B4.

7AB2
Process Industries B

Energy Balances within the Process Industries

Topic 2

Heat Balances under Steady-Flow

without Reaction

Version 1 July 2013 © Heriot-Watt University 1

 Learning objectives:

After studying this Topic, you should be able to:

• Apply the First Law of Thermodynamics to basic steady-
flow processes without chemical reaction.
• Apply the steady-flow energy equation to heat
exchangers without phase change.
• Apply the steady-flow energy equation to heat
exchangers with phase change.
• Apply the steady-flow energy equation to combined
mixing and heat exchange processes.
• Apply the steady-flow energy equation to a flash
vaporisation process.
Version 1 July 2013 © Heriot-Watt University 2
 2.1 Introduction
The steady-flow energy equation will be used throughout this
topic:
•Writing it in terms of intensive quantities and ignoring work,
kinetic and potential energy terms it reduces to the following:

q12  h2  h1 

• Converting from intensive to extensive quantities depends

on whether the enthalpy is specific (kJ/kg) as below:
Q  m h  h 
12 2 1 ↔ m  mass flow (kg/s)
• Or, the enthalpy is molar (kJ/kmol) as below:

Q  n h  h 
12 2 1
↔ n  mole flow (kmol/s)

In both cases the rate of heat flow Q 12 is in (kW).

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 Introduction
Estimating the enthalpy change, whether specific or
molar, depends on the type of fluid:
• Ideal Gas:
T2

h 2  h 1   C P dT
T1

• Incompressible Liquid:
T2

h 2  h 1   C P dT  vP2  P1 
T1

If liquid pressure drop is small then the second,

pressure dependent, term may be dropped.
In this course the first equation will be used throughout.
Version 1 July 2013 © Heriot-Watt University 4
 2.2 Steady-Flow Energy Equation
Heat Exchangers
In terms of molar enthalpy, the steady-flow energy
equation for heat exchangers reduces to
Q  n h  h 
12 2 1

• For low pressure gases and liquids with small

pressure drops
T2

h 2  h 1   C P dT
T1

In Heriot-Watt tables the heat capacity will be the molar

heat capacity (kJ/kmol K) – mass flow may have to be
converted to mole flow!
Version 1 July 2013 © Heriot-Watt University 5
 Flow Symbols: different flow symbols are often used in
different texts – take “f ” to be mole flow (kmol/s):

Q 12  f h2  h1  ↔ Q  n h  h 
12 2 1

• Also “C” and “H” may be used for cold and hot fluids
respectively in which case the above becomes:
Q  f h
c c c
Q H  f H hH
Summing the two equations should lead to zero – heat lost
(negative) will equal heat gained (positive).
f C hC   f H hH ↔ NO LOSSES
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Example 2.2.1

Problem:
In a bio-fuel plant there is a need to cool a liquid ethanol
stream from 70oC to 50oC. The mass flow of this stream is
2.5 t/hr and the heat exchanger is water cooled. Assuming
that external heat losses are negligible and, given water
inlet and outlet temperatures of 20oC and 35oC respectively,
calculate the following:
•The rate of heat transfer (kW) and the mass flow of water
(t/hr).
•If only 2.0 (t/hr) of cooling water is available, calculate the
final outlet water temperature for the same cooling duty

Version 1 July 2013 © Heriot-Watt University 7

Example 2.2.1

Solution:
Both ethanol and water molar heat capacities (kJ/kmol K) may
be estimated using the following correlation:

C P  A  BT  CT 2

Molar Mass
A B C
(kg/kmol)
Ethanol 46 281.56 -1.4350 29.030E-04
Water 18 72.433 10.393E-03 -1.497E-06

(a) For the ethanol stream which is being cooled 70oC to 50oC:
323
hH   A  BT  CT dT
2

343

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Example 2.2.1

Solution:
• Calculate molar enthalpy of ethanol

hH  A323  343 

B
2
 C
 
323 2  343 2  323 3  343 3
3


hH  5631  9557  6440  2514 kJ/kmol

• The mass flow of ethanol is 2.5 t/hr – convert this to

(kmol/s)

kg  1 kmol  1 hr 
f H  2500     0.0151 kmol/s
hr  46 kg  3600 s 

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Example 2.2.1 Solution:
• Calculate the rate of heat flow (kW) of stream “H”; the
mole flow (kmol/s) times the molar enthalpy (kJ/kmol).
Q H  f H hH  0.0151  (2514)  38 kW

• Calculate the rate of heat transfer to cooling water

“CW” is equal and opposite – no external heat losses:

 Q  f h  38 kW
c c c
• Knowing the inlet and outlet temperatures of the CW,
write down the molar enthalpy change of cold stream “C”
308
hC   A  BT  CT dT
2

293

Version 1 July 2013 © Heriot-Watt University 10

 Example 2.2.1 Solution:
• Substitute in the values and solve for the CW enthalpy,
first molar enthalpy and then specific enthalpy:
hC  A308  293 
B
2
 C

308 2  2932  3083  2933
3
 
hC  1086  47  2  1131 kJ/kmol

kJ  1 kmol 
 hC  1131    62.8 kJ/kg
kmol  18 kg 

• The flow of coolant (kg/s) can be found by solving the CW

heat balance, write down this heat balance:
Q  f h  38 kW
c c c

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 Example 2.2.1 Solution:
• Solve for the flow of coolant – first in (kg/s) then in (t/hr):
f  38 / 62.8  0.605 kg/s
c
kg  3600 s  1 tonne 
 f C  0.605     2.18 t/hr
s  1 hr  1000 kg 

(b) If only 2 (t/hr) of cooling water is available first convert

this from (t/hr) to (kmol/s) – then identify heat balance
kg  1 kmol  1 hr 
f C  2000     0.0309 kmol/s
hr  18 kg  3600 s 

Q  f h  38
c c c

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 Example 2.2.1 Solution:

• From the CW heat balance and the mole flow, identify

the coolant enthalpy change (kJ/kmol)
 h  38 / 0.0309  1230 kJ/kmol
c
• Knowing the CW enthalpy and the inlet temperature,
the outlet temperature can found by trial-and-error
Tout

hC   A  BT  CT dT
2

293

B C
h  A T  293  T  293  T  293   1230 (kJ/kmol)
    2 2 3 3

2 3
C out out out

Tout  309.3 K ↔ T  36.3 C

out
o

This is 1.3oC higher because CW flow is only 2 (t/hr)

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Example 2.2.2

Problem:
Now consider both sensible and latent heat transfer.

In the same bio-fuel plant liquid ethanol, mole flow 0.03

kmol/s, enters a “kettle reboiler” at 30oC and a pressure of 1
atm. The reboiler is designed to heat the ethanol up to its
boiling point of 78.3oC and then to vaporise one-third of the
ethanol.

Calculate the “duty” of the exchanger (kW).

The latent heat of vaporisation is 38,770 kJ/kmole

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 Example 2.2.2

Problem:

Consider this to be a two-step process: label “1-2” as the

sensible heat transfer step; label “2-3” the latent heat
transfer step.

• This is a steady-flow process. Consider the preheat step

and then write down theoretical equations to be solved:
Q 12  f h2  h1 
T2

h 2  h 1  h12   C P dT
T1

• The integration will be from 30oC to 78.3oC (NBP)

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 Example 2.2.2 Problem:

• Write down and then calculate the enthalpy change of

the ethanol between these two temperatures:
351.3
h1 2   A  BT  CT dT
2

303

h1 2  A351.3  303 

B
2
351.3 2  303 2   351.33  303 3 
C
3

h1 2  13599  22675  15034  5958 kJ/kmol

• Use the steady-flow energy equation to find the preheat

duty (kW) – the rate of heat transfer for preheat step:
Q 12  f h1 2  0.03  5958  179 kW

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 Example 2.2.2 Problem:

• Write down the enthalpy change of the ethanol for the

latent heat step.
h2 3  38770 kJ/kmol
• Use the steady-flow energy equation to find the latent
heat duty (kW).
 f 0.03
Q23  h2 3   38770  388 kW
3 3
• Thus total duty (kW) both sensible plus latent
Q  Q  Q  Q
Total 13 12 23

 Q Total  179  388  567 kW

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 2.3 Steady-Flow Energy Equation
Stream Mixing
For heat exchanger problems the two key expressions are:
•Steady-flow equation for a heat exchanger.
•An equation for the fluid enthalpy change.

Q 12  n h2  h1  ↔ Molar Enthalpy (kJ/kmol)

T2

h 2  h 1   C P dT
T1

• Effectively the inlet temperature is being used as datum

temperature – now consider a lower temperature than T1
(say Tref) is to be used as the reference temperature.

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 • The inlet an outlet enthalpies would have to be
expressed as Δh values w.r.t. this datum temperature.
T2

h  h   C dT
2 1 P
T1

• Is this difference still equal to the integral on the RHS of

the above? - the inlet and outlet enthalpy changes are
now measured w.r.t. reference temperature:
T1 T2

h   C dT
1 P
h   C dT
2 P
Tref Tref

• Subtract the two expressions – the second minus the

first then use the properties of integrals to combine
them: T2 T1 T2

h  h   C dT   C dT   C dT
2 1 P P P
Tref Tref T1

QED – The Same!

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 General Mixing Processes:
Consider the mixing process where streams “1”, “2”……”n”
are all mixed together to form mixed stream “m”:
•The individual flows “f ” have units (kmol/s), while the
subscripts refer to the stream numbers.
•The enthalpies (relative to some datum temperature) are
given in (kJ/kmol) – again, the subscripts refer to stream
numbers:

&
Mixing
& Process &
&
&

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 Material and Energy Balances:
First consider material balance: in terms of many streams
entering and a single mixed stream leaving – all in (kmol/s)
n
f m  f 1  f 2  f 3  ......  f n   f i
i 1

Next consider the energy balance: consider one stream

entering and one stream leaving (enthalpies referenced to
inlet stream) the steady-flow equation is written as
f h2  h1   0

But for many streams entering/one stream leaving and

using a common reference temperature for all enthalpies
f 1 h1  f 2 h2  f 3 h3  ......  f n hn  f m hm

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 Enthalpy Balance:

The equation below is called an “enthalpy balance”

f 1 h1  f 2 h2  f 3 h3  ......  f n hn  f m hm

Enthalpy balances are applications of the steady-flow

energy equation, but only apply whenever:
•There is only mixing or separation.
•And there is no exchange of heat or work between system
and surroundings – see three situations below:

1- Mixing 2- Separation

↔ Flash expansion is Separation

3- Flash expansion
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 Example 2.3

Problem:
Mix together 50 kmol/hr of liquid benzene, at 80oC, with 30
kmol/hr liquid toluene at 20oC and then cool the mixture
down to 25oC. Given the above, calculate the following:
a)The temperature of the mixed stream (before cooling).
b)The rate at which heat must be removed (kW) to achieve
a final mixed temperature of 25oC.

It is a good idea to start with a drawing and label all streams:

Benzene Heat
Exchanger
o
80 C Mixed
Mixed
Mixer
o o
XC 25 C
Toluene

o
20 C

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 Example 2.3

Solution:
It is better to split the problem conceptually into two
separate parts – see drawing:
•First step is to mix the pure components together. The
temperature of this stream is unknown (xoC) and must be
found using an enthalpy balance.
•The second step is cool the mixture down in a heat
exchanger and calculate its duty (kW).
Benzene Heat
Exchanger
o
80 C Mixed
Mixed
Mixer
o o
XC 25 C
Toluene

o
20 C

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 Example 2.3, Solution:
a) The coefficients for the molar heat capacity correlation
are listed below:
Species
A B C D

Benzene -6.211 56.502E-02 -31.410E-05 -

Toluene 125.82 56.452E-03 13.593E-05 -

• First write down the overall material balance for this case:
two inlet streams one outlet stream.
f1  f 2  f 3

• Then write down the “enthalpy balance” for this case:

f 1 h1  f 2 h2  f 3 h3

The solution plan is to solve last equation for Δh3 and then T3
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 Example 2.3, Solution:
• Calculate the enthalpy of benzene at 80oC (0oC datum):
353
h1   A  BT  CT dT
2

273

h1  A353  273 

B
2
353 2  273 2   3533  2733 
C
3

h1  497  14148  2475  11176 kJ/kmol

• Then find the energy content of benzene stream “1”:

kJ  1 hr 
f 1 h1  11176  50    155.22 kW
hr  3600 s 

The next step is to repeat all of the above for the toluene
steam (stream “2”) – this allows the total energy content of
both inlet streams to be found.
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 Example 2.3, Solution:
• Calculate the enthalpy of toluene at 20oC (0oC datum):
293
h2   A  BT  CT dT
2

273

h2  A293  273 

B
2
 C
 
2932  2732  2933  2733
3


h2  2516  320  218  3054 kJ/kmol

• Then find the energy content of toluene stream “2”:

kJ  1 hr 
f 2 h2  3060  30    25.45 kW
hr  3600 s 

The last step is to find the overall flow and calculate the
enthalpy of the mixed stream w.r.t. 0oC reference
temperature.
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 Example 2.3, Solution:

• First solve the overall material balance expression:

f1  f 2  f 3
f 3  50  30  80 kmol/hr

• Then calculate the enthalpy of the mixed stream:

f 1 h1  f 2 h2 (155.22  25.45)  3600
h3    8130 kJ/kmol
f3 80

• The component concentrations are needed if the average

coefficients are to be found:
nB f 50
yB   1   0.625
nT f 3 80 ↔ “B” for Benzene
f 2 30
yT    0.375 ↔ “T” for Toluene
f 3 80

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 Example 2.3, Solution:
• Calculate the coefficients for stream “3”. Most plant
streams are mixed so use stream number:
A3  y B AB  yT AT  0.625  6.211  0.375  125.82  43.301

B3  y B BB  yT BT  37.431E  02
C 3  y B C B  yT CT  14.534 E  05

• Calculate Stream “3” enthalpy (use 0oC datum):

T3

h3   A
273
3 
 B3T  C 3T 2 dT  8130

A3 T3  273 
2

B3 2 C
 
T3  2732  3 T33  2733  8130
3

Use Mathcad or Excel to solve for final mixed temperature
T3T
. 3  56.9 o C
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 Example 2.3, Solution:
b) Now find stream “4” energy content at 25oC (use 0oC
datum). The coefficients for “3” and “4” are the same:

h    A  B T  C T dT
298
2

4 4 4 4
273

h4  A4 298  273 

B4
2
298  273 
2 2

C4
3
2983  2733   
h4  1083  2672  296  3459 kJ/kmol

kJ  1 hr 
f 4 h4  3459  80    76.9 kW
hr  3600 s 

The duty of the heat exchanger is the outlet stream energy

content minus the inlet stream energy content.

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 Example 2.3, Solution:
• The energy content of stream “3” is easily found because
it is simply energy content of “1”+”2”, write this down:
f h 155.22  25.45  180.67 kW
3 3

• The duty of the heat exchanger is then the energy content

of the outlet stream(stream “4”) less the energy content
of the inlet stream(stream “3”) , calculate the duty:
Q  f h  f h  76.9 - 180.67
34 4 4 3 3

Q  103.8 kW
34
↔ Minus means Cooling

All the steady-flow energy equation is stating is that if the

energy content of two adjacent streams differ – then an
equal amount of energy must be supplied or removed.
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 2.4 Steady-Flow Energy Equation
Flash Vaporisation
If a high-pressure liquid (close to its boiling point) suddenly
expands to a lower pressure, then the single-phase liquid can
“flash” into a two-phase liquid/vapour mixture:
• A drop in pressure occurs
across the valve.
Flash • The boiling point inside the
Drum
drum is lower.
• The mixture, at lower boiling
point, will “flash” into two
phases.

Notice the symbols used – each item of process equipment

tend to use their own particular symbols.
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 Mass and energy balances are powerful tools when it
comes to analysing any process:

Overall material balance:

F V  L ↔ Units either kg/s or kmol/s
Overall energy balance:

FhF  VhV  LhL ↔ Units will be kW

Choose datum temperature for enthalpies carefully.

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 Example 2.4.1

Problem:
Liquid butane at a pressure of 8 bar and a temperature of 340 K
is expanded through a valve to a downstream pressure of
1.33 bar. Calculate how much vapour is formed and the
temperature inside the flash drum, given the following:
•The molar mass of butane is 58 (kg/kmol).
•The constant specific heat capacity of liquid butane is 2.27
(kJ/kg K).
•The heat of vaporisation of butane at 270 K is 387.5 (kJ/kg).
•The heat of vaporisation of butane at 280 K is 380.9 (kJ/kg).

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 Example 2.4.1, Solution:
• The boiling point of pure butane varies with pressure:
Pressure 1 2 3 4 5 6 7 8
(bar)
Boiling 272.4 292.2 305.2 315.3 323.6 330.8 337.1 342.7
Point (K)

• Interpolate to find BP at 1.33 bar as follows:

Linear Interpolation:

x  272.4 1.33  1

292.2 292.2  272.4 2 1
X
272.4 x  272.4  (0.33  19.8)

1 2 3
x  278.9 K
1.33

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 Example 2.4.1, Solution:

• The boiling point at 1.33 bar is 278.9 K (linear variation)

• The heat of vaporisation at this temperature is found the
same way: Linear Interpolation:

y  387.5 278.9  270


380.9
380.9  387.5 280  270
y
y  387.5  (6.6  0.89)
387.5

y  381.6 kJ/kg
270 280

278.9

• By linear interpolation the enthalpy of vaporisation (heat

of vaporisation) at 278.9 K is 381.6 kJ/kg.

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 Example 2.4.1, Solution:

• Basis: 1 kg/s of feed splitting into x (kg/s) of vapour and

(1-x) kg/s of liquid. Write down the energy balance:
hF  xhV  (1  x)hL
• The enthalpies need a datum state. A good approach is to
use the lowest stream temperature.
• The temperature inside the flash drum is 278.9 K – use this
as the datum temperature (Tref) for enthalpies.
• Calculate enthalpy of liquid stream (stream “L”):
TL

 hL  C
Tref
P dT  C P (TL  Tref )

 hL  C P (TL  Tref )  2.27  (278.9  278.9)  0 kJ/kg

Expected??
Version 1 July 2013 © Heriot-Watt University 37
 Example 2.4.1, Solution:
• Calculate enthalpy of feed stream (stream “F”):
TF

h   C dT  C (T  T )
F P P F ref
Tref

 hF  C P (TF  Tref )  2.27  (340  278.9)  138.7 kJ/kg

• Calculate enthalpy of vapour stream (stream “V”) – there

is sensible heat and latent heat:
Tb

 hV   P    P (Tb  Tref )  hvap

liq liq
C dT hvap C
Tref

• But the reference or datum temperature is Tb.

 h V  381.6 kJ/kg → Not zero even though Tb = Tref

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 Example 2.4.1, Solution:
• Apply flash vaporisation energy balance (using “basis”):
hF  xhV  (1  x)hL

138.7  381.6 x  0
 x  0.363 kg/s
• The overall flash process may be visualised as follows:

The energy content of “F” is 138.7 kW.

138.7 (kW)
3 (vapour)
1 (Feed) The energy content of “L” is 0 kW.
0 (kW)
2 (liquid) This 138.7 kW of energy is capable of
vaporising 0.363 kg/s of the feed
stream – all energy supplied by feed!

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 Example 2.4.2

Problem:
This is a worked example for the student to verify by hand
and write up into the manual.

Instead of choosing liquid butane at 278.9 K, take liquid

butane at 298 K (25oC) to be the new datum state, i.e. take a
reference temperature of 298 K, or 25oC.

The temperature inside the flash drum is still 278.9 K and the
enthalpy of vaporisation at this temperature remains
381.6 kJ/kg.
Expect to get exactly the same answer!!

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 Example 2.4.2

Solution:
• First the new liquid enthalpy (datum 25oC) – stream “L”:
TL

hL  C
Tref
P dT  C P (TL  Tref )  2.27  (278.9  298)

 h  43.36 kJ/kg
L

• Then the new feed enthalpy (datum 25oC) – stream “F”:

TF

hF  C
Tref
P dT  C P (TF  Tref )  2.27  (340  298)

 h  95.34 kJ/kg
F

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 Example 2.4.2, Solution:
• Then the new vapour enthalpy (datum 25oC) – stream “V”:
Tb TV

h V       P dT
liq vap
C dT P hvap C
Tref Tb

• Work out these three parts separately:

C Pliq (Tb  Tref )  2.27  (278.9  298)  43.36 kJ/kg

hvap  381.6 kJ/kg

TV

 dT  0
vap
C P
Tb

• Then add them all together to find vapour enthalpy:

h  43.36  381.6  0  338.24 kJ/kg

V

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 Example 2.4.2, Solution:
• Applying the flash vaporisation energy balance:
hF  xhV  (1  x)hL

95.34  338.24 x  43.36(1  x)

 x  0.363 kg/s

• Alternatively, the percentage of the feed vaporised is

 x  36.3%

Thus the calculation yields the same result, as it should.

However, it is less efficient and more work is needed for
enthalpies!!

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