CONCEPTS OF

THERMODYNAMICS

A part of a universe set aside

for studies
Must have enclosing boundaries
outside which must be the
surrounding
Examples include:

reservoir gas flowing to the

wellbore,
gas undergoing a compression in a
mechanical compressor
Gas flowing vertically in a tubing
etc.

It states that energy can neither be created

nor destroyed but can be transformed from
one form to the other.
Accounts for transfer of energy to and from
a system and changes of energy within a
system
Two accounting procedures are:

Control mass and

Control volume

It is a selected piece of matter (gas)

Any assembly is a control mass

This method calculates the properties of

given pieces of matter as a function of time

It is any defined region in space

This method gives the properties of whatever
piece of matter happens to be in a given
region of space at any given instant

The general methodology of energy balance

analysis is:
Define the control-mass or control-volume, indicating
its boundaries on a sketch
Indicate what flows of energy across the boundaries will
be considered and set up the sign conventions in the
drawing

Indicate the time basis for the energy balance

Write the conservation of energy in general terms
make appropriate idealizations and bring in equation of
state or other information necessary to allow solution

Energy carried with the fluid(gas) include:

The internal energy(U)

The energy of motion (kinetic energy,

Energy of position (Potential energy,

The pressure energy (PV), carried by the system

because of its introduction into or exit from flow
under pressure

Energy transferred between a fluid or system

and its surrounding is of two kinds:
1. Heat absorbed by the flowing material or system
as a result of temperature difference between the
system and the surrounding (+ve)
2. The work done (w) by the system on the
surrounding (shaft work). It does not include lost
work due to friction

Heat and work are the only means of

transferring energy between the system and
the surrounding.

An energy balance of flow of a system between

point1 to point2 and the surroundings assuming no
accumulation of material at any point in the system
is given by the equation:
(1)

By definition

Therefore,
(2)

Enthalpy is defined as:

Change in enthalpy is given as:

Hence equation (2) becomes:

Where H is the total heat content (BTU)

Between two thermodynamic states (pressure and

temperature), the change in enthalpy can be
defined as:

Or

Where:

m=
n=
h=
h=

pound-mass of gas
pound-mole of gas
specific enthalpy of the fluid (Btu/lbm)
molal specific enthalpy of the fluid (Btu/lb-mol)

For natural gas, the molal specific enthalpy is

a function of pressure, temperature and
composition i.e:

For a given gas composition,

Taking the differential

And integrating gives:

Considering a functional relation,

,the difference
in energy between two states separated by
infinitesimal
temperature
and
specific
volume
differences, dT and dv, is:

The derivative,
volume

is called specific heat at constant

While the derivative

constant pressure

is called specific heat at

The specific heat at constant volume is related to the

specific heat at constant pressure by the relation:

The ratio
of the specific heats is very useful
in adiabatic compression of gases for which ideal
gases follow the relationship:

The specific heats of gases

and liquids are determined
experimentally
in
a
calorimeter usually at a
pressure of 1 atm.

For natural gases, specific

heat at 1atm pressure is a
function of temperature and
gas gravity or molecular
weight

Specific heat of hydrocarbon gases at 1atm (after Brown)

Entropy of a system is defined as:

But the change in entropy is analogous to the

change in energy; hence

Where

Example 1: calculate the molal enthalpy

and molal entropy change, h and s

when a given quantity of 0.7 gravity
natural gas is compressed from
14.7psia and 100oF to 800psia and
300oF

From Thomas, Hankinson and Phillips

equation:
But change in enthalpy can be defined as:

From this equation, change in enthalpy can

be divided into two processes:
Change in enthalpy at constant pressure and

Change in enthalpy at constant temperature

Considering change in enthalpy at constant

pressure of 14.7psia from 100oF to 300oF
will give:

Average temperature = 200oF

The specific heat at constant pressure at
average pressure is obtained from chart
= 11.1 Btu/ib-mol oF

Hence change in enthalpy at constant

pressure is:

Again, lets consider the enthalpy change at

constant temperature. That is from 14.7psia
to 800psia at 300oF

or

Calculate the reduced properties

From table, the z-factor equations for

and 1.4 Tpr 3.0 is:

Therefore,

0.2ppr1.2

Hence, change in enthalpy at constant

temperature will be:

Total enthalpy change will be:

Change in entropy
the change in entropy equation can be modified to
reflect 100oF instead of 32oF as:

= 11.1 Btu/ib-mol oF at 200 oF

The average z-factor from z-factor chart is:

Averaging gives:

Therefore,

Hence, change in entropy is:

=-4.99Btu/lb-mol oF

Very useful in the analysis of steady-state process

Enthalpy is the important thermodynamic property
in the steady-flow energy balance
Entropy is the principal property of concern with
respect to the second law

Hence, the coordinates of h-s in the diagram

represents the two major properties of interests in
the both laws

Only applicable to gases

If a gas is cooled below its dew point, condensation occurs
and heat removal cannot be determined directly from the
charts

These charts are made for different range of specific

gravity gases (from 0.6-1.0)

These charts are useful in finding the temperature change

on expanding or compressing gases

They are also used for finding the reversible work of

compression or expansion

Using Enthalpy-entropy
diagrams (Mollier
Diagrams)
From browns h-s
diagram of 0.7 gravity
natural gas

Determination of enthalpy change

At 14.7psia and 100oF ,
h1=680Btu/lb-mol

At 800Psia and 300oF

h2 = 2600Btu/lb-mol

Therefore,
Enthalpy change from 1 -2 will be :

Determination of Entropy Change

At 14.7psia and 100oF ,
s1=1.2 Btu/lb-mol oF

At 800Psia and 300oF

S2 = -3.7Btu/lb-mol oF

Therefore,
Entropy change from 1 -2 will be :

Example 2

(a)

From the diagram, read the intersection of 600oF

line and the 200-psia line

h1= 6100Btu/lb-mol

Then follow the 200-psia line to its intersection

with the 100oF line and read the enthalpy
h2 = 500Btu/lb-mol

Heat removed = h1-h2

= 6100- 500
= 5600 Btu/lb-mol

(b)
At 200 psia and 300oF the enthalpy is
h3 =2600Btu/lb-mol

Heat added = h3-h2

= 2600-500
= 2100 Btu/lb-mol