ENERGY BALANCES ON NONREACTIVE PROCESSES (PART A)

Reference: Chapter 8 of R.M. Felder & W. Rousseau, Elementary Principles of Chemical

Processes, 3rd ed. 2005 (Wiley).

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Hypothetical process paths

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Example:
Suppose that we wish to calculate for a process in which solid phenol at 25oC and 1 atm is
converted to phenol vapour at 300oC and 3 atm. If we had a table of enthalpies for phenol like
water, we could simply subtract at the initial state from at the final state, or
However, we do not have such a table. Our task is then to construct a hypothetical process path
from the solid at 25oC and 1 atm to the vapour at 300oC and 3 atm.

Exercise: identify Type (1-5) of each step on the hypothetical path.

Test yourself:
Construct a path that utilizes as many known enthalpy changes as possible for cyclohexane
vapour at 180oC and 5 atm is cooled and condensed to liquid cyclohexane at 25oC and 1 atm. We
know for the condensation of cyclohexane at 80.7oC and 1 atm.

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where

Expressions for Cv(T) for many substances can be determined from data in the text.

For all but large pressure changes and small temperature changes, the first term of equation 8.310b is usually negligible relative to the second term.
Dimensions of Cp or Cv (Heat Capacity)
Energy/mass (or mol)/ T
Units of CP or Cv:

Conversion:

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Heat Capacity data

Data available in

Equations

Tables

Charts
CP equations (from Table B.2 of Felder & Rousseau):

Substitute into

The hard way: Integrate term by term, substitute upper and lower temperature limits.
The easy way: Use the Physical Property data base on the ICPP CD. Click on the en ha pies
tab, select the desired substance under ompounds, enter the initial and final temperatures, and
hit enter. The enthalpy change will appear in the window at the upper right.
Estimation of Heat Capacity
1.
Estimate of CP for solids, liquids, mixtures: Kopps rule (Section 8.3c and Table B.10).
Use when you cant find the data in table B.2.

At room temperature, CP of a compound is sum contributions of CP for each atomic

element.

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Example:
For Na2CO3 (solid)
CP (Na2CO3) = 2CP(Na)+ CP (C)+3 CP (O)
CP (Na2CO3) = 2(26)+ 1(7.5)+3(17)
= 110.5 J/mol. oC
From a table of data, for Na2CO3 (solid)
CP (Na2CO3) = 121 J/(mol. oC) for T: 15 98oC

Table B.2:

error from using Kopps rule = (121-110.5)/(121) x 100% = 8.7%

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Example:
CP (air) = 0.21CP(O2) + 0.79CP(N2)

For dilute solutions, CP of solution CP of solvent in solution.

Example: Estimate CP of a 21.6 wt% brine.

CP CP of water contributing to solution
= (1-0.216) CP,Water(l)
= (0.784)(1.0) cal/(g.oC)
= 0.784 cal/(g.oC)
cf. experimental value = 0.806 cal/(g.oC)

error = 2.7%

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CALCULATION OF ENTHALPY CHANGES

At constant pressure, for a change in temperature from T1 to T2:

1.

from Heat Capacity Equation

Form 1:

Form 2:

Example:
Calculate

for CO2 gas for T increasing from 70oC to 150oC using CP equation for CO2.

Solution:
CP equation for CO2.(g) is of form 1:
a = 36.11 x10-3, b = 4.23 3 x 10-5, c = -2.887x10-8, d = 7.464x10-12
(T in oC, for T: 0 1500oC; CP in kJ/(mol.oC))
T1 = 70oC; T2 = 150oC

2.
from Tabulated CP-T Data

obtained by graphical or numerical integration.

Example:
Data for CO2(g) (Mayhew & Rogers):
T(K)
300
325
350
375
400
450
500
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CP (kJ/kg.K)
0.846
0.871
0.895
0.918
0.939
0.978
1.014
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Calculate
for CO2 gas for T increasing from 70oC (343K) to 150oC(423K).
Plot CP versus T:

T1 = 343K, CP = 0.888 kJ/kg.K (by interpolation)

T2 = 423K, CP = 0.957 kJ/kg.K (interpolation)
Calculate by graphical integration:

3.

from Mean CP Data

Mean heat capacity defined over temperature interval Ti - Tj

CPm data available for certain materials, tabulated as a function of T over relatively large T
intervals, with a reference state specified.
In general,
is calculated using:

Example: Calculate
using mean CP data.

for CO2 gas at 1atm with a temperature change from 70oC to 150oC

CPm data for CO2 gas. Reference: 0oC, 1atm.

T(oC)
18
25
100
200
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CPm (cal/mol.oC)
8.595
8.706
8.716
9.122
9.590
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Solution:
Find CPm at 70oC by interpolation between 25 oC and 100 oC:

Similarly, for 150oC:

Comparison:

for CO2 gas for T = 70 oC to 150 oC

Method
CP equation
CP-T data (graphical integration)
Mean CP data

(kJ/mol)
3.233
3.248
3.248

Example: Energy Balance on Single-Phase Systems

In a steady-state process, 10 mol/s of O2 at 100oC and 10 mol/s of N2 at 150oC are mixed in a
vessel which has a heat loss to the surroundings equal to 209(T-25) J/s, where T is temperature
of the gas mixture in oC. Assuming the gases are well mixed, and the heat of mixing negligible,
estimate the temperature of the exit stream.
Solution:

Data:
From Table B.2:
O 2:
N 2:

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Basis: 1 second
Material balance at steady state:
O2:
In
=
Out
10 mol =
10 mol = nO2
N2:

In
=
10 mol =

Out
10 mol = nN2

General energy balance:

Q = -209(T2 25) J

=Q

solve for T2

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Solve

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T2 = 98.7oC

NB: if no heat loss, or system is adiabatic:

Q = 0 = H

Solve

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T2 = 124oC

12

Latent heats vary considerably with temperature but little with pressure at a given
temperature of phase transition.

Example: Water
T (oC)
25
50
100
121.8

P (bar)
0.03166
0.1233
1.01325
2.1

(kJ/kg)
2441.8
2382.1
2256.7
2198

For practical purposes, moderate variation of latent heats with pressure may be ignored.
Only the temperature where the transition occurs is taken into account.
i.e.

Standard Latent Heats

Defined as latent heats at total pressure of 1 atm and at its normal boiling or boiling point.
Example: For ethanol (from Table B.1, F&R)
= 38.56 kJ/mol at (78.5 oC, 1 atm) , i.e., at normal boiling point: 78.5 oC
= 5.021 kJ/mol at (-114.6oC, 1 atm), i.e., at normal melting point: -114.6oC

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Example:
At what rate in kilowatts must heat be transferred to a liquid stream of ethanol at its normal
boiling point in order to generate 1500 g/min of saturated ethanol vapour?

Solution:
Basis: 1 minute
Mass balance:

mL = mV = 1500 g = 1.5 kg

Energy balance:

from Table B.1 (Felder & Rousseau) for ethanol:

M.W. (C2H5OH) =46 g/mol

= 38.6 kJ/mol at 78.5oC, 1 atm

Rate of heat supplied

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ENERGY BALANCE CALCULATIONS WITH PHASE CHANGES

Phase changes often occur at temperatures other than the temperature for which latent heat and other
data are tabulated.
must select a hypothetical process path that permits available data to be used and facilitates the
calculations. This is possible since enthalpy is a state function.
When applying energy balance on a process in which a component exists in two phases, a reference
condition must be selected for that component. All calculations of enthalpy for the component in all
process streams must be made relative to this condition.
Example:
Determine the energy required to vaporise completely 10 kg of ethanol liquid at 1 atm pressure if the initial
temperature of the alcohol is 20oC.

Solution:
Energy balance:
where:
Consider process paths:
[1] (liq., 20oC) [2] (vap., TB)

[3] (liq., TB)

16

Data:
from Table B.1 for ethanol: TB =78.5oC;
= 38.6 kJ/mol
from Table B.2 (Felder and Rousseau) for ethanol (liq.):
(T : 0 100oC)

Energy required: Q = 9702 kJ

Example:
Water at 60 bar and 200oC passes through an adiabatic expansion valve, instantly forming a mixture of
liquid and vapour (steam) at 1.2 bar. If the steam is saturated, estimate its mass fraction (dryness fraction)
in the mixture.

Basis: 1 kg of liquid water feed

Mass (water) balance:
Energy balance:

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Data:
Inlet:

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P1 = 60 bar, T1 = 200oC
From S.T. @ 60 bar, TSat = 275.6oC inlet water is sub-cooled
From Table B.7 @ 60 bar and 200oC,

Outlet:
P2 = 1.2 bar, saturated steam and water
From Table B.6 @ 1.2 bar, TSat = 104.8oC = T2

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Example:
An equimolar liquid mixture of benzene and toluene at 10oC is fed continuously to a still in which the
mixture is heated to 50oC at a pressure of 34.8mmHg. The liquid product is 40mol% benzene and the
vapour product contains 68.4mol% benzene. How much heat must be transferred per gmol of feed?

Basis: F = 100mol
Material balance:
Benzene:
0.5 (1) = 0.684 V + 0.4 L
Toluene:
0.5 (1) = 0.316 V + 0.6 L
Solving (1) and (2):

V = 35.2 mol; L = 64.8 mol

(1)
(2)

Vapour phase: B = (35.2) (0.684) = 24.1 mol

T = 35.2 24.1 = 11.1 mol
Liquid phase:
B = (64.8) (0.4) = 25.9 mol
T = 64.8 25.9= 38.9 mol
Let Reference State: Benzene & Toluene @ 10oC, liquid
Species
Benzene (L)

50

25.9

Toluene (L)

50

38.9

Benzene (V)

24.1

Toluene (V)

11.1

Species
Benzene (L)
Energy balance:
Toluene (L)

25.9
?
(all other energy terms = 0)
38.9
?

Benzene (V)

24.1

37.525

Toluene (V)

11.1

25.9

Species
Benzene (L)

Toluene (L)
38.9
Let Reference State = liquid at 10oC
24.1
Benzene (V)

11.1
Toluene (V)

?
37.525
42.960

Species
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Benzene (L)

25.9

5.338

138.2

Toluene (L)

38.9

6.341

246.7

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(liq, 10oC) (vap, 50oC)

(liq, Tb,B) (vap, Tb,B)

Thermodynamic Data for Benzene:

Tb = 80.1oC;
CP,L (kJ/mol. oC) = 126.5x10-3 + 23.4 x10-5T
CP,V (kJ/mol.oC) = 74.06 x10-3 + 32.95 x10-5T - 25.2x10-8T2

Species
Benzene (L)

50

25.9

Toluene (L)

50

38.9

Benzene (V)

24.1

Toluene (V)

11.1

Species

Benzene (L)
(liq, 10oC)
Toluene (L)

(liq, TBenzene

b,T)
(V)

25.9
(vap, 50oC)
38.9

(vap,24.1
Tb,T)

?
?
37.525

Toluene (V)

Species

Benzene (L)

11.1

25.9

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Toluene

(L)

38.9

Benzene (V)

24.1

37.525

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Thermodynamic Data for Toluene:

Tb = 110.6oC;
CP,L (kJ/mol.oC) = 148.8x10-3 + 0.324T x10-5
CP,V (kJ/mol.oC) = 94.18 x10-3 + 38x10-5T - 27.86x10-8T2

Species
Benzene (L)

50

25.9

Toluene (L)

50

38.9

Benzene (V)

24.1

Toluene (V)

11.1

Benzene (L)

25.9

Toluene (L)

38.9

Benzene (V)

24.1

37.525

Toluene (V)

11.1

Benzene
Species(L)

25.9

Benzene
(L)
Toluene (L)

50
38.9

0?

25.9

Benzene
Toluene (V)
(L)

24.1
50

37.525
0

38.9

Benzene
(V)
Toluene (V)

0
11.1

0
42.960

24.1

Species(V)
Toluene

11.1

Benzene
Species(L)

25.9

5.338

138.2

Benzene
(L)
Toluene (L)

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25.9
38.9

?
6.341

246.7

Benzene
(V)
Toluene (L)

24.1
38.9

37.525
?

904.3

Benzene
Toluene (V)

11.1
24.1

42.960
37.525

476.9

Species

Species

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ENERGY BALANCES ON NONREACTIVE PROCESSES (PART B)

Reference: Chapter 8 of R.M. Felder & W. Rousseau, Elementary Principles of Chemical
Processes, 3rd ed. 2005 (Wiley).

Psychrometric (Humidity) Charts

Plots of several properties of a gas-vapour mixture. Also known as psychrometric charts.

Most common charts for air-water system at 1 atm, used extensively in analysis of humidification, airconditioning, drying processes

Examples of humidity charts in Felder & Rousseau (Fig. 8.4-1), Perrys (p. 12-4&5)

Ordinate moisture content or humidity:

Abscissa dry-bulb temperature (TDB): ordinary temperature measured for air

Wet-bulb temperature (TWB) or Saturation temperature: temperature of air at saturation, a
function of TDB and humidity. TDB & H change along constant wet bulb temperature line
(adiabatic saturation line)
Dew-point temperature (TDew): temperature at which air with given H is saturated if cooled at
constant pressure. Follow any point horizontally to the left until you reach the saturation curve.
Curves of constant Relative Humidity:

100% RH Saturation curve (TDB = TWB)

Specific (Humid) Volume: volume of air-water vapour mixture /mass dry air (m3/kg)

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Humid Heat Capacity: heat capacity of air-water vapour mixture based on 1 kg of dry air:
CS = CP,Dry Air + CP,H2O Vapour.H
Specific enthalpy of air at saturation:

(kJ/kg dry air)

Reference: H2O (liq), 0oC, 1atm

Specific enthalpy of unsaturated air:

+ Enthalpy deviation

Example:
Use the humidity chart to estimate H , TWB, TDew,

for an air at 38oC and 50%RH.

Answers:
H = 0.021 kg H2O/kg dry air
TWB = 28.8oC
TDew = 25.8oC
= 0.912 m3/kg dry air (by interpolation)
= 93.0 kJ/kg dry air
Enthalpy deviation = - 0.48 kJ/kg dry air (by interpolation)

= 93.0 - 0.48 = 92.5 kJ/kg dry air

CS = CP,Dry Air + CP,H2O Vapour.H

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Use of Humidity Chart for M&EB Calculations

simplifies solution of problems involving constant pressure air-water systems:

heating or cooling humid air at T > TDew horizontal path, ie at H = constant

if superheated air is cooled at 1 atm, the system follows a horizontal path until the saturation
curve (@ TDew) is reached; then process follows saturation curve
best basis of calculation is quantity of dry air in a feed or product stream

Example:
Air at 38oC and 50% RH is cooled to 18oC at 1 atm. Use the humidity chart to determine the final condition
of the air, and calculate the fraction of water that condenses, and the rate at which heat must be removed
to process 100m3/h of the air.
Solution:
Using humidity chart, find
- inlet air:

H
TDew

= 0.021 kg H2O/kg DA
= 25.8oC
= 0.912 m3/kg DA (by interpolation)
= 93.0 - 0.48 = 92.5 kJ/kg DA

- outlet air:
TDB = TWB = 18oC
H = 0.013 kg H2O/kg DA
= 0.842 m3/kg DA (by interpolation)
=

= 50.0 kJ/kg DA

Basis: 1 kg dry air (DA)

Mass balance:
Water:

L = 0.008 kg H2O

fraction of water condensed

= 0.008/0.021 = 0.38

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Energy balance:

Reference: H2O (liq), 0oC, 1atm

= 92.5 kJ/kg dry air
= 50.0 kJ/kg dry air

H = 1(50) + 0.008(75.3) 1(92.5) = 41.9 kJ

Q = 41.9 kJ: heat removed (per 1 kg dry air)
Basis: 100m3/h air in
Rate of heat removed:

Adiabatic Humidification

In adiabatic cooling (or humidification), inlet air is both cooled and humidified:
Evaporation

of cooling water, with the latent required for vaporisation provided by sensible
heat lost by the air as it cools: TAir Out < TAir In

Water vapour produced

increases humidity of air at exit:

HAir Out > HAir In

Adiabatic process:

Process follows the Adiabatic saturation line (const Wet-bulb Temperature line):

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Example:
Air at 38oC and 10% RH is humidified in an adiabatic spray tower operating at atmospheric pressure. The
emerging air is to have a 60% RH.
Use the humidity chart to determine the rate at which water must be added to humidify 1000 kg/h of the
entering air, and the temperature of the exiting air
Solution
Using humidity chart, find
- inlet air: H

= 0.0042 kg H2O/kg DA

- exit air: H

= 0.0105 kg H2O/kg DA

Rate of water added:

Temp of exit air TAirOut = 22.5oC (from chart)

If exit air is saturated (100% RH):
TAirOut = TAS = 17.5oC Adiabatic saturation temperature
Notes:
1.

The procedure employed for humidification calculation using humidity chart assumes that the
sensible heat change undergone by the liquid water is negligible compared to the heat of
vaporisation of water. This is feasible with a large amount of cooling water recirculated
compared to quantity of water evaporated.

2.

If the water undergoes a substantial temperature change, the full energy balance must be used
instead of the humidity chart approach.

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ENERGY BALANCES WITH MIXING AND SOLUTION

In mixing of different substances, attractive forces are overcome between molecules of the feed
materials and new forces develop between molecules of the product mixture or solution.

net absorption or release of energy, resulting in internal energy and enthalpy differences between
components and the mixture.

Thermal effects due to mixing and solution are:

low for gases or liquid mixture of similar compounds
large for liquid mixtures of different compounds

Ideal Solutions/Mixtures:

Non-Ideal Solutions/Mixtures:

Specific Enthalpy change due to mixing of

Liquid mixture Heat of mixing

Solution Heat of solution

Heats of Solution and Mixing

Integral Heat of Solution

Change in enthalpy for a process where 1 mole of a solute (gas or solid) is dissolved in n moles of a
liquid solvent at a constant temperature T.
Example:
HCl(g) + 5H2O(l)
HCl.5H2O (aq)
or

HCl(g) + 5H2O(l)
HCl (5H2O)
= - 64.047 kJ/mol HCl(g)

at 25oC, 1atm is standard heat of solution,

for common solutions (eg. Felder & Rousseau, Table B.11).

Use of

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. Data of

are available

as for chemical reactions

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Example:
What is the standard heat of formation of a 25%mol HCl-water solution?
Solution:
25 mol HCl(g) + 75 gmol H2O 1 mol HCl(g) + 3 mol H2O
Formation reaction for the solution HCl(3H2O):
[1] H2(g) + Cl2(g) + 3H2O
HCl(3H2O)
Related reactions:
[2]

HCl(g) + 3H2O(l)
HCl(3H2O)

[3]

H2(g) + Cl2(g)
HCl (g)

= - 56.85 kJ/mol HCl

= - 92.31 kJ/mol HCl

Since [1] = [2] + [3]:

{HCl(3H2O)} = (- 56.85) + ( 92.31) = -149.16 kJ/mol

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Example:
HCl acid id produced by absorbing gaseous HCl in water. Calculate the heat that must be transferred to/from
an absorber if HCl(g) at 100oC and H2O(l) at 25oC are fed to produce 100 kg/h of 20 wt% HCl(aq) at 40oC.

Solution Basis: 1 hour

P = 100 kg 20 wt% HCl(aq)

Energy balance:

Data:
Std heat of solution (Table B.11):
= - 68.231 kJ/mol HCl
CP of solution (Perrys handbook, p. 3-145, Table 3-187, gives data as function of mol% HCl in solution)
Given: 1/(1+8.1)= 11 mol% HCl,
CPsoln = 0.724 kcal/kg. oC at 40oC

CP,HCl(g) = 29.13 0.1341x10-2T(oC) J/moloC

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Q = H = - 34,040 kJ

Rate of heat removed = 34,040 kJ/h = 9.5 kW

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Enthalpy-Concentration Diagram

Plot of specific enthalpy of a mixture/solution versus concentration (mass or mol percent) of one
component with temperature as a parameter.

Extremely efficient way of presenting enthalpy data, although limited to binary solutions.

Figure 8.11

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Example:

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-x (wt%) chart for NaOH-water in Fig. I.3, Himmelblau. Note reference states:
(i)

forH2O: liquid @ 32oF

(ii)

for NaOH: infinite dilute solution @ 68oF

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Example: Use of

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-x diagram

A 5 wt% NaOH solution at 80oF is to be concentrated to 25.0 wt% by evaporation of water. The
concentrated solution and water vapour emerge at 230oF and 1 atm. Calculate the rate of heat supplied to
process 1000lb/h of the feed solution

Solution:
Basis: 1hr, F = 1000 lb
Mass balance: 1000 = V + L

(1)

NaOH: 1000(0.05) = V(0) + L(0.25)

(2)

L = 200 lb;

V = 800 lb

Energy balance around evaporator:

Using enthalpy-conc diagram for NaOH-H2O

Reference states: H2O(l, 32oF), NaOH(aq, 68oF, n=)

= 45 Btu/lb @ 80oF and 5wt% NaOH

= 170 Btu/lb @ 230oF and 25wt% NaOH

For V( H2O vapour @ 230oF(110oC), 1atm), use steam tables:

26,90kJ/kg =1,156 Btu/lb

Rate of heat supplied: 914x103 Btu/h

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Enthalpy-Concentration Diagram for 2-phase systems

Useful for energy balance calculations involving phase changes in binary systems at equilibrium

Example:

-x (mol%) chart for Ethanol-water in Fig. I.1, Himmelblau.

o Liquid and vapour phases in equilibrium at 1 atm.

o Tie-lines (constant temperature) connect liquid and vapour compositions in equilibrium
o Reference states: pure liquids @ 32oF

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Example: Equilibrium flash vaporization

A 50 wt% ethanol-water liquid mixture at 100oF is fed to a flash tank operating at 1 atm pressure. Heat is
supplied to partially vaporise the liquid, forming a vapour containing 72wt% ethanol. Determine:
i.

temperature of the process

ii. composition of the liquid product

iii. heat supplied per 100 lb of feed
Solution:

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i)

Temperature of the process?

HCMUT-CheEng

Assume V and L are saturated vapour and liquid in equilibrium at temperature T.

From

- x diagram for EtOH-water:

At yEtOH = 0.72
ii)

T = 184.5oF (84.7oC)

Composition of L?

at T = 184.5oF

xEtOH = 0.30 (from diagram)

Composition of L: 30wt% EtOH + 70wt% H2O

iii)

Q?

Basis: 100 lb feed

Mass balance:
Stream: F = V + L = 100 lb

(1)

EtOH:

100(0.5) = V(0.72) + L(0.3)

(2)

Solve

V = 47.6 lb; L = 52.4 lb

Energy balance:

From

- x diagram, read:

Q = 33,600 Btu supplied per 100 lb feed

Chng 8

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