ENERGY BALANCES ON A

NONREACTIVE SYSTEMS
CHAPTER 8, FELDER

1
 Energy Balances on Nonreactive
Processes
It is expected that students will be able to:

• Define the variables Cv (T) (heat capacity in constant volume), Cp (T) (heat
capacity at constant pressure), Hm (heat fusion or heat melting), Hv (heat of
vaporization),

• Calculate Û and Ĥ for the species at the process state relative to the species
at the reference state.

• Estimate the heat capacity of a liquid and solid species using Kopp’s rule.

• Use the Psychrometric chart to carry out material and energy balance
calculations on a heating, cooling, humidification, or dehumidification
process
involving water. 2
 Hypothetical Process Path

 We will learn how to calculate ∆H and ∆U changes associated

with certain process specifically:

 Changes in P at constant T and state of aggregation

 Changes in T at constant P and state of aggregation
 Phase changes at constant T and P – melting, solidifying,
vaporizing, condensing, and sublimation
 Mixing of two liquids or dissolving of a gas or a solid in a
liquid at constant T and P.
 Chemical reaction at constant T and P

 Calculate the overall ∆H using the summation of each ∆Hi

steps in system. 3
 Hypothetical Process Path

Suppose that we wish to calculate ∆Ĥ for a process in which solid

ice at -5oC and 1 atm is converted to water vapor at 300oC and 5
atm.

Since Ĥ is a state property, we could simply subtract ∆Ĥ at the

initial state from ∆Ĥ at the final state

∆Ĥ = Ĥ (vapor, 300oC, 5 atm) - Ĥ (solid, -5oC, 1 atm)

Suppose that we do not have such a table, our task is then to

construct a hypothetical process path from the solid ice at -5oC and
1 atm to the water vapor at 300oC and 5 atm
4
 Hypothetical Process Path

ˆ = H
H ˆ + H
ˆ + H
ˆ + H
ˆ + H
ˆ + Hˆ
1 2 3 4 5 6

Ice True Path Vapor

-5oC, 1 atm
ˆ1 Hˆ 300oC, 5 atm
H
Ĥ 6
Hypothetical Ice
Path ˆ 0oC, 1 atm
H2

Liquid Vapor
0oC, 1 atm Hˆ 5 300oC, 1 atm
ˆ3
H
Hˆ 4

Liquid Vapor
100oC, 1 atm 100oC, 1 atm
5
 Hypothetical Process Path
ˆ = H
H ˆ + H
ˆ + H
ˆ + H
ˆ + H
ˆ + H
ˆ
1 2 3 4 5 6
Ice True Path Vapor
-5 oC, 1 atm 300 oC, 5 atm
ˆ
H Hˆ
1

Ĥ 6
Ice
0 oC, 1 atm
0 oC(Ice) to 0 oC (liquid) 
Ĥ 2
melting process
Liquid Vapor
0 oC, 1 atm Hˆ 5 300 oC, 1 atm
ˆ3
H
100 oC(liquid) to 100 oC Hˆ 4
(vapor)  vaporization process
: Table B.1, or from steam Liquid Vapor
table, 99.6 oC, 1 bar or 1 atm 100 oC, 1 atm 100 oC, 1 atm
(water/ steam only)
6
 Example 1

Calculate the specific enthalpy requirement to transform water

liquid at 0oC and 0.01 bar to water vapor at 300oC and 5 bar

DĤ = Ĥ (vapor, 300oC, 5 bar) - Ĥ (liquid, 0oC, 0.01bar)

Table B.7, Ĥ (300oC, 5 bar) = 3065 kJ/kg

Table B.5, Ĥ (0oC, 0.01 bar) ~ 0 kJ/kg

Hence, DĤ ~ 3065 kJ/kg

Suppose that we do not have such a table, construct a hypothetical

process from water liquid at 0oC and 0.01 bar to water vapor at
300oC and 5 atm
7
 Example 1 - Hypothetical Process Path of Enthalpy
Requirement to Generate Steam at 300 oC, 5 bar
ˆ = H
H ˆ + H
ˆ + H
ˆ + H
ˆ + H
ˆ = 3065.6 kJ/ kg
1 2 3 4 5

Liquid
True Path Vapor
0 oC, 0.01 bar
300 oC, 5 bar
Ĥ 1  0 kJ/ kg ΔĤ = 3065 kJ/ kg
Hypothetical
ΔĤ 5 = -9 kJ/ kg
Path
Liquid
0 oC, 1 bar Vapor
Ĥ 2 = 419 kJ/ kg 300 oC, 1 bar
ΔĤ 4 = 398.6 kJ/ kg
ΔĤ 3 = 2257 kJ/ kg

Liquid Vapor
99.6 oC, 1 bar 99.6 oC, 1 bar
8
 Working Session 1

Cyclohexane vapor at 180oC and 5 atm is cooled and

condensed to liquid cyclohexane at 25oC and 5 atm. The
change enthalpy for the condensation of cyclohexane at
80.7oC and 1 atm is known. Construct a hypothetical process
path of the above process

9
 Changes in Pressure at Constant
Temperature
 Internal energy is nearly independent of pressure on solid and
liquid at fixed temperature, as is specific volume.
 If the pressure of liquid and solid change at constant temperature,
you may write

ˆ »0
U and H  = U+

ˆ  PV
  
ˆ  » V
ˆ P

 Both Û and Ĥ are independent of pressure for ideal gas.

 Consequently, you may generally assume Û  0 and Ĥ  0

for a gas undergoing isothermal pressure changes unless gas at
temperature well below oC or well above 1 atm are involved
10
 Sensible Heat and Heat Capacities

 Sensible heat signifies heat that must be transferred to raise or

lower the temperature of a substance or mixture of substances.

 The quantity of heat required to produce a temperature change

in a system is given by the first law of thermodynamics,
neglecting the changes in kinetic and potential energies and as
well as work.

Q = U (closed system)
Q = H
 (open system)
11
 Heat Capacity at Constant Volume

∆U for constant V, and changes in T

 ˆ    U
U ˆ
V̂ = constant C v  T  =  lim  =  
 T  0 T
   T  v
Û  J/ kg
Û slope of the curve, Cv(T). Only
∆T “linear” in a very narrow range

ˆ = C (T)dT
dU v
T1 T1 + ∆T
T (oC) T1 + T
Û =  T1
C v (T)dT

12
 Heat Capacity at Constant Volume

DU for variable T and V


A T1 , V
1
ˆ
ˆ 
U 1
 A T
1
, V 2
ˆ  Uˆ
2

                  
 ˆ
 A T2 ,V 2 
ˆ = U
U ˆ + Uˆ
1 2

Û1 »0 For any substance

T2 Ideal gas: exact

Û2 »  C v (T)dT Solid or liquid: good approximation
T1
Real gas: valid only if V is constant

13
 Example 2 : Evaluation of an Internal Energy
Change from Tabulated Heat Capacity

Calculate the heat required to raise 200 kg of nitrous oxide from 20 oC to 150oC in a
constant-volume vessel. The constant-volume heat capacity of N 2O in this temperature
range is given by the equation where T is in oC.

 
C v kJ/ kg ×o C = 0.855 + 9.42 ×10 -4 T
 kJ 
Û  kJ/ kg =  
150o C

-4
0.855 + 9.42 ×10 T  o  dT
20o C
 kg × C 
150o C
150o C 9.42 ×10-4 T 2
Û  kJ/ kg  = 0.855T + 9.42 ×10 T -4
+
20o C 2 20 o C

= 111+10.4  kJ/ kg = 121 kJ/ kg

The energy balance for this closed system

ˆ = m(kg)U(kJ/
Q = U ˆ kg) = (200 kg)(121kJ/ kg) = 24,200 kJ
14
 Heat Capacity at Constant Pressure

∆H for constant P and variable T

 ˆ    H
H ˆ
C p  T  =  lim  =  
P = constant
 T  0 T
   T p
Ĥ  J/ kg
Ĥ slope of the curve, Cp (T). Only
∆T “linear” in a very narrow range
ˆ = C (T)dT
dH p

T1 T1 + ∆T
T1 + T
T (oC) Ĥ = T1
C p (T)dT

15
 Heat Capacity at Constant Pressure

DH for variable T and P

 For a process A(T1, P1)  A(T2, P2) we may construct two-step process path

A  T1 ,P1    A  T1 ,P2    A  T2 ,P2 

ˆ
H ˆ
H
1 2

                 
ˆ = H
H ˆ + H ˆ
1 2

 For the first step change (DH1) in pressure at constant temperature

Ĥ1 = 0 (ideal gas)

»V ˆ P (solid or liquid)

16
 Heat Capacity at Constant Pressure

 For the second step change (∆Ĥ2) in temperature at constant pressure

T2
Ĥ2 =  T1
C p (T)dT Solid, liquid & ideal gas

 Hence, ∆Ĥ = ∆Ĥ1 + ∆Ĥ2

T2

Ideal gas: Exact
Ĥ = C p (T)dT Nonideal gas : Exact only if P constant
T1

T2
ˆ ˆ
H = VP +  C p (T)dT Solid or Liquid
T1

17
 Specific Heat Capacity Formulas

Cp = a + bT + cT2 + dT3
 Values for a, b, c and d are obtain from:
 Table B.2
 Perry’s Handbook (Section 3)

 When reading the coefficients from Table B.2 do not mistake their orders
of magnitude
 72.4 is read from column labeled b . 105 means that b = 72.4 x 10-5

 Simple relationship exist between Cp and Cv for two cases:

For liquids and solids: Cp ~ Cv

Ideal gases: Cp = Cv + R (R = gas constant)

18
 Specific Heat Capacity
Formulas (cont’d)

 The heat required to raise the temperature of m (kg) of a liquid from

T1 to T2 at constant pressure is
T2
ˆ = m C (T)dT
Q = mH  (1) p T1

The above formula is sometimes simplified as

(2)= mC p  T2 - T1 
Q = mC p T

What assumption about Cp is required to simplify Equation (1) to

Equation (2)?
19
 Example 3: Evaluation of Cp & Cv

The constant-pressure heat capacity of carbon monoxide (CO)

is given by the expression

 
C p cal / mol.o C = 6.890 + 0.001436T  C
o

a. Write an expression for the heat capacity at constant volume

for CO, assuming ideal gas behaviour
b. Derive an expression for Cp(Btu/Ib-mole.oF) as a function of
T(oF). (Remember that the temperature unit in the
denominator refers to a temperature interval)

20
 Working Session 2

Estimate the specific enthalpy of steam at 350 oC and 100 bar

relative to steam at 100 oC and 1 atm using

a. The steam tables

b. Table B.2 and assuming ideal gas behavior

What is the physical significance of the difference between the

values of Ĥ calculated by the two methods?

21
 Example 4 : Evaluation of DH
using Heat Capacity
 Fifteen kmol/min of air is cooled from 430 to 100 oC. Calculate the
required heat removal rate using
 Heat Capacity from Table B.2
 Specific Enthalpies from Table B.8

Air (g, 430oC)  Air (g, 100oC)

With DEk, DEp, and Ws deleted, the energy balance is

Q = H = n H 
air air,out
- n
 
H
air air,in
= n
 air
H
100o C
Q = 430o C
CP dT

 Assuming ideal gas behavior, so that the pressure changes do not effect
specific enthalpy 22
 Solution : The Hard Way
(using Heat Capacity from Table B.2)
 Integrate the heat capacity formula in Table B.2

Ĥ  kJ/ mol =

100o C
 430o C
C p dT

Ĥ  kJ/ mol =  0.02894 + 0.4147 ×10 

100o C

-5
T + 0.3191×10 -8 T 2 -1.965 ×10 -12 T3 dT
430o C

0.4147 ×10-5
Ĥ  kJ/ mol =  0.02894 100 - 430  +
2

100 2 - 430 2 
-12
0.3191×10-8
+
3
3

100 - 430 - 3

1.965 ×10
4

100 4 - 430 4   kJ/ mol

Ĥ  kJ/ mol =  -9.5502 - 0.3627 - 0.0835 + 0.0167  kJ/ mol = - 9.98 kJ/ mol

23
 Solution : The Easy Way
(using Specific Enthalpies from Table B.8)
 Use Tabulated enthalpies form Table B.8 ( …. What is the reference
temp.?)
 
Ĥ 100 o C = 2.19 kJ/ mol Table B.8
Ĥ  430 C  = 11.24 + 0.30(14.37 -11.24) kJ/ mol = 12.17 kJ/ mol
o

Ĥ =  2.19 -12.17  kJ/ mol = - 9.98 kJ/ mol

ˆ= 15 kmol 103 mol - 9.98 kJ 1min 1kW

Q = H
 = nH = - 2500 kW
min 1kmol mol 60 s 1kJ/ s

 Table B.8 and B.9 apply strictly for heating and cooling at a constant
pressure of 1 atm and may also be used for non-isobaric heating and
cooling of ideal gas
24
 Example 5 : Evaluation of DU using
Heat Capacity Relationship
 Fifteen kmol of air is cooled from 430 to 100 oC in a constant-volume
vessel. Calculate the required heat removal rate using

 Cv = Cp - R & Heat Capacity from Table B.2

Air (g, 430oC)  Air (g, 100oC)

With DEk, DEp, and Ws deleted, the energy balance is

ˆ
Q = U = nair U - n ˆ
U = n Uˆ
air, final air air, initial air
100o C
Q=  430o C
C V dT

25
 Assuming ideal gas behavior
 Solution : The Hard Way
(using CV & Cp relationship and
Heat Capacity from Table B.2)
 substitute Cv by Cp - R & apply the heat capacity formula in
Table B.2
R (KJ/mol-C)
Ĥ  kJ/ mol = C - R  dT
100o C
 430o C P

Ĥ  kJ/ mol =  0.02894 + 0.4147 ×10 

100o C

-5
T + 0.3191×10 -8 T 2 -1.965 ×10-12 T3 - 0.008314 dT
430o C

0.4147 ×10-5
Ĥ  kJ/ mol =  0.020626 100 - 430  +
2
100 2 - 430 2  
-12
0.3191×10-8
+
3
3
100 - 430 - 
3

4

1.965 ×10
100 4 - 430 4   kJ/ mol

Ĥ  kJ/ mol =  -6.8066 - 0.3627 - 0.0835 + 0.0167  kJ/ mol = - 7.236 kJ/ mol

26
 Solution : The Easy Way
(using CV & Cp relationship and
Heat Capacities from Table B.8)
 Use H = U + PV correlation & Table B.8

ˆ  kJ/ mol = U
H ˆ + RT
ˆ  kJ/ mol = H
U ˆ - RT
 kJ 1K 
ˆ  ˆ ˆ 
U  kJ/ mol = H100o C - H430o C -  0.008314

o  100 - 430  C
mol- K 1 C 
o

Û  kJ/ mol = 2.19 -12.17 + 2.7436

Û  kJ/ mol = - 7.236

3
ˆ 15 kmol 10 mol - 7.236 kJ 1min 1kW
Q = U = nU = = -1809 kW
1kmol mol 60 s 1kJ/ s
27
 Working Session 3 - Problem 8.3
(Modified)
The constant-volume heat capacity of hydrogen sulfide (H2S) at low pressures is
given by the expression

 
C v kJ/ mol×o C = 0.0252 + 1.547x10 -5 T - 3.012x10-9 T2

where T is in oC. A quantity of H2S is kept in a piston-fitted cylinder with initial

temperature, pressure and volume equal to 25oC, 2 atm and 3 liters, respectively.

a. Calculate the heat (kJ) required to raise the gas temperature from 25 oC to 1000
o
C if the heating takes place at constant volume.
b. Calculate the heat (kJ) required to raise the gas temperature from 25 oC to 1000
o
C if the heating takes place at constant pressure.
c. What would piston do during the heating process in part (b). What is the
physical significance of the difference between the values of Q calculated in
part (a) and part (b)? 28
 Working Session 4 - Problem 8.9

Chlorine gas is to be heated from 100oC and 1 atm to

200oC

a. Calculate the heat input (kW) required to heat a stream

of the gas flowing at 5 kmol/s at constant pressure
b. Calculate the heat input (kJ) required to raise the
temperature of 5 kmol of chlorine in a closed rigid
vessel from 100oC and 1 atm to 200oC
c. What is the physical significance of the numerical
difference between the values calculated in part (a) and
part (b)?
29
 Working Session 5 - Problem 8.15

A stream of water vapor flowing at a rate of 250 mol/h is

brought from 600 oC and 10 bar to 100 oC and 1 atm

a. Estimate the cooling rate (kW) using (i) steam tables,

(ii) Table B.2 and (iii) Table B.8
b. Which of the answers is part (a) is most accurate?
Why?
c. What is the physical significance of the numerical
difference between the values calculated with methods
(i) and (ii)?

30
 Estimation of Heat Capacities

 You may use the following approximation to find heat capacity if you don’t
have enough data:
 For a mixture of gases and liquids, calculate the total enthalpy change as
the sum of the enthalpy changes for the pure mixture components.

 For a highly dilute solutions of solids or gases in liquids, neglect the

enthalpy change of the solute. The more dilute the solution, the better this
approximation.

 The calculation of enthalpy changes for the heating or cooling of a mixture

of known composition can be simplified using this formula:
C 
p mix
(T) = all
yiCpi (T)
Ĥ =  C 
T2
p mix
(T)dT
T1
mixture
components
31
 Estimation of Heat Capacities

 Kopp’s rule is an empirical method for estimating heat capacity

of a solid or liquid at or near 20oC.
 Cp of a molecular compound is the sum of contributions of each
element in the compound.
 The values for the coefficients are given in Table B.10
 Heat capacity of solid calcium hydroxide, Ca(OH)2 is estimated
as

C   
p Ca O H
2
 
= Cpa
Ca
 
+ 2 Cpa
O
 
+ 2 Cpa
H

= 26 +  2 ×17  +  2 × 9.6   J/ (mol×o C)

= 79 J/ (mol×o C)
32
 Example 6 -
Heat Capacity of a Mixture
 Calculate the heat required to bring 150 mol/h of a stream containing 60%
C2H6 and 40% C3H8 by volume or mole from 0oC to 400oC. Determine the
heat capacity for the mixture as part of the problem solution.

 The polynomial heat capacity formula for ethane and propane given in
Table B.2 are substituted:

 
(Cp )mix kJ/ (mol×o C = 0.600(0.04937 +13.92 ×10 -5 T - 5.816 ×10- 8T2 + 7.280 ×10-12 T3 )
+ 0.400(0.06803 + 22.59 ×10 -5 T - 13.11×10 -8 T 2 + 31.71×10-12 T3 )
= 0.05683 +17.39 ×10 -5 T - 8.734 ×10 -8 T 2 + 17.05 ×10-12 T3 )

400o C
Ĥ = 
0o C
(C p )mix dT = 34.89 kJ/ mol
33
 Example 6 - Heat Capacity of a
Mixture (cont’d)
 Alternatively …. calculate DH of each component, multiply by its mole fraction,
respectively & then sum them up, i.e.
400o C kJ
ĤC2H6 = 0 C P
o
C dT = 29.69
mol
o

=  o CP dT = 42.691 kJ
400 C
ĤC3H8
0 C mol
then Hˆ=
 yiHˆ i
i

and ˆ = 0.6(29.69) + 0.4(42.691) = 34.89 kJ

H
mol
 If the potential and kinetic energy changes and shaft work are neglected, the
energy balance becomes

ˆ = 150 mol 34.89 kJ

Q = H
 = n H = 5230 kJ/ h
h mol
 As usual, we assumed that the gases are sufficiently close to ideal for the formula
for Cp at 1 atm is valid. 34
 Working Session 6 - Problem 8.19 &
8.21 (Modified)
 A gas mixture containing one-third methane by volume and the
balance oxygen at 350 oC and 3 bar. Calculate the specific
enthalpy of this stream in kJ/kg relative to pure component at
25oC and 1 atm. State clearly all assumptions.

 Propane is to be burned with 15 % excess air. Before entering

the furnace the air and propane are uniformly mixed and
preheated from 0 oC to 300 oC. At what rate (Btu/h) must heat be
transferred to the propane-air mixture if the feed rate of propane
is 3820 SCMH [m3(STP)/h]?

35
 Energy Balances on a Single-Phase
Systems
 If the process only involves heating or cooling a single species from
T1 to T2, the procedure is straight forward.
 Evaluate the
T2 T2 Correct pressure
Û = 
T1
C v (T)dT Ĥ = 
T1
C p (T)dT
Changes if necessary

 For a closed system at constant volume ˆ

U = nU

 For a closed system at constant pressure ˆ

H = nH

 For a open system, calculate H ˆ

 = n H

36
 Procedure for Energy Balance
Calculations
 Perform all required material balance calculations

 Write the appropriate form of energy balance (closed or open system) and
delete any of the terms that are either zero or negligible for the given
process systems

 Choose a reference state – phase, temperature, and pressure – for each

species involved in the process
 For water look at the steam tables
 Choose the reference state used to generate the table
 Choose the inlet or outlet states as the reference state of the species (so
that at least one orÛ may Ĥ be set to zero)
37
 Procedure for Energy Balance
Calculations (cont’d)
 For a closed constant-volume system, construct a table with columns
 for initial and final amounts of each species (mi or ni) and

specific internal energies relative to the chosen reference states  Uˆ 

i

 For an open system, construct a table with columns

 for initial and final amounts of each species (mi or ni) and

 specific internal energies relative to the chosen reference states

 Hˆ 
i

References : Ac ( l,20oC, 5 atm), N2 (g, 25oC, 1 atm)

Substance nin (mol/s) Hˆ in Nout (mol/s) Hˆ out

Ac (v) 66.9 Ĥ1 3.35 Ĥ3
Ac (l) - - 63.55 0
N2 33.1 33.1
Ĥ2 Ĥ4
38
 Procedure for Energy Balance
Calculations (cont’d)
 Calculate all required values of internal energy and enthalpies
and insert in the appropriate places in the table.

 Calculate

Closed System : U =  n Uˆ -  nUˆ

final
i i
initial
i i
or  m Uˆ -  m Uˆ
out
i i
in
i i

O pen System : H = i i  i i

n
 ˆ - n Hˆ
H
final initial
or  i i  i i
m
 ˆ - m
H
out
 ˆ
H
in

39
 Procedure for Energy Balance
Calculations (cont’d)
 Calculate any work, kinetic energy, or potential energy terms
that you have not dropped from the energy balance.

 Solve the energy balance for whichever variable is unknown

from the equation given below (often Q )

Closed System : Q - W = U+ Ek + Ep

O pen System : Q - W
 = H
s
 + E + E
k p

40
 Example 7 - Recalling Example 5 to
Demonstrate the use of Reference States

 Fifteen kmol/min of air is cooled from 430oC to 100oC. Calculate the

required heat removal rate (KW)

Air (g, 430oC) Cooler Air (g, 100oC)

With DEk, DEp, and Ws neglected and assuming ideal gas behavior, so that
the pressure changes do not effect specific enthalpy the energy balance is

Q = H
 = n H
air
ˆ
air,out ˆ
- H air,in 
To C
Ĥair,i = 
Tref o C
CP dT if using Table B.2
ˆ =H
H ˆ - H ˆ if using Table B.8
air,i air,i air, ref
41
 Example 7 - Recalling Example 5 to
Demonstrate the use of Reference States
Reference : Air (g, 25oC, 1 atm)
nin nout
Substance Ĥin Ĥout
(kmol/min) (kmol/min)
Air 15 Ĥ1 15 Ĥ2

if using Table B.2 if using Table B.8

430o C kJ ˆ kJ ˆ = 2.19 kJ ,
Ĥ1 =25o C CP dT = 12.171
mol
H air, ref
= 0
mol
, H1
mol
o
100 C kJ kJ
Ĥ2 =  o CP dT = 2.191 Ĥ2 = 12.18
25 C mol mol
kJ kJ
ˆ =H
H ˆ =  2.191-12.171 kJ = - 9.98 kJ
ˆ -H Ĥ =  2.19 -12.18  = - 9.99
2 1
mol mol mol mol

3
15 kmol 10 mol - 9.98 kJ 1min 1kW
Q = H = nHˆ = = - 2500 kW
min 1kmol mol 60 s 1kJ/ s
42
 Example 7 - Recalling Example 5 to
Demonstrate the use of Reference States

 Hypothetical Process Path

Air (g, 430oC) H

 Air (g, 100oC)

H

1
H

2

Reference state
Air, 25oC

43
 Example 8 - Problem 8.25

Saturated steam at 300oC is used to heat a counter-currently flowing

stream of methanol from 65oC to 260oC in an adiabatic heat exchanger.
The flow of the methanol is 5500 L(STP)/min. and the steam condenses
and leaves the heat exchanger as water liquid at 90oC.
Saturated steam, 300 oC
a. Calculate the required
flow rate of the entering
steam in m3/min
methanol, 260 oC
b. Calculate the rate of heat
transfer from the water to
5500 L(STP)/min
the methanol (kW) methanol, 65 oC

Liquid water, 90 oC
44
 Working Session 7 - Problem 8.31
(Modified)
In the manufacture of nitric acid (NO3), ammonia (NH3) and preheated
air are mixed to form a feed gas containing 10 mole% NH3 at 600oC. NH3
enters the mixer at 25oC and 520 kg/h and the preheated air enters the
mixer at 700oC. Calculate the rate of heat loss (kW) from the mixer to its
surrounding.
NH3
25 oC
520 kg/h NH3 –Air mixture
n1 mol/s 600 oC
n3 mol/s
Air 0.1 mol NH3/mol
700 oC 0.9 mol Air/mol
n2 mol/s

Q

45
 Test #2 (Question 3 –
Session 2005/06)
Distillation is often used for separating
binary mixture. To facilitate the operation, ms kg/hr
Saturated steam
the feed temperature should be the same as 1 atm
the tray temperature at which the feed
stream is fed. This is normally
1 kg/hr
accomplished using a pre-heater. In one
30 oC
process, a benzene-toluene mixture feed 70 oC 40 wt % Benzene
stream is heated from 30oC to 70oC in a 60 wt % Toluene
shell and tube heat exchanger using steam,
condensing at 1 atm. If the benzene
composition in the mixture is 40% by Saturated liquid
1 atm
weight, determine the amount of steam
required for every kg/hr of benzene-
toluene feed.
46
 Processes Involving Phase Changes

Processes of phase change

Liquid to vapor – vaporization

Vapor to liquid – condensation
Solid to liquid - fusion (melting)
solid to vapor -sublimation

47
 Latent Heats

 Latent Heats
 Specific enthalpy change associated with the transition of a
substance from one phase to another at constant temperature and
pressure.
 Normally tabulated in Table B1 usually apply to a substance at its
normal boiling and melting point and at pressure 1 atm.

 Two commonly encountered phase changes Latent Heats are:

 Heat of Fusion (or heat of melting). ∆Ĥm (T,P) is the specific

enthalpy difference between the solid and liquid forms of a species
at T and P.

 Heat of vaporization ∆Ĥv (T,P) is the specific enthalpy difference

48
between the vapor and liquid forms of a species at T and P.
 Example 1 : Heat of Vaporization

At what rate in kilowatts must heat be transferred to a liquid stream of

methanol at its normal boiling point to generate 1500 g/min of saturated
methanol vapor?

From table B.1 DĤv = 35.3 kJ/mol at Tbp = 64.7oC. The energy balance
with potential and kinetic energy changes neglected is

Q = H ˆ
 = n H
v

1500 g CH3O H 1mol 35.3 kJ 1min 1kW

Q = = 27.6 kW
min 32.0 g CH3O H mol 60 s 1kJ/ s

49
 Example 2: Vaporization and Heating

One hundred g-moles per hour of liquid n-hexane at 25oC and 7 bar is
vaporized and heated to 300oC at constant pressure. Neglecting the effect
of pressure on enthalpy, estimate the rate at which heat must be supplied.

An energy balance yields

Q = H
 =  W = E
p
= 0, Ek » 0 

100 gmol C6H14 (l) 100 gmol C6H14 (v)

Process
@ 25 C , 7 bar
o
@ 300oC , 7 bar

50
 Solution

From Figure 6.1-4 the temperature at which the vapor pressure of

n-Hexane is 7 bar (104 psia) is approximately 295oF (146oC) and
this the temperature at which vaporization actually occur

From Table B1 the normal boiling point for n-Hexane

Ĥv = 28.85 kJ/ mol at 69 o C

We must therefore find a path that takes hexane from a liquid to

vapor at 69oC rather than the true vaporization at 146oC.
51
 Possible Path for n-Hexane Process

State 1 C State 4 F State 7

n -C6H14 (l) n -C6H14 (v) n -C6H14 (v)
25oC , 7 bar 25oC , 7 bar 300oC , 7 bar
A G
State 2 D State 5
n -C6H14 (l) n -C6H14 (v)
69oC , 1 atm 69oC , 1 atm
B H
State 3
E State 6
Since we know the ∆Ĥv at 69oC
n -C6H14 (l) n -C6H14 (v)
then the path of ADG is
146oC , 7 bar 146oC , 7 bar selected
52
 Path of DHA

 
o
ˆ =Vˆ P + 69 C C
H A o p 25 C C6 H14 (l)
dT

Table B.1  SG = 0.659  r = 0.659 kg/L

Table B.2  Cp = 0.2163 kJ(moloC)
1 atm = 1.013 bar

ˆ =
H
1L 1.013 - 7.0  bar 86.17 kg 0.008314 kJ/ (mol×K)
A
0.659 kg 1000 mol 0.08314 L×bar / (mol×K)
 69 - 25
o
0.2163 kJ C
+ o
=  -0.0782 + 9.517  kJ/ mol = 9.44 kJ/ mol
mol× C

53
 Path of ∆HD and ∆HG

ˆ = H
HD
ˆ
v  C 6H14
 69 C, 1 atm  =
o
28.85 kJ/ kg

C 
300o C
ĤG = 
69o C p C H (v)
6 14
dT (from equation 8.3 -10a)

 
C p kJ/ mol×o C  = 0.13744 + 40.85 ×10 -5 T - 23.92 ×10-8 T 2 + 57.66 ×10-12 T3
 

ĤG = 47.1 kJ/ mol

For the overall process ˆ = H

Q = H ˆ + H
ˆ + H
ˆ = 85.5 kJ/ mol
A D G

100 mol 85.5 kJ 1h 1kW

Q = = 2.38 kW
h mol 3600 s 1kJ/ s

54
 Phase Change in Closed System

 Evaluate ∆Û for phase change in the closed system using the equation
given below:
U  
ˆ = H -  PV
ˆ

 For phase change such as Fusion, which involve only liquids and
solid, changes
PVˆ in are generally negligible

ˆ » H
U ˆ
m m

 For vaporization PVˆ for the vapor (which equals RT if ideal gas
behavior may be assumed)

ˆ = H
Uv v  
ˆ -  PV
ˆ ˆ - RT
» H v

55
 Example 10 - Problem 8.36

Calculate the specific enthalpy (kJ/mol) of n-hexane vapor at 200oC and 2

atm relative to n-hexane liquid at 20oC and 1 atm, assuming ideal gas
behaviour. Show clearly the process path you used the ideal gas
assumption.
liquid True Path Vapor
20oC, 1 atm 200oC, 2 atm
Hypothetical Ĥ
Path Ĥ4
Ĥ1
Vapor
200oC, 1 atm
Ĥ3
Ĥ2
Liquid Vapor
68.74oC, 1 atm 68.74 oC, 1 atm

Hˆ = Hˆ 1 + Hˆ 2 + Hˆ 3 + Hˆ 4

56
 Working Session 8 - Problem 8.38

Benzene vapor at 580oC is cooled and converted to a liquid at 25oC in a

continuous condenser. The condensate is drained into 1.75-m3 drums, each of
which takes 2 minutes to fill. Calculate the rate (kW) at which heat is
transferred from the benzene in the condenser.

Process path :-
Ĥ1 ˆ
-H vap
(vapor, 580oC) (vapor, Tbp, 1 atm= 80.1oC) (liquid, Tbp, 1 atm=80.1oC)

(liquid, 25oC)
Ĥ2

Q = n H 
ˆ = n H
ˆ - H
1
ˆ + H
vap
ˆ
2 
57
 Definition of Polarity

Polar Molecules

In chemistry, a polar molecule is a molecule

in which the centers of positive and negative
charge distribution do not converge. These
molecules are characterized by a dipole
moment which measures their polarity.

A commonly-used example of a polar compound is

water (H2O). The electrons of water's hydrogen
atoms are strongly attracted to the oxygen atom,
thus, water has a relatively strong negative charge
on the top and a positive charge at the bottom

58
 Estimation and Correlation of Latent
Heats
 Trouton’s Rule
 A simple formula for estimating standard heat of vaporization (DĤv at

the normal boiling point)

 Provides an estimate to within 30 % accuracy

 Where Tb is the normal boiling point

 0.088Tb (K) (nonpolar liquid)

Ĥv  kJ/ mol
 0.109Tb (K) (water, low molecular weight alcohols)

 Chen’s Equation
 Where Tb is the normal boiling point and Tc is the critical temperature

in Kelvin and Pc is critical pressure in atm

Tb 0.0331 Tb / Tc  - 0.0327 + 0.0297log10 Pc 
Ĥv  kJ/ mol =
1.07 -  Tb / Tc  59
 Latent Heat of Vaporization

 Clausius-Clapeyron Equation
 ∆Ĥv is constant over the range of temperature encompassed by the

vapor pressure data

 The latent heat of vaporization may be determined from plot of ln
p* versus 1/T
Ĥv
lnp* = - +B
RT

 When the heat of vaporization varies with temperature it is

d  lnp *
necessary to use Clapeyron Equation
ˆ
H v
=-
d(1/ T) R 60
 Watson’s Correlation

 Procedure for calculating the latent heat of vaporization at one

temperature from a known value at any other temperature.

0.38
 Tc - T2 
Hv  T2  = Hv  T1  
ˆ ˆ 
 Tc - T1 

 Where Tc is the critical temperature of the substance

61
 Estimation of Heat of Vaporization

The normal boiling point of methanol is 337.9 K, and the critical

temperature of this substance is 513.2 K. Estimate the heat of vaporization
of methanol at 200oC

Trouton’s Rule

Ĥv  337.9 K =  0.109   337.9  = 36.8 kJ/ mol

Watson’s Correlation - Using the estimated DHv by Trouton’s Rule

0.38
 513.2 - 473 
Ĥv  473 K == 36.8   = 21.0 kJ/ mol
 513.2 - 337.9 
62
 Heat of Fusion

 A formula for approximating a standard heat of fusion

is
 0.0092Tm (K) (metallic elements)
Ĥm  kJ/ mol  0.0025Tm (K) (inorganic compounds)
 0.050Tm (K) (organic compounds)

63
 Example 11 - Problem 8.44

Estimate the heat of vaporization (kJ/mol) of benzene at a

pressure of 100 mm Hg, using

a. The normal boiling point given in Table B.1, the boiling point at
100 mm Hg as determined by the Antoine equation and Watson’s
correlation
b. The Clausius-Clayperon equation and the boiling points at 50 mm
Hg and 150 mm Hg as determined from the Antoine equation
c. The normal boiling point given in Table B.1, the boiling point at
100 mm Hg as determined from Antoine equation and the heat
capacity data given in Table B.2

64
 Energy Balances on Process involving
Phase Changes

 An energy balance on a process in which a component exists in two

phases
 Choose a reference state for that component by specifying both a
phase and a temperature
 Calculate the specific enthalpy of the component in all process
streams relative to a reference state
 If the substance is a liquid at its reference state and a vapor in a
process stream, Ĥ may be calculated using process path calculations

65
 Example 12 - Problem 8.50
(Modified)
A mixture of hexane vapor and air leaves a solvent recovery unit and flows
through a 70 cm-diameter duct at a velocity of 3 m/s. At sampling point in
the duct the temperature is 40oC, the pressure is 850 mm Hg, and the dew
point of the gas sample is 25oC. The gas is fed to a condenser in which it is
cooled at constant pressure, condensing 60% of the hexane in the feed.
Calculate the required condenser outlet and cooling rate (kW).

70 cm-ID duct Q
v=3 m/s P= 850 mm Hg
T= 40 oC Tc= ? oC
P= 850 mm Hg Condenser nc = ? mol/s
Tdp= 25 oC
yh,c=? mol hexane/mol
nf = ? mol/s yair, c=? mol air/mol
yh,f=? mol hexane/mol
yair,f=? mol air/mol 60 % of hexane in feed
nhex = ? mol/s
66
 Problem 8.50 (Modified)
Assuming an ideal gas air-hexane mixture entering the condenser,

nf = PV/RT = 50.3 mol/s

Tdp= 25oC , thus the partial pressure of condensable species (i.e. hexane), using
Antoine equation, p*h = 151.3 mm Hg

hence, p*h = yh,f P …… yh,f = 0.178 mol hexane/mol and yair,f = 0.822 mol air/mol

then, nhex = (0.6)(0.178)(50.3) = 5.372 mol/s hexane condensed !

and nc = 50.3 – 5.372 = 44.928 mol/s

yair, c = (0.822)(50.3)/44.928 = 0.92 mol air/mol
yh,c = 0.08 mol hexane/mol

p*h = yh,c P …… p*h = (0.08)(850) = 68 mm Hg 67

from Antoine equation, Tc (p*h = 68 mm Hg ) = 7.83 oC

 Problem 8.50 (Modified) – (cont’d)

Energy balance for open system, neglecting changes in kinetic and potential
energy and enthalpy is independent of pressure change,

Q =  n iHi - n iHi
out in

References : Hexane ( liquid,7.8oC), Air (gas, 25oC)

Substance nin (mol/s) Ĥin(kJ/mol) nout (mol/s) Ĥout(kJ/mol)
Hexane (v) 8.95 3.58
Hexane (l) - - 5.37 0
Air 41.35 41.35

68
 Problem 8.50 (Modified) – (cont’d)

Inlet stream
68.74 40
ˆ
Ĥhexane (v) = 7.8
C p,ldT + H vap,68.74
+  Cp,vdT
68.74

= 13.181 + 28.85 – 4.568 = 37.463 kJ/mol

40
Ĥair = 25
C p,vdT= 0.436 kJ/mol

Outlet stream

7.8
Ĥair =
 25
C p,v dT = - 0.499 kJ/mol
68.74 7.8
ˆ
Ĥhexane (v) = 7.8
C p,ldT  H vap,68.74
  Cp,vdT
68.74

= 13.181 + 28.85 – 9.303 = 32.728 kJ/mol

Ĥhexane (l) = 0 kJ/mol 69
 Problem 8.50 (Modified) – (cont’d)

Q =  nH
 i i - n iHi
out in

References : Hexane ( liquid,7.8oC), Air (gas, 25oC)

Substance nin (mol/s) Ĥin(kJ/mol) nout (mol/s) Ĥout(kJ/mol)

Hexane (v) 8.95 37.463 3.58 32.728
Hexane (l) - - 5.37 0
Air 41.35 0.436 41.35 -0.499

Q = -257 kW

70
 Example: Heat Balance on a Distillation
Column
An equimolar liquid mixture of benzene (B) and toluene (T)
at 10oC is fed continuously to a vessel in which the mixture is heated
to 50oC. The liquid product is 40 mole% B and the vapor product is
68.4 mole% B. How much heat must be transferred to the mixture
per mole of feed?

nv (mol), 50oC, 34.8 mmHg

0.684 mol B/mol
0.316 mol T/mol
1 mol, 10oC Q(J)
0.500 mol B/mol nl (mol), 50oC
0.500 mol T/mol 0.400 mol B/mol
0.600 mol T/mol
71
 Example: Heat Balance on a Distillation
Column (cont’d)

Total mass balance: 1.00 = nv + nl nv = 0.352 mol


Benzene balance : 0.500 = 0.684nv + 0.400nl nl = 0.648 mol
References: B(l, 10oC), T(l, 10oC)
Substance nin (mol) Ĥin nout (mol) Ĥout
(kJ/mol) (kJ/mol)
B(l) 0.500 0 0.259 H1
T(l) 0.500 0 0.389 H2
B(v) - - 0.241 H3
T(v) - - 0.111 H4

72
 Example: Heat Balance on a
Distillation Column (cont’d)

B(l,50 C): C6H6 (l, 10oC)  C6H6 (l, 50oC)

C 
50o C
Ĥ1 =  p C H (l)
dT = 5332 J/ mol
10o C 6 6

T(l,50 C): C7H8 (l, 10oC)  C7 H8 (l, 50oC)

C 
50o C
Ĥ2 =  10o C p C H (l)
7 8
dT = 6340 J/ mol

B(v,50oC): C6H6(l, 10oC)  C6H6(l, 80.1oC)  C6H6(v, 80.1oC)  C6H6(v, 50oC)

C    C 
80.1o C 50 o C
ˆ = ˆ (80.1 C)+
 + H 
o
H3 o p v p = 37520 J/ mol
10 C C 6H6 (l) 80.1o C C 6H6 (v)

73
 Example: Heat Balance on a
Distillation Column (cont’d)

T(v,50oC): C7H8(l, 10oC)  C7H8(l, 110.62oC) C7H8(v, 110.62oC)  C7H8(v, 50oC)

C  C 
110.62o C 50 o C
ˆ = ˆ (110.62 o C) +
H 4 
10o C p
C 7 H8 (l)
+ H v  110.62o C p
C7 H8 (v)
= 42930 J/ mol

The energy balance is

Q = H =  n Hˆ -  n Hˆ
out
i i
in
i i
 Q= 17.7 kJ

74
 Example: Heat Balance on a
Distillation Column (cont’d)
∆H and ∆ U

Are tabulated No Choose a

enthalpies reference state
available? • T, P “SOA”
Yes
Use the given Calculate Ĥ and Û
T and P to find using known Cp or
Ĥ Û estimated Cp
and
(* SOA -State of Aggregation, i.e., liquid, vapor or aqueous )

75
 Working Session 9 - Problem 8.52
(Modified)
A liquid containing 50 mole% benzene (Bz) and the balance toluene (Tl)
at 25oC is fed to a continuous single-stage evaporator at a rate of 1320
mol/s. The liquid and vapor streams which are in equilibrium with each
other leaving the evaporator at 95oC. The liquid product stream contains
42.5 mole% benzene. Using Raoult’s law, calculate the vapor product
compositions, the system pressure (atm). Estimate the heating
requirement for this process in kW.
V mol/s
T= 95oC
F = 1320 mol/s yBz mol Bz/mol
T= 25oC (1-yBz ) mol Tl/mol
Evaporator
50 mole% Bz
50 mole% Tl
L mol/s
Q T= 95oC
0.425 mol Bz/mol
0.575 mol Tl/mol 76