Dr. Mandar M.

Lele

Pure Substance
Pure Substance is one with uniform and invariant chemical composition. Eg: Elements and chemical compounds are pure substances. (water, stainless steel) Mixtures are not pure substances. (eg: Humid air)
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Dr. Mandar M. Lele

Pure Substance
Exception!! Air is treated as a pure substance though it is a mixture of gases. In a majority of cases a minimum of two properties are required to define the state of a system. The best choice is an extensive property and an intensive property
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Dr. Mandar M. Lele

Properties of Substance
Gibbs Phase Rule determines what is expected to define the state of a system F=C+2-P F= Number of degrees of freedom (i.e.., no. of properties required) C= Number of components P= Number of phases E.g.: Nitrogen gas C=1; P=1. Therefore, F=2

Dr. Mandar M. Lele

Properties of Substance
To determine the state of the nitrogen gas in a cylinder two properties are adequate. A closed vessel containing water and steam in equilibrium: P=2, C=1 Therefore, F=1. If any one property is specified it is sufficient. A vessel containing water, ice and steam in equilibrium P=3, C=1 therefore F=0. The triple point is uniquely defined.

Dr. Mandar M. Lele

Properties of Liquids
The most common liquid is water. It has peculiar properties compared to other liquids. Solid phase is less dense than the liquid phase (ice floats on water) Water expands on cooling ( a fully closed vessel filled with water will burst if it is cooled below the freezing point). The largest density of water near atmospheric pressure is at 4c.
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Dr. Mandar M. Lele

Properties of Liquids
The zone between the saturated liquid and the saturated vapour region is called the two phase region - where the liquid and vapour can co-exist in equilibrium.

Dr. Mandar M. Lele

Quality or Dryness Fraction

If in 1kg of liquid-vapour mixture, x kg is the mass of vapour and (1- x) kg of mass of liquid, then x is known as the quality or dryness fraction of the liquid-vapour mixture. Therefore, quality indicates the mass fraction of vapour in a liquid vapour mv mixture , or

x=

mv + ml

Where, mv = mass of vapour ml = mass of liquid

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Dr. Mandar M. Lele

Quality or Dryness Fraction

The value of x varies between 0 and 1. For saturated water when water just starts boiling, x = 0, and for saturated vapour, when vaporization is complete, x = 1, for which the vapour is said to be dry saturated.
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Dr. Mandar M. Lele

Dr. Mandar M. Lele

Characteristics of the critical point

It is the highest temperature at which the liquid and vapour phases can coexist. At the critical point hfg ,ufg and vfg are zero. Liquid vapour meniscus will disappear. Specific heat at constant pressure is infinite. A majority of engineering applications (eg: steam based power generation; Refrigeration, gas liquefaction) involve thermodynamic processes close to saturation.
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Dr. Mandar M. Lele

Characteristics of the critical point

The simplest form of vapour pressure curve is ln p= A+B/T valid only near the triple point.(Called Antoines equation) The general form of empirical vapour pressure curve is ln p=ln pc+ [A1(1-T/Tc) + A2(1-T/Tc)1.5+ A3(1T/Tc)2+]/(T/Tc) (Called the Wagners equation) Definitions: Reduced pressure pr =p/pc; Reduced temperature Tr =T/Tc
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Dr. Mandar M. Lele

Characteristics of the critical point

For saturated phase often its enthalpy is an important property. Enthalpy-pressure charts are used for refrigeration cycle analysis. Enthalpy-entropy charts for water are used for steam cycle analysis. Note: Unlike pressure, volume and temperature which have specified numbers associated with it, in the case of internal energy, enthalpy (and entropy) only changes are required. Consequently, a base (or datum) is defined - as you have seen in the case of water.
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Dr. Mandar M. Lele

Let V be total volume of liquid vapour mixture of quality x, Vf the volume of saturated liquid and Vg the volume of saturated vapour, the corresponding masses being m, mf and mg respectively. Now, m = mf + mg V = V f + Vg So, m v = mf vf + mg vg = (m mg) vf + mg vg
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Dr. Mandar M. Lele

mg mg v = 1 vg vf + m m v = (1 x) v f + x vg m vg = specific volume of saturated vapour v f = specific volume of saturated liquid v = specific volume of mixture of quality x
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where, x =

mg

Dr. Mandar M. Lele

Similarly s = (1 x) s f + x s g h = (1 x) h f + x hg u = (1 x) u f + x u g

Where s, h, u refer to the mixture of quality x. the suffix f and g indicates the conditions of Saturated liquid and saturated vapour respectively
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Dr. Mandar M. Lele

v = (1 x) v f + x vg v = v f + x (vg v f ) v = v f + x v fg Similarly, h = h f + x h fg s = s f + x s fg u = u f + x u fg
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Dr. Mandar M. Lele

However ,

f + x fg

Volume fraction of vapour or voidage, vg = v m = mg + m f

v = f v f + g v g = f (v v g ) + g v g = (1 ) f + g
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Dr. Mandar M. Lele

Steam Tables
The properties of water are arranged in the steam tables as function of pressure and temperature. Separate tables are provided to give the properties of water in the saturation states and in the liquid vapour phases. The internal energy of saturated water at the triple point (t = 0.01 0C) is arbitrarily chosen zero. Since h = u + pv, enthalpy of saturated water at 0.01 0C is slightly positive because of the small value of (pv) term. The entropy of saturated water is also chosen to be zero at the triple point
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Dr. Mandar M. Lele

Saturation States
When a liquid and its vapour are in equilibrium at certain pressure and temperature, only the pressure or the temperature is sufficient to identify the saturation state. If pressure is given, the temperature of the mixture gets fixed, which is known as saturation temperature, or if the temperature is given, the saturation pressure gets fixed. Saturation liquid or saturated vapour has only on independent variable, i.e. only one property is required to b known to fix up the state.
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Dr. Mandar M. Lele

Liquid Vapour Mixture

Let us consider a mixture of saturated liquid water and water vapour in equilibrium at pressure p and temperature t. The composition of the mixture by mass will be given by its quality x

v = v f + x v fg u = u f + x u fg h = h f + x h fg s = s f + x s fg
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Dr. Mandar M. Lele

Superheated Vapour
When the temperature of vapour is greater than the saturation temperature corresponding to given pressure, the vapour is said to be superheated. The difference between the temperature of superheated vapour and saturated temperature at that pressure is called the superheat or degree of superheat i.e. (tsup-tsat)
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Dr. Mandar M. Lele

Compressed Liquid
When the temperature of liquid is less than the saturation temperature corresponding to given pressure, the liquid is called compressed liquid. The properties of liquid vary little with pressure- so the properties are taken from the saturation tables at the temperature of compressed liquid The difference between the temperature of subcooled liquid and saturated temperature at that pressure is called as subcooling or degree of subcoolingi.e. (tsat-tsub)
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Dr. Mandar M. Lele

Charts for Thermodynamic Properties

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Dr. Mandar M. Lele

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Dr. Mandar M. Lele

Superheating and Subcooling T-s chart

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Dr. Mandar M. Lele

The presentation of properties of substances in the form of a chart has certain obvious advantages. The manner of variation of properties is clearly demonstrated in the chart and there is no problem of interpolation. T-s chart its scale is small and limited in use. h-s plot or Mollier chart has a larger scale to provide data suitable for many computations
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Dr. Mandar M. Lele

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Dr. Mandar M. Lele

Measurement of Steam Quality

The state of a pure substance gets fixed if two independent properties are given. A pure substance is thus said to have two degrees of freedom. Of all thermodynamic properties, it is easiest to measure the pressure and temperature of a substance. Therefore, whenever pressure and temperature are independent properties, it is the practice to measure them to determine that state of the substance.
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Dr. Mandar M. Lele

Measurement of Steam Quality

This is done in the compressed liquid region or the superheated vapour region where the measured values of pressure and temperature would fix up the state. But when the substance is in the saturation state or twophase region the measured values of pressure and temperature could apply equally well to saturated liquid point f, saturated vapour point g, or to mixtures of any quality, points x1, x2, x3 Of the two properties, p and t, only one is independent; the other is a dependent property. 29

Dr. Mandar M. Lele

Measurement of Steam Quality

If pressure is given, the saturation temperature gets automatically fixed for the substance, In order to fix up the state of the mixture, apart from either pressure or temperature, one more property, such as specific volume, enthalpy or composition of the mixture (quality) is required to be known. Since it is relatively difficult to measure the specific volume of a mixture, devices such as calorimeters are used for determining the quality or the enthalpy of the mixture.

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Dr. Mandar M. Lele

Measurement of Steam Quality

In the measurement of quality, the object is always to bring the state of the substance from the twophase region to the single-phase or superheated region, , where both pressure and temperature are independent, and measured to fix the state, either by adiabatic throttling or electric heating.
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Dr. Mandar M. Lele

Measurement of Steam Quality

Types of Calorimeters used for measurement of Steam Quality Barrel Calorimeter Separating Calorimeter Throttling Calorimeter Combined Separating and Throttling calorimeter Electrical Calorimeter

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Dr. Mandar M. Lele

Barrel Calorimeter

Dryness fraction of steam can be found out very conveniently by barrel calorimeter as shown in figure. A vessel contains a measured quantity of water. Also water equivalent of the vessel is determined experimentally and stamped platform of weighing machine. Sample of steam is passed through the sampling tube into fine exit holes for discharge of steam in the cold water.

The steam gets condensed and the temperature of water rises. The weighing machine gives the steam condensed.
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Dr. Mandar M. Lele

From the law of conservation of energy,

Heat Lost = HeatGain m {x hfg +(ts t2)}= Cp M (t2 t1) x= Cp{M m(t2 t1) (ts t2)} hfg

where, x = quantity of steam in the main pipe hfg = latent heat of vaporization at pressure p Cp = specific heat of water at constant pressure p m = mass of steam condensed M =Equivalent mass of water at commencement tS =Sat. temperature; t1 = temperature of Water at commencement t2 = final temperature after steam has condensed
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Dr. Mandar M. Lele

Separating Calorimeter The condensate thus collected in collector tank and dry steam moves upwards to condenser

The wet steam enters at the top from the main steam pipe through holes in the sampling pipe facing up stream which should be as far as possible downstream from elbows and valves to ensure representative sample of steam when in operation the wet steam entering passes down the central passage and undergoes a sudden reversal of direction of motion when strikes perforated cup.
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Dr. Mandar M. Lele

Advantages: Quick determination of dryness fraction of very wet steam Disadvantages: It leads to inaccuracy due to incomplete separation of water Dryness fraction calculated is always greater than actual

Separating Calorimeter

mv x= mv + ml

Where, mv = mass of steam read from gauge of condenser and weighed ml = mass of water separated in specific time interval
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Dr. Mandar M. Lele

Throttling Calorimeter

In the throttling calorimeter, a sample of wet steam of mass m and at pressure P1 is taken from the steam main through a perforated sampling tube .Then it is throttled by the partially-opened valve (or orifice) to a pressure P2 measured by mercury manometer, and temperature t2, so that after throttling the steam is in the superheated region

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Dr. Mandar M. Lele

The process is shown on the T-s and h-s

Throttling Calorimeter

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Dr. Mandar M. Lele

The steady flow energy equation gives the enthalpy after throttling as equal to enthalpy before throttling. The initial and final equilibrium states 1 and 2 are joined by a dotted line since throttling is irreversible (adiabatic but not isentropic) and the intermediate states are non-equilibrium states not describable by thermodynamic coordinates. The initial state (wet) is given by P1and x1 and the final state by P2 and t2 (superheated).
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Dr. Mandar M. Lele

Now

h1 = h2 h f p1 + x1 h fg p1 = h2 or x1 =
Throttling Calorimeter With P2 and t2 being known, h2 can be found out from the superheated steam table. The values of hf and hfg are taken from the saturated steam table corresponding to pressure P1. Therefore, the quality of the wet steam x1 can be calculated.
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h2 h f p1 h fg p1

Dr. Mandar M. Lele

For example, if P2 = 1 atm., then t2 = 105C and the state 2 after throttling gets fixed as shown in above Fig.. From state 2, the constant enthalpy line intersects the constant pressure P1 line at 1. Therefore, the quality x1 is the minimum quality that can be measured simply by throttling. If the quality is, say, x1than x1 then after throttling to P2 = 1 atm., the superheat after throttling is less than 5C. If the quality is x1 then throttling to 1atm. does not give any superheat at all..
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Dr. Mandar M. Lele

To be sure that steam after throttling is in the single-phase or superheated region, a minimum of 5C superheat is desired. So if the pressure after throttling is given and the minimum 5C superheat is prescribed, then there is the minimum quality of steam (or the maximum moisture content) at the given pressure P1 which can be measured by the throttling calorimeter.
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Dr. Mandar M. Lele

Advantages: Dryness fraction of very dry steam can be found out easily Disadvantages: It is not possible to find dryness Throttling Calorimeter fraction of very wet steam

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Dr. Mandar M. Lele

Combined Separating and Throttling calorimeter When the steam is very wet and the pressure after throttling is not low enough to take the steam to the superheated region, then a combined separating and throttling calorimeter is used for the measurement of quality.

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Dr. Mandar M. Lele

Combined Separating and Throttling calorimeter Steam from the main is first passed through a separator where some part of the moisture separates out due to the sudden change in direction and falls by gravity, and the partially dry vapour is then throttled and taken to the superheated region.
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Dr. Mandar M. Lele

Now

In Fig. process 1-2 represents the moisture separation from the wet sample of steam at constant pressure P1 and process 2-3 represents throttling to pressure P2. With P2 and t3 being measured, h3 can be found out from the superheated steam table.

h3 = h2 = h f p1 + x2 h fg p1
Therefore x2, the quality of steam after partial moisture separation can be evaluated
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Dr. Mandar M. Lele

Combined Separating and Throttling calorimeter If m kg of steam, is taken through the sampling tube in t s, m1 kg of it is separated, and m2 kg is throttled and then condensed to water and collected, then m = m1 + m2 and at state 2, the mass of dry vapour will be x2 m2. Therefore, the quality of the sample of steam at state l, x1 is given by . .

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Dr. Mandar M. Lele

Combined Separating and Throttling calorimeter

mass of dry vapour state 1 x1 = mass of liquid vapour mixture at state 1 x m = 2 2 m1 + m2

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Dr. Mandar M. Lele

Electrical Calorimeter The quality of wet steam can also be measured by an electric Calorimeter. The sample of steam is passed in steady flow through an electric heater, as shown. The electrical energy input Q should be sufficient to take 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 is the voltage across the coil, then at steady state Q = VI x 10-3 kW.

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Dr. Mandar M. Lele

Electrical Calorimeter If m is the mass of steam taken in t seconds under steady flow condition, then the steady flow energy equation for the heater (as control volume) gives w1 h1 +Q = w1h2 Where, w1 = steam flow rate in kg/s Therefore, h1 +Q/w1 =h2 h1 = hfp1 +x1 hfgp1, hence x1 can be calculated
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