4.

0 Energy Balances

4.1 The 1st Law of Thermodynamics

 Energy in all its forms is conserved

The energy if a system may be made of:

Per unit mass

2
 Kinetic ½Mv ½v2

Note that for a single component system, Û is a function of any two chosen functions (e.g.
T, P)

We can distinguish between:

 Open systems:

 Closed systems:

 Isolated systems:

4.1.1 Energy conservation: Closed (batch system)

Note for closed systems, energy can cross the CV in the form of heat transfer or work done.

This course shall use the following convention:

Thus the 1st Law implies:

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We normally split work into two components:

 PV work, WF due to moving the CV surface against a force

 Other work, termed shaft work, WS which is usually work done at system
boundaries.

Thus the first law for a closed system is:

dU = dQ + dWs − PdV

dU • • dV
or = Q+ W S − P
dt dt

N.B: this neglect any change in kinetic and potential energy of the control
volume.

4.1.2 Energy Conservation: Open (continuous) systems

General statement of 1st Law is now:

dU • • dV
= Q + WS − P + ∑ Energy flow in - ∑ Energy flow out
dt dt in out

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What is “energy flow”?

 Consider a small mass ∆M1 entering at point 1. The energy flow will include

1) its own internal energy, ∆U1

2) the work need “to push” the fluid into the system, P1∆V1

3) kinetic energy in (½∆M1v2) and potential energy (∆M1gh1)

 these are usually ignored for simplicity

 ∧ ∧

Hence the energy flows in at appoint 1: = ∆U1 + P1∆V1 = ∆M 1 U1 + P1 V1 
 
∧ ∧
Therefore the energy flow in = ∆M 1 H1 and similarly energy flow out at point 2 = ∆M 2 H 2

Therefore the first law is now:

dU • • dV • ∧ • ∧
= Q + WS − P + ∑ MK HK − ∑ MK HK
dt dt IN OUT

 applies for any control volume (closed systems included)

 neglects kinetic and potential energy terms (see later)

Special case:

dU dV • • •
 by definition of steady state: = 0; = 0 and ∑ M K = ∑ M K = M
dt dt IN OUT

• • • ∧ • ∧
 hence Q + WS = ∑ MK HK − ∑ MK HK
OUT IN

∧
 letting ∆ H = the total enthalpy change per unit mass of substance flowing through
the control volume

• ∧ • •
⇒ M ∆ H = Q + WS

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4.1.3 Closed System Example

For the following two cases determine how much heat is required and what fraction of that
heat is used to do expansion (PV work) work.

(a) Boiling 1 kg of water at 100oC and 1 atm

(b) Heating 1 kg of steam at 1 at from 100oC to 500oC

Answer: in each case consider a closed system of 1 kg

(a) 1st Law of Thermodynamics:

 Since no shaft work:

 Since P is constant and M = 1 kg

Steam tables:
∧ ∧
 Water, 100oC, 1 atm: U = 419.0 kJ/kg V =0.001044 m3/kg

∧ ∧
 Steam, 100oC, 1 atm: U = 2506.5 kJ/kg V =1.673 m3/kg

Hence Q =

∧
P∆ V =

∧
P∆ V
Hence fraction that is doing PV work = =
Q
(b)

 Since P is constant and M = 1 kg:

Steam tables:
∧ ∧
 Steam, 500oC, 1 atm: U = 3132 kJ/kg V =1/0.280 m3/kg

Hence Q =

∧
P∆ V =

∧
P∆ V
Hence fraction that is doing PV work = =
Q

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4.1.4 Open System Example

A steam-heated “jacket” on a reactor is fed at 0.1 kg/s with 5 bara steam at 10oC superheat.
Saturated water is removed at 5 bara. The plant is at steady state. How much heat is being
supplied to the reactor?

Answer

 Steady state open system:

Steam tables:

∧
H in =

∧
H Out =

•
Q=

•
( Q is negative as heat flow out of the jacket into the reactor)

So heat supplied to reactor =

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4.1.5 The general energy balance equation

If we include kinetic and potential energy terms, we get the following general equation
which is valid for both closed and open system:

d 1  • • dV •
 ∧ 1  •
 ∧ 1 
U + M  v 2 + gh  = Q + WS − P + ∑ M k  H K + vk2 + ghk  − ∑ M k  H K + vk2 + ghk 
dt  2  dt in  2  out  2 

Where v is velocity, h is height and g is the acceleration due to gravity.

This may look messy, but it is actually quite simple, particularly at steady state. We will
need to use this form when velocity changes are significant (e.g. for fluid flow with a
changing pipe diameter).

Special case 1: Closed system

•
dM
In this case material is not entering or leaving, so M k = 0 and =0
dt

dU d 1  • • dV
Hence: + M  v 2 + gh  = Q + WS − P
dt dt  2  dt

Special case 2: Open system at steady state

In this case (e.g. steady flow of fluid in a pipe) must obey:

•
 ∧ 1  • • •
 ∧ 1 
M  H1 + v12 + gh1  + Q + WS = M  H 2 + v22 + gh2 
 2   2 

• •
∧ 1 Q W ∧ 1
Or H1 + v12 + gh1 + • + •S = H 2 + v22 + gh2
2 M M 2

This so-called “steady flow energy equation” is particularly useful for gas flow calculations.

For liquid flow calculations, the density is roughly constant (i.e. incompressible fluid). In
that case, if we additionally assume the flow is thermodynamically reversible and there is no
shaft work, then we can derive Bernoulli’s equation, which is used in fluid mechanics, from
this!

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4.2 Entropy balance

4.2.1 Second Law of thermodynamics

 1st Law requires energy is conserved

 The 2nd Law tells us something about how energy can be interconverted from one
from into another e.g. heat to work.

There are number of manifestations and equivalent statements of the 2nd Law. For instance:

 There is a limit to the work that you can get out of a cyclic system (Carnot 1824)

 Heat cannot pass spontaneously form a cooler body to a hotter body (Kelvin;
Clausius)

 Entropy of the universe must increase (Clausius)

 Entropy is related to “randomness” and “disorder” in a system (S = klnW –

Boltzmann 1900)

 There are also 2nd Law statement by Carathéodory (1909) and Planck (1927)

For this course we will follow Sandler’s approach and state the 2nd Law as

a) Entropy is a state function

•
b) When heat crosses a control volume surface at temperature, T and rate Q then the
•
Q
entropy is added at a rate
T

c) Entropy is not conserved. It will be generated in any processes that is performed

irreversibly.

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We can thus write an “entropy balance”

•
• ∧ • ∧ •
dS Q
= + ∑ M K S K − ∑ M K S K + S GEN
dt T IN OUT

•
 S GEN = 0 for a reversible process i.e. one in which the system and surroundings can
return to their original condition after the process and reverse process have been
performed (e.g. by carrying out the process infinitesimally slowly)

 In differential terms:

dQ
dS ≥
T

dQreversible
dS =
T

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