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Determination of Changes in Internal Energy and Enthalpy:: Thermodynamics Session - 7

The document discusses determination of changes in internal energy and enthalpy using formulas. It explains that for any process between two states, the change in internal energy is given by the integral of heat capacity over temperature change, regardless of the path taken. It also introduces the concept of compressibility factor and theory of corresponding states to describe deviations of real gases from ideal behavior, using reduced temperature and pressure.

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83 views

Determination of Changes in Internal Energy and Enthalpy:: Thermodynamics Session - 7

The document discusses determination of changes in internal energy and enthalpy using formulas. It explains that for any process between two states, the change in internal energy is given by the integral of heat capacity over temperature change, regardless of the path taken. It also introduces the concept of compressibility factor and theory of corresponding states to describe deviations of real gases from ideal behavior, using reduced temperature and pressure.

Uploaded by

mukesh3021
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Thermodynamics Session 7

Determination of changes in internal energy and enthalpy:


No matter what is the process the internal energy and enthalpy are determined using the following formulae.

dU CV dT dH CP dT
If the process is isochoric, then dU CV dT dQ . If the process is isobaric, then dH CP dT dQ . Let us recall that 1. For ideal gases internal energy is a function of temperature only. 2. The change in internal energy is a state function. Let us take an adiabatic process and determine change in internal energy.

2
p

1
V

Consider two states (1) and (2) on an adiabatic path. There is one isotherm for each state as shown. Adiabatic curve at (1) is steeper than the isotherm. Whether the process follows adiabatic path or another curve shown in the figure or any arbitrary path, as long the initial and final state are same, we get the same change in internal energy.

2
p
a

1
V
Let us replace adiabatic path by two steps 1. 2. 1 a constant volume process followed by a 2 isothermal process

to accomplish the same change in the state.

U 1 2 U 1 a U a 2

Since step 1 a is a constant volume process, dU CV dT will have to be used. The step a 2 is isothermal and therefore dU = 0.

U12 CV dT 0
T1

Ta

Since Ta T2 ,

U12 CV dT
T1

T2

Any process between any two states can be replaced by either an isothermal process followed by constant volume process or constant volume process followed by an isothermal process. The total change in internal energy is the change in internal energy for constant volume step only. Thus no matter what process the change in internal energy is given by dU CV dT .

Same idea may be extended to change in enthalpy.

Deviations of real gases form ideal behavior:


The deviation from ideal behavior is measured using what is known as

compressibility factor defined as the ratio of volume determined using ideal gas law
to the actual volume at any given temperature and pressure.
Z Vactual pV Videal RT

For ideal gases, Z = 1. Higher the value Z away from one higher will be the non-ideality. Following figure gives the value of Z as a function pressure for different gases. All gases approach ideal gas behavior at low pressures. This figure is called compressibility chart. There will be as many curves as there are number of gases. The chart that is given here is for one temperature. Therefore this figure becomes highly cumbersome if applied for all gases and all temperatures.

N2 1.0 Z

CH4

C2H6 p
Theory of corresponding states: It states that all fluids, when compared at the same reduced temperature and reduced pressure, will have same compressibility factor and all deviate from ideal behavior to the same extent.

The reduced pressure and temperature are defined by

pr Tr

p pC T TC

Tr 1.5 Tr 2.5

Z
Tr 1.0

pr
Here all gases with the same reduced temperature and pressure lie on the same curve. This chart is called generalized compressibility chart. Different gases are indicated by different points on the curve. There will be as many curves as there are temperatures. This is less cumbersome compared to compressibility chart.

T N2 CH4 189. 3 286.0 5

p 83.7 5 114. 5

Tc 126. 2 190. 7

p
c

T 33. 5 45. 8
r 1. 5 1.

pr 2. 5 2. 5

The above table gives two gases with the same Z for different T and p. The reason is that the critical values are different.

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