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1

Properties of Fluids

• To evaluate heat and work interactions of a

thermodynamic system, aknowledgeof properties is

essential.

• Aswell astherelationshipbetweenproperties

(P, v, T, U andHetc.)

Pure substance:

• A substancewhichhassinglechemical species

(Air isnot apuresubstance)

Phase:

• Commonly physical states of aggregation of any

substance

(a) solid(b) liquid(c) gas

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2

• Phase: Different states in which a pure substance can

exists

• Generally, A system which is uniform in chemical

compositionandphysical state, iscalledaphase.

• System consisting different phases, all phases are

separatedbyphaseboundaries.

• Thermodynamic properties of substance change abruptly

at phase boundary even though the temperature and p y g p

pressuresaresame.

• Mixturesalsoexist indifferent phases.

Example: liquid and vapour phases of alcohol-water

system

Phase Change of Water

• Consider a piston cylinder device containing

liquid water at 20°C and 1 atm pressure

• water exists in the liquid phase, is called a

compressed liquid, or a subcooled liquid.

• As temperature rises, liquid water expands

slightly, specific volume increases.

• As more heat is transferred, the temperature

keeps rising until it reaches 100°C. At this

point water is about to vaporize, called a

saturated liquid.

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3

• Once boiling starts, the temperature

stops rising until the liquid is

completelyvaporized.

• As heating continue mixture of • As heating continue, mixture of

saturated liquid and saturated

vapour exist inequillibrium.

• At end, theentirecylinder isfilledwith

vapor vapor.

• A vapor that is about to condense is

calledasaturated vapor.

• Further heating to saturated vapor,

rise of temperature and specific

volume, superheated vapour

• Again, cooling results in same

reversible process (superheated

vapour tosubcooledliquid)

• Saturation temperature and • Saturation temperature and

Saturation pressure

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4

Thermodynamic diagrams

(Phase change of pure substance)

P-T Diagrams

• Sublimation

• Fusion or melting

• Vapourization

• Critical point

For H

2

O, T

C

=374˚C &

P

C

=218 atm

• Triple point

T-V Diagram

Figure: T-V diagram for pure substance

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5

• boilingat higher temperatureat higher pressure

• Above the critical state, no line that separates the

compressedliquidandsuperheatedvapor.

• Saturatedliquidlineandsaturatedvapour linemeet at

thecritical point

• Compressed liquid region, superheated vapor region, p q g , p p g ,

saturated liquid–vapor mixture region, or the wet

region

P-V Diagram

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6

• Shapeof theP-V diagram, muchliketheT-V diagram, T=

constant linesaredownwards

• P-V linefor compressedliquidregionisalmost vertical.

• P-V linefor superheatedvapour regionislesssteep.

• For amixtureof saturatedliquidandsaturatedvapour

Qualityor drynessfraction=

Massof sat vapour / Total massof mixture Massof sat. vapour / Total massof mixture

X =m

g

/m

• Total volumeof mixtureisgivenby,

mv=(m– m

g

)v

f

+m

g

v

g

…………. (1)

Where, v

g

=specificvolumeof saturatedvapour and

v

f

=specificvolumeof saturatedliquid

v =specificvolumeof themixture

Dividebytotal massm, Dividebytotal massm,

v = (1 – X ) v

f

+ X v

g

• Put m=m

f

+m

g

inequation(1),

(m

f

+m

g

)v =m

f

v

f

+m

g

v

g

Rearranging,

(v

g

– v) / (v– v

f

) =m

f

/m

g

(lever rule)

• Similarly, specificenthalpyof aSat. liquid-vapour mixture,

h=(1– X)h

f

+Xh

g

8/31/2011

7

• Specific entropy of a liquid-vapour mixture,

s =(1 – X)s

f

+Xs

g

• Above the critical temperature, no amount of pressure can

condensethevapor toaliquid. p q

• abc

8/31/2011

8

• Table 2

• Table 3

8/31/2011

9

• Table 4

• Table 5

8/31/2011

10

Example (Use of Sat. Temp. table)

A vessel having a capacity of 0.05 m

3

contains a mixture of

saturated water and saturated steamat a temperature of 245°C.

Themassof theliquidpresent is10kg. Findthefollowing:

(i) The pressure (ii) The mass (iii) The specific volume (iv) The

ifi h l ( ) Th ifi d( i) Th ifi specific enthalpy (v) The specific entropy and (vi) The specific

internal energy.

Solution:

Given, V =0.05 m

3

, Sat. liq. vap. mixture, T =245˚C, m

f

=10 kg

From steam tables, corresponding to 245°C :

P

sat

=36.523 bar, v

f

=0.001240 m

3

/kg, v

g

=0.0546 m

3

/kg, h

f

=

1061.6 kJ /kg, h

g

=2801.6 kJ /kg, s

f

=2.748 kJ /kg K, s

g

=6.106

kJ /kgK

(i) Pressure =Sat. pressure =36.5 bar (3.65 MPa)

(ii) Mass (m):

We have, Volume of liquid =V

f

=m

f

v

f

=10 ×0.00124 =0.0124 m

3

So, Volume of vapour, V

g

=0.05 – 0.0124 =0.0376 m3

and mass of vapour =m

g

=V/v

g

=0.0376/0.0546 =0.689 kg

So, total mass of mixture =m

f

+m

g

=10 +0.688 =10.689 kg

(iii) The specific volume (v) :

Here, Quality of the mixture x =m

g

/ (m

g

+m

f

) =0.064

Now, v =x.v

g

+(1 - x)v

f

=0.00356 m

3

/kg

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11

(iv) Specific enthalpy, h :

h =x.h

g

+(1 – x).h

f

=1172.96 kJ/kg

(v) Specific entropy, s :

s =x.s

g

+(1 – x).s

f

=2.9629 kJ/kg K

g

( )

f

g

(vi) Specific internal energy, u :

u =h – pv=1172.96 – 3650 ×0.00356 =1159.97 kJ/kg

Example (Use of superheated tables)

Steam at 120 bar has a specific volume of 0.01721 m

3

/kg, find the

temperature, enthalpy and the internal energy.

Solution:

Given: Pressure of steam(p) =120 bar and specific volume (v) =

0.01721m

3

/kg

(i) Temperature:

With use of Sat. pressure steam table,

At 120 bar, v

f

=0.001527 and v

g

=0.014285 m

3

/kg

H (001721

3

/k ) > (0014285

3

/k ) Here, v

actual

(0.01721 m

3

/kg) >v

g

(0.014285 m

3

/kg)

So, steam is superheated.

From the superheat steam volume tables at 120 bar, the specific volume

is 0.01721 m

3

/kg at a temperature of 350°C.

So, steam temperature =350˚C

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12

(ii) Enthalpy:

From superheated steam enthalpy table,

Specific enthalpy at 120 bar and 350°C, h =2849.7 kJ/kg

(iii) Internal energy: ( ) gy

u =h – pv

=2849.7 – (12000)(0.01721)

=2643.18 kJ/kg

Vander waal’s Equations of State

(Real Gases)

• Manyattemptsmadetorepresent P-V-T dataaccurately.

• V WEquation:

• Takesintoaccount theeffect of volumeof molecules

• Aswell asattractionforcebetweenmolecules Aswell asattractionforcebetweenmolecules

• V WEq. cubicinmolar volume,

For T <T

C

,Threereal rootsat somePandT.

For T >T

C

,onereal andtwoimaginaryroots

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13

• Critical isotherm must show a point of inflection at

critical point.

• a = 27R

2

T

C

2

/ 64P

C

and b = RT

C

/8P

C

Compressibility Factor

• Gases deviate from ideal‐gas behavior significantly

(e.g. near the saturation region and critical point)

• Accounting of deviation from ideal‐gas behavior by

use of compressibility factor (Z)

• Defined as:

= Ideal Volume/ Actual Volume

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14

• Z = 1 for ideal gas

• For non ideal gas behaviour, Z = f(P

r

, T

r

)

Where, T

r

= Reduced temperature = T/T

c

and P

r

= Reduced pressure = P/P

c

T

c

= Critical temperature of gas

P

c

= Critical pressure of the gas

• Critical properties can be obtained from tables • Critical properties can be obtained from tables

Compressibility Charts

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15

• At very low pressures (P

r

<< 1), all gas behaviour as

ideal gas regardless of temperature.

• At high temperatures (T

r

> 2), ideal‐gas behavior can

be assumed with good accuracy regardless of

pressure (except when P

r

>> 1).

Th d i ti f f id l b h i i • The deviation of a gas from ideal‐gas behavior is

greatest in the vicinity of the critical point.

Example: Onekmol of ammoniais filledina0.1m3vessel at a

temperature of 200˚C. Using the generalized compressibility

chart determinethepressurewhichammoniaexerts.

(Given: T

C

=405.5 K, P

C

=112.77 bar)

Solution:

Here, T

r

=473/405.5 =1.17

P

r

=P / P

C

=P

ideal

(assume) / P

C

=(RT/v) / P

C

=(8.314*473.15/0.1) / 11277 =3.5

Use, generalized compressibility charts,

Z =0.57 (for P

r

=3.5 and T

r

=1.17)

So, New P =ZRT/v =(0.57* 8.314*473.15/0.1) =22423 kPa

8/31/2011

16

New P

r

=P/P

C

=22423 / 11277 =2

Again, use of generalized compressibility charts,

Z =0.52 (for P

r

=2 and T

r

=1.17)

So, New P =ZRT/v =(0.52* 8.314*473.15/0.1) =20455 kPa

And New P

r

=P/P

C

=20455 / 11277 =1.81

Again, use of generalized compressibility charts,

Z 053(for P 181andT 117) Z =0.53 (for P

r

=1.81 and T

r

=1.17)

So, New P =ZRT/v =(0.53* 8.314*473.15/0.1) =20.8 MPa

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