CET 1156: Engineering Thermodynamics

Textbook: Chemical, Biochemical and Engineering Thermodynamics, by S. I. Sandler, 5 th Edition

First Law of Thermodynamics and Applications (Chapter 3: Conservation of Energy)

1. In a generalized form, the First Law of Thermodynamics represents energy balance on a control volume
as shown below. We will write it, like we did unsteady state material balance,
Accumulation of energy = rate at which energy comes in – rate at which energy leaves

Pext Shaft work ̇

Incoming or outgoing stream ‘i’ Control Volume

Specific Internal Energy, ‘Ui’ Total mass or moles Mt
Pressure ‘Pi’ Total Volume ‘Vt’ Rate at which Heat is
Velocity, ‘Vi’ Pext Specific Internal Energy, ‘U’ supplied or removed ̇
Height ‘hi’ Velocity, ‘V’
Pext
Mass or molar flow rate ̇ Height ‘h’

Pext

 2   2  
It can be written as: {  ( + + ℎ)} = ∑ {̇ ( + + + ℎ )} + ∑ ̇ + ̇ −  . Here,
    

the left-hand side represents the accumulation of energy in all forms in the control volume.
2
 ℎ terms have units of J/kg.


‘U’ and ‘Ui’ are the specific internal energy of the control volume and of stream ‘i’. It would have units of
‘J/kg’ or ‘J/gmol’.
‘Mt’ represents the total mass or moles in the control volume, ̇ represent mass flow rate or molar flow
rate of stream ‘i’.
 
∑ ̇ = ∑  ̇ = are the rate of heat flow and net rate of shaft work into the control volume,
 

respectively.
 
Pext is the pressure acting on the surface of the control volume.  represents _______________.


Answer the following questions:

2
(i) What care must be taken about  ℎ, if ‘U’ has units of J/gmol? __________________


(ii) If units of ‘U’ are to be J/gmol, then the units of ̇ should be: _____________________
(iii) If the Units of ‘U’ are to be J/kg, then the units of ‘Pext’ should be _____________ and that of ‘Vt’
should be _________________
2. When a stream with a mass or molar flow rate ̇ enters the control volume it would have ______ sign
and when it leaves, it would have _______ sign. Similarly, when the heat or shaft work, ̇  ̇ are
entering the control volume, they would have _______ sign and when they are going out of the control
volume they would have _________ sign.
  2  
3. Equation given in 1, simplifies to:  = ∑ ̇ ( + + ℎ ) + ̇ + ̇ −  , when using the
  

following two simplifications: (i)_______________ and (ii) _________________

4. Internal Energy ‘U’ represents the following forms of energy: ______________________________
5. The Enthalpy, H = U + PV represents in addition to ‘U’ the ______________________________

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6. When there is no mass coming in or going out of the control volume, ̇ = 0, we call it as a __________
system. When ̇ ≠ 0, we call it as a ___________ system.
7. When ̇ = 0, we call it as an ______________ system.
8. For a closed system with no shaft work, no change in the velocity and potential energy of the control
volume, and if the external pressure is same as pressure of the control volume, then, the equation given
in 1, simplifies to: ___________________________, hey remember, this is what you have been taught
as First law of Thermodynamics 
. See, it is simply an extension of MEBC.

9. For a control volume at steady state, with no heat coming in or leaving, and no shaft work, the equation
reduces to ________________________. Wow, this is the Bernoulli Equation that you have already
. There is one small modification that needs to be done, which you will study in the subject of
seen 

Momentum Transfer.
10. In many applications, we need to deal with a control volume where stream enter and/or leave, heat is
supplied or removed, etc. Let us use the generalized energy balance given in 1 above to solve some
problems now:
11. Imagine a car containing a CNG tank. CNG is getting filled into the tank in the car from a large storage
tank of CNG at a filling station. For this problem, treat CNG as pure methane. The pictures will help
you to visualize the process.

Very Large CNG flow

storage tank CNG
through pipe
of CNG at the tank in
petrol pump the car

Let us make the following assumptions: (i) The storage tank of CNG in the car has a volume (capacity)
of 100 lit, (ii) At the start of the filling process, the CNG tank in the car is at a pressure of 2 bar absolute
and a temperature of 40oC, (iii) When the filling is complete the CNG tank in the car should have a
pressure of 200 bar absolute, (iv) The Storage tank at the petrol pump is very large (typically hundreds
of m3) as compared to the CNG tank in the car, so that even when several such cars gets filled, the
pressure and temperature of the CNG storage tank at the petrol pump do not change significantly. For
the purpose of this problem, we can consider that the storage tank at the petrol pump is at 40oC and
350 bar absolute pressure, (v) Assume that methane behaves as an ideal gas under all conditions of
temperature and pressure with CP = 36 J/gmol K, (vi) The process of filling CNG in the tank in the car is
quick (of the order of few minutes), so that we can assume the process to be adiabatic, (vii) The velocity
of the gas entering the tank is very small as compared to internal energy and the potential energy
changes are negligible, (viii) Assume that, as the gas gets filled in the tank in the car, it experiences no
friction with tank walls and the heat transfer with tank walls is negligible.
Try to visualize the situation. The CNG in the cylinder in the car is getting compressed adiabatically by
the gas coming in from the large storage tank at the petrol pump. So, when the filling process is
complete and the pressure in the tank in the car reaches 200 bar absolute, the temperature of the gas
in the tank in the car would be more than 40oC. Try to answers the following questions on your own:
(a) What would be the temperature of the gas in the tank in the car at the end of the filling process?
(b) How many kgs of CNG were there in the tank in the car at the start of the filling process?

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 (c) How many kgs of CNG are there in the tank in the car at the end of the filling process?
(d) At the end of the filling process the connecting pipe is removed and the gas in the tank in the car is
allowed to reach 40oC. What would be the pressure now in the tank in the car?
In case you are unable to answer, you can get help by answering the following questions: Let us analyze
this situation, using the first law of thermodynamics given in 1. Consider the control volume as the CNG
storage tank in the car. In this case, ̇ = _____, ̇ =______, Does Vt change? Yes / no? Let us
denote stream number 1 as the CNG entering the tank in the car. The equation given in 1 now simplifies

to:   = ∑ 


The LHS can be written as a sum of two terms:

 
  +   = ∑ 
 

Realize that the gas coming into control volume is at constant temperature and pressure, so its specific

Enthalpy remains constant at all times. Now, mass balance on the control volume is = ̇ . Using


this, the above equation simplifies to:

 
 =  
 

Now that both the sides of the equation are derivatives with time, (d/dt), it can be dropped, since we are
not interested in how temperature and pressure vary with time, but only, the values of temperature and
pressure at the end.
To proceed further, we need a way to evaluate ‘U’ and ‘H’ as a function of temperature and pressure.
For now, since we have assumed that methane behaves as an ideal gas, we can further assume that
‘U’ and ‘H’ are only functions of temperature (T) only. We will prove this later. So, U & H = f(T). We
 
define CV and CP as:  = |   = | . Recall that in MEBC, we defined a reference
   

temperature, say 25oC. Let us denote the specific enthalpy and internal energy at this reference
temperature (Tref) as Href and Uref. So now, ‘H’ and ‘U’ at any temperature would be:
H = Href + CP(T – Tref) and U = Uref + CV(T – Tref).
Also note that, Href = Uref + PV = Uref + RTref and CP – CV = R.
 
Use these relationships in the equation above we get: =

Since we have written ‘H’ and ‘U’ in terms of CP and CV and the value of CP is given per unit mole, ‘Mt’
should be the moles of CNG in the tank. Now, using ideal gas law, the moles in the tank can be

expressed in terms of temperature and pressure. This gives,  = , note that T1 is the
 1  

temperature of the CNG entering and ‘T’ is the temperature of the CNG in the tank in the car at any
instant. Now integrate and find the answer to all the questions above. This problem is similar to
Illustration 3.4-3 in Sandler’s book.
12. Let us now look at another problem involving removal of CNG from the tank in the car. Imagine that the
CNG cylinder in the car is full, meaning, the temperature is 40oC, volume is 100 lit and pressure is 200
bar absolute. Now the person starts driving the car on a highway
at a constant speed of 60 km/hr. The car gives a milage of 20 CNG flowing out CNG
at constant rate tank in
km per kg of CNG. CNG now flows from the cylinder to the to engine the car
engine of the car where it gets burnt to provide the mechanical
power to drive the car. At what rate will the CNG flow out from the tank? Ans: ____________ kg/hr.

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 Again, assume for the purpose of this problem that the tank is adiabatic and CNG is pure methane with
CP = 36 J/gmol K. Let us visualize the situation first. As the CNG flows out of the tank, it carries enthalpy
with it. Since the tank is adiabatic, the internal energy of the gas remaining in the tank would reduce,
resulting in a _______________ in the temperature of the gas in the tank.
What would be the temperature and pressure of the gas in the tank after 1 hour?
Try to calculate this on your own. If you do get stuck, use the following set of instructions to arrive at
the answer.
As before, let us start with generalized energy balance (1st Law of Thermodynamics):
 2   2  
{ ( + + ℎ)} = ∑ {̇ ( +  +  + ℎ )} + ∑ ̇ + ̇ −  . The control volume is the
    

CNG in the tank. The process is adiabatic, there is no shaft work and Vt is constant at all times. There
is no change in the kinetic energy and potential energy of the gas in the tank and the velocity and
potential energy of the gas leaving the tank is negligible as compared to its internal energy. Under these
assumptions, the equation simplifies to:

  = ∑ . This is identical to what we had in the previous problem. The only difference is that,

 
now, the material balance on the tank gives: ̇ = − . This is because, the gas is flowing out of the


tank, as a result the total mass of gas inside the tank will reduce with time. Using this, and as before,
  
writing the LHS as a sum of two terms, we get:   +  =  .
  

Since all the terms are derivatives with respect to time, it can be dropped. This is because we are not
interested in how temperature and pressure changes with time. We only want to find out the temperature
and pressure at the end of 1 hour. Again using the expressions for enthalpy and internal energy change
 
with respect to temperature, we get: = . Since we have written ‘H’ and ‘U’ in terms of C P

and CV and the value of CP is given per unit mole, ‘M t’ should be the moles of CNG in the tank. The
above equation can now be integrated.
The above problem is actually a simplified version of Illustration 3.4-5 in Sandler’s book.
13. Solve the above two problems again, but this time assuming that the C P of methane is a function of
temperature, given by: CP = 19.875 + 0.05021 T, where CP is in J/gmol K and ‘T’ is temperature in K.
Remember that for ideal gas, CP – CV = R, is still valid.
14. Solve on your own, Illustrations 3.4-6 and 3.4-8, Problems 3.11 and 3.20.
15. Actually, methane at all the conditions involved in the problem, does not behave as an ideal gas. What
would we do then. We would need to know how to evaluate ‘H’ and ‘U’ as a function of Pressure. Till
we learn this, someone needs to give us values of ‘H’ and ‘U’ as a function of temperature and pressure.
For steam, the values of ‘H’ and ‘U’ as a function of temperature and pressure are given in steam tables
or Mollier Charts. You have already seen this. Here is a Chart for Methane:

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 Let us solve a problem using this chart now:
16. In a process, methane is to be compressed at a mass flow rate of 1000 kg/hr, from 200K, 10 bar abs.
pressure to 400 K and 100 bar abs. pressure in an adiabatic compressor operating at steady state.
Calculate the compressor power required. If the cost of electricity is Rs. 10 per kW-hr, calculate the
compression cost in terms of Rs. per kg of methane. Solve this problem on your own.
If not, here are instructions to help you. First, let us
visualize the process in the form of a process block
Methane Compressor Methane
1000 kg/hr 1000 kg/hr
diagram. Let us denote streams 1 and 2 as entering 200K, 10 bar 400K, 100 bar
Ws
and leaving streams respectively. Simplify the
generalized energy balance. You should get: ∑  + ̇ = 0
Use the chart to note down the enthalpy of streams 1 and 2. H 1 = ______ kJ/kg and H2 = ______ kJ/kg.
This gives ̇ = ___________/ℎ = _______________. Compression cost = _______ Rs/kg of methane.
17. Revise the use of Mollier Charts or Steam tables for solving problems related to steam. Solve on your
own, Illustration 3.4-1 and Problem 3.16 from Sandler’s book.
18. You would have realized the following issues: (1) We would need a chart or table for every substance
covering a very wide range of temperatures and pressures. (2) Charts and Tables are cumbersome to
use requiring interpolation. (3) We can not carry all the charts and Tables everywhere we go. (4) Using
Charts and Tables makes the calculations manual and laborious. Wouldn’t it be nice, if we can make
the calculations automated on a computer, using Python or excel? This is precisely what the whole
World does. Humanity has moved on from Tables and Charts. We use computers! Let’s learn how 


19. You are now equipped and ready to take on the World, armed with the confidence of applying energy
balance wherever needed.

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