<<

ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India

Phase Diagrams

1 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Increasing the temperature isobarically

T-v diagram of constant- -change processes of a pure substance at various

numerical values

are for water. 2 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Temperature - Volume diagram

3 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Pressure – Volume diagram

The pressure is gradually reduced by removing the weights

4 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India P-v-T surfaces Remembering:

(i) The State Postulate: The state of a simple compressible substance is fixed by any two independent, intensive properties

and

(ii) Any equation with two independent variables in the form z = z (x, y) represents a surface

5 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India

P-v-T Surface of a substance that expands on .

Orthogonal projection of P-v-T surface

6 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India

P-v-T Surface of a substance that contracts on freezing.

Orthogonal projection of P-v-T surface

7 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India P-v diagrams

Critical point Critical point

solid

liquid vapor

Solid +liquid Solid +liquid

liquid + vapor liquid + vapor

Triple line Triple line

solid + vapor solid + vapor

8

Substances that contract on freezing Substances that expand on freezing ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India PVT surface for ideal

9 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Phase transformations Sublimation line: Solid and Vapor phase is in equilibrium

Fusion line: Solid and Liquid phase is in equilibrium

Vaporization line: Liquid and Vapor phase is in equilibrium

Triple point: All the three phases are in equilibrium

For water,

Ttp = 0.01°C Ptp = 0.6117 kPa

Above critical point: No sharp distinction in the liquid and vapor

phases 10 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Phase diagrams Along AB line: rate at which solid sublimes to form a =rate at which gas condenses to form a solid Along BC line: rate at which liquid boils to form a gas=rate at which gas condenses to form a liquid Along BD line: rate at which solid melts to form a liquid=rate at which liquid freezes to form a solid The is the temperature and pressure at which all three phases can exist in equilibrium. Above the critical point, molecules are unable to liquify. The heat of fusion is the amount of energy given off when a substance freezes (or the amount of energy the substances requires to liquefy). The heat of is the amount of energy given off when a gas liquefies (or the amount of energy needed to vaporize the liquid).

(Note the difference between the two figures) 11 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Phase diagram of water

Allotropic forms of solid phases:

Pure substances can exist in a number of different solid phases

Pure substances can have multiple ‘triple points’ but there exists only one triple point where all the three phases can exist together.

The other ‘triple points’ can have two solid phases and one liquid phase or three solid phases

12 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India

These two examples, usually cited, as NOT due to regelation Regelation

Regelation is the phenomenon of under pressure and freezing again when the pressure is reduced.

Regelation occurs only for substances, such as , that have the property of expanding upon freezing, for the melting points of those substances decrease with increasing external pressure.

The of ice falls by 0.0072 °C for each additional atm of pressure applied. For example, a pressure of 500 atmospheres is needed for ice to

melt at −4 °C. 13 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Phase diagram of Carbon-dioxide

Therefore, the commonly observed The triple-point pressure is greater than phase- transition under conditions of normal atmospheric pressure which is atmospheric pressure of about 100 very unusual. kPa is a sublimation from solid directly to vapor, without passing At one atmosphere, we see CO either as 2 through a liquid phase, which is why a gas or as a solid. solid carbon dioxide is commonly

referred to as dry ice. 14 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Supercritical fluids

Supercritical N2

Supercritical CO2

15 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Property tables

• For most substances, the relationships among thermodynamic properties are too complex to be expressed by simple equations.

• Therefore, properties are frequently presented in the form of tables.

• Some thermodynamic properties can be measured easily, but others cannot and are calculated by using the relations between them and measurable properties.

• The results of these measurements and calculations are presented in tables in a convenient format.

In your text book, Please see Tables A-4 and A-5

Table A-4: Saturation properties of water  temperature basis Table A-5: Saturation properties of water  pressure basis

16 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Enthalpy: A new property

It’s a Combination Property

The product pressure  volume has energy units.

(N/m2 )*(m3)

The combination (u + Pv) is frequently encountered in the

analysis of control volumes. 17 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India A quick look at the property tables

Table A4/A5

18 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Table A-4

19 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Table A-5

20 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Table A-6 and A-7 vapor Compressed liquid water

21 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Van der Waals

22 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Percentage error: Equations of State

23

©Sameer Khandekar For Nitrogen ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India

Percentage error with ideal gas law

For Water 24 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Compressibility chart

25 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Compressibility chart

26 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India Compressibility chart

27 ©Sameer Khandekar ESO201A Department of Mechanical Engineering Thermodynamics Indian Institute of Technology Kanpur Instructor: Dr. Sameer Khandekar Kanpur 208016 Tel: 7038; e-mail: [email protected] India

End of Lecture

28 ©Sameer Khandekar