by a mercury manometer and temperature t2, so that after throttling the steam is in the superheated region

Combined separating and throttling calorimeter

When the steam is very wet and the pressure after throttling is not enough to take the steam to the superheated region then a combined separating and throttling calorimeter is used for the measurement of quality. As shown in the figure, process 1-2 represents moisture separation from the wet sample of steam at constant pressure P1. process 2-3 represents throttling to pressure P2 with P2 and T3 being measured, h3 can be found out from th superheated steam table: h3 = h2 = hf1 + x2 hfg1

m = m1 + m2 The mass of dry vapor at state 2 will be x2*m2 Therefore, the quality of the sample of the steam at state 1(x1) is given by:

Electric Calorimeter

The sample of steam is passed in steady flow through an electric heater. Electrical energy input Q should be sufficient to taken the steam to the superheated region where pressure P2 and temperature T2 are measured. If I is the current flowing through the heater in amperes and V the voltage across the coil at steady state Q=VI. If m is the mass of steam taken in t seconds under steady flow condition, then the steady flow energy equation for heater is given by: m1h1 + Q = m1h2

With the known values of h2, Q and m1, h1 h1 = hf1 + x1 hfg1