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Chapter 12 - Thermodynamic Property Relations

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SEM 1 (2015/2016)

1

Objectives

basis for many thermodynamic relations.

• Develop the Clapeyron equation and determine

the enthalpy of vaporization from P, v, and T

measurements alone.

• Develop general relations for cv, cp, du, dh, and

ds that are valid for all pure substances and real

gases.

2

THE MAXWELL RELATIONS

The equations that relate the partial derivatives of properties P, v, T, and s

to each other of a simple compressible system are called the Maxwell relations.

They are obtained from the four Gibbs equations by exploiting the

exactness of the differentials of thermodynamic properties.

Helmholtz function

Gibbs function

valuable in thermodynamics because

they provide a means of determining

the change in entropy, which cannot

be measured directly, by simply

measuring the changes in properties P,

v, and T.

These Maxwell relations are limited to

simple compressible systems.

Maxwell relations

3

4

THE

CLAPEYRON

EQUATION

5

Clapeyron

equation

to determine the enthalpy of

vaporization hfg at a given

temperature by simply measuring

the slope of the saturation curve

on a P-T diagram and the specific

volume of saturated liquid and

saturated vapor at the given

temperature.

diagram is constant at a constant T or P.

General form of the Clapeyron

equation when the subscripts 1

and 2 indicate the two phases.

6

0.036012 – 0.0008160 0.035196 m3/kg

(0.035196 m3/kg)

182.60 kJ/kg

The Clapeyron equation can be simplified for liquid–vapor and solid–vapor

phase changes by utilizing some approximations.

At low pressures

Treating vapor as

an ideal gas The Clapeyron–Clausius

equation can be used to

Substituting these equations into the Clapeyron determine the variation of

equation saturation pressure with

temperature.

It can also be used in the

solid–vapor region by

replacing hfg by hig (the

enthalpy of sublimation) of

the substance.

Clapeyron–Clausius

equation

8

GENERAL RELATIONS FOR du, dh, ds, cv, AND cp

• The state postulate established that the state of a simple compressible system is

completely specified by two independent, intensive properties.

• Therefore, we should be able to calculate all the properties of a system such as

internal energy, enthalpy, and entropy at any state once two independent,

intensive properties are available.

• The calculation of these properties from measurable ones depends on the

availability of simple and accurate relations between the two groups.

• In this section we develop general relations for changes in internal energy,

enthalpy, and entropy in terms of pressure, specific volume, temperature, and

specific heats alone.

• We also develop some general relations involving specific heats.

• The relations developed will enable us to determine the changes in these

properties.

• The property values at specified states can be determined only after the selection

of a reference state, the choice of which is quite arbitrary. 9

Internal

Energy

Changes

10

Internal

Energy

Changes

11

The enthalpy to be a function of T and P, that is, h=h(T, P), Enthalpy

and take its total differential:

Changes

12

13

Entropy Changes

14

Specific Heats cv and cp

15

16

Mayer

relation

17

Mayer

relation

Conclusions from Mayer relation:

1. The right hand side of the equation is always

greater than or equal to zero. Therefore, we

conclude that

zero as the absolute temperature approaches

zero.

3. The two specific heats are identical for truly

incompressible substances since v constant.

The difference between the two specific heats

is very small and is usually disregarded for

substances that are nearly incompressible, such

as liquids and solids.

The volume expansivity (also called the coefficient of

volumetric expansion) is a measure of the change in

volume with temperature at constant pressure.

18

19

THE ∆h, ∆u, AND ∆s OF REAL GASES

• Gases at low pressures behave as ideal gases and obey the relation

Pv = RT. The properties of ideal gases are relatively easy to evaluate

since the properties u, h, cv, and cp depend on temperature only.

• At high pressures, however, gases deviate considerably from ideal-

gas behavior, and it becomes necessary to account for this deviation.

• In Chap. 3 we accounted for the deviation in properties P, v, and T by

either using more complex equations of state or evaluating the

compressibility factor Z from the compressibility charts.

• Now we extend the analysis to evaluate the changes in the enthalpy,

internal energy, and entropy of nonideal (real) gases, using the

general relations for du, dh, and ds developed earlier.

20

Enthalpy Changes of Real Gases

The enthalpy of a real gas, in general,

depends on the pressure as well as on

the temperature. Thus the enthalpy

change of a real gas during a process

can be evaluated from the general

relation for dh

the first term vanishes. For a constant-

pressure process, dP = 0, and the

second term vanishes.

An alternative process path to evaluate

the enthalpy changes of real gases.

21

Using a superscript asterisk (*) to denote an ideal-gas state, we can express

the enthalpy change of a real gas during process 1-2 as

departure, and it represents the variation of the

enthalpy of a gas with pressure at a fixed temperature.

The calculation of enthalpy departure requires a

knowledge of the P-v-T behavior of the gas. In the

absence of such data, we can use the relation Pv = ZRT,

where Z is the compressibility factor. Substituting,

22

Enthalpy

departure

factor

The values of Zh are presented in graphical form as a function of PR

(reduced pressure) and TR (reduced temperature) in the generalized

enthalpy departure chart.

Zh is used to determine the deviation of the enthalpy of a gas at a given P

and T from the enthalpy of an ideal gas at the same T.

For a real gas

during a

process 1-2

from ideal gas tables

Using the definition

23

Entropy Changes of Real Gases

General relation for ds

the entropy changes of real gases during

process 1-2.

24

Entropy

departure

factor

Entropy departure

pressure) and TR (reduced temperature) in the generalized entropy

departure chart.

Zs is used to determine the deviation of the entropy of a gas at a given P

and T from the entropy of an ideal gas at the same P and T.

during a

process 1-2

25

EXAMPLE 12-11

Thermodynamics Analysis with Non-Ideal Gas Properties

Propane is compressed isothermally by a piston-cylinder

device from 95˚C and 1400 kPa to 5500 kPa. Using the

generalized charts, determine the work done and the heat

transfer per unit mass of propane.

ANS:

Wb,in = 105.1 kJ/kg

qout = 326.4 kJ/kg

26

THANK YOU..

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