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CHAPTER 8

BALANCES ON NONREACTIVE
PROCESSES

By : Ms. Nor Helya Iman Bt


Kamaludin
Email: helya@unimap.edu.my

Introduction
Non-reactive processes
Processes that undergo without chemical

reaction.
Depends on the physical/environmental
factors like temperature, volume, pressure,
boiling and melting, as well as vaporization.
Normally in chemical process unit, W s=0;

Ep=0; Ek=0; Then energy balance


equation become:
Close System
Open System
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Different symbols between close and


open system
CLOSE SYSTEM
n (amount)

OPEN SYSTEM
(molar flow rate)

U (internal energy)

(rate of enthalpy)

(specific internal
energy)

(specific enthalpy)

Introduction (contd)
For this chapter, we will learn the

procedure for evaluating U and


H when table and are not
available for all process species.
Example enthalpy change () for
solid phenol at 25 C and 1 atm
converted to phenol vapor at 300
C and 3 atm.
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Introduction (contd)
To evaluate changes in enthalpy or internal energy,
we can make up any process path we want to simplify
the calculations. They can often be evaluated for:
1. changes in P at constant T
2. changes in T at constant P
3. changes in T at constant V
4. changes in phase at constant T and P (e.g., heats of
vaporization)
5. mixing at constant T and P (heats of mixing)
6. chemical reactions at constant T and P (heats of
reaction)Chapter 9
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Hypothetical Process Path


State properties

Properties that depend on the state of the species


(primarily on

its temperature and state of aggregation, and also


pressure).
Specific enthalpy () and specific internal energy () are state

properties species
When a species passes from one state to another state, both

and for the process are independent of the path taken


from the first state to the second state.
We can construct a hypothetical process path which can
consist of several step based on our convenience, as
long as we reach to the final state, starting from their
initial state.
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Hypothetical Process Path (Examples)


= (vapor, 300C, 3 atm) (solid,
25C, 1 atm)
Cannot determine directly form enthalpy
table must use hypothetical process path
consist of several step.
Check Table B.1 for Phenol : P= 1 atm; Tm=
42.5C and Tb= 181.4C

Procedure Energy Balance Calculations

1. Perform all required material balance


calculations.
2. Write the appropriate form of the energy balance
(closed or open system) and delete any of the
terms that are either zero or negligible for the
given process system.
3. Choose a reference state phase, temperature,
and pressure for each species involved in the
process.
4. Construct inlet-outlet table for specific internal
energy (close system) or specific enthalpy (open
system)

For closed 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

Procedure Energy Balance


Calculations (contd)
5. Calculate all required values of i or i and insert
the values in the appropriate places in the table.
6. Then calculate or for the system.
Closed System:
Open System:
7. Calculate any work, kinetic energy, or
potential energy terms that you have not dropped
from the energy balance.
8. Solve the energy balance for whichever variable
is
unknown (often Q or
).
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Class Discussion
EXAMPLE 8.1-1: Energy Balance on a
Condenser
The flowchart

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Solution
STEP 1: Perform required material balance
calculations.
-None are required in this example because
there are no
material balance involved in this process.
STEP 2: Write and simplify the energy
balance.
For open steady-state system:

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Delete any of the terms that are either zero or

negligible in process system.


-No moving parts and no energy is transferred in the
system:
-No significant vertical distance separates the inlet and
outlet
ports:
-Phase changes and nonnegligible temperature
changes occur:
So, the energy balance become:

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STEP 3: Choose reference states for acetone


and nitrogen.
N2 (g, 25C, 1 atm) : convenient (Table B.8)
Ac (l, 20C, 5 atm) : choose from one of the
process stream.
STEP 4: Construct an inlet-outlet enthalpy
table.
References: Ac (l, 20C, 5atm); N2 (g, 25C,
1atm)

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STEP 5: Calculate all unknown specific enthalpies


In this step we need to find
i.
ii.

For changes in pressure (P) at constant T


For changes in temperature (T) at constant P

iii. For changes in phases at constant P and T

Use heat of vaporization


or heat of
melting
at
normal boiling point and normal melting point,
respectively. (can be obtained from Table
B.1)
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The process path involved for determination

of

= (0.0297 + 4.68 + 30.2 + 0.753) kJ/mol


= 35.7 kJ/mol

*Use the same manner to obtain the values for


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-insert all specific enthalpies into inlet-outlet


enthalpy table

STEP 6: Calculate

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STEP 7: Calculate nonzero work, kinetic energy and


potential
energy terms
-no need to be calculated since there are no shaft work
and we
are neglecting kinetic and potential energy.
STEP 8: Solve the energy balance for
= -2320 kJ/s
= -2320 kW
Heat must be transferred from the condenser at a rate of
-2320
kW to achieve the required cooling and condensation.
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Changes in P at Constant T
(no phase change or reactions)

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Ideal gases:
Independent of pressure ( unless undergo
very large pressure
changes)
Real gases:
must evaluate from:
1. enthalpy departure charts
2. an equation of state
3. tabulated data
Liquids and solids:
Nearly independent of pressure

Changes in T and Constant P


(no phase change or reactions)
Called sensible heat, heat that must be
transferred to RAISE
or LOWER the temperature of substance or
mixture of
substance and we usually find:
Heat capacities help us calculate this change
in enthalpy. The
heat capacity at constant pressure is
defined by:
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Changes in T and Constant P


(no phase change or reactions)

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Changes in T at Constant V
(no phase change or reactions)
Here, we use the heat capacity at
constant volume,
defined by:

Ideal gases:
Liquids and solids:
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Heat Capacity Formulas


Definition:
Heat capacities, Cp and Cv are physical
properties of materials
and are tabulated in standard references.
Units:
J/(mol.K) and Btu/(lbm.F)
Relationships exist between C p and Cv :

where R = gas constant


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Heat capacity, Cp
Estimation of heat capacities, Cp
Kopps rule- simple empirical method for
estimating Cp of
solid or liquid at or near 20C based on the
summation of atomic heat capacities (Table B.10)
of the molecular compound.
(Cp)Ca(OH)2 = (Cpa)Ca + 2(Cpa)O + 2(Cpa)H
= 26 + (2x17) + (2x9.6)
= 79 J/mol.C
Polynomial expressions for Cp in Table B.2
based on the experimental data for the listed
compound.
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Heat capacity, Cp (contd)


Table B.2 demonstrated the heat capacities as a

function of temperature (at low pressures) in the


equation form for a number of solid, liquid, and
gaseous substances. This is your source of idealgas heat capacities.
Tables of specific enthalpies eliminate the need for

use of heat capacities, i.e., someone has already


done the integrations for you. For "combustion
gases" you should use the tables of molar
enthalpies given in Table B.8 and Table B.9.
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Heat capacity, Cp (contd)


Mixtures:

Where
= heat capacity of the
mixture

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= mass or mole fraction of


the ith component
= heat capacity of the ith
component

Class Discussion
EXAMPLE 8.3-1
EXAMPLE 8.3-2
EXAMPLE 8.3-3
EXAMPLE 8.3-4
EXAMPLE 8.3-5

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Phase Change Operations


Phase change such as melting and evaporation are usually

accompanied by large changes in internal energy and


enthalpy
Latent heat

Specific enthalpy change associated with the


transition of a substance from
one phase to another at constant T & P.
Heat of fusion or heat of melting, m (T,P)
Specific enthalpy different between solid and liquid
forms of species at T & P

Heat of solidification (liquid to solid) is ve value of


heat of fusion.
Heat of vaporization, v (T,P)

Specific enthalpy different between liquid and vapor


forms of species at T & P

Heat of condensation (vapor to liquid) is ve value of

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Estimation of Heat of
Vaporization
1. Troutons rule accuracy between 30%

2. Chens equation accuracy between 2%

3. Clausius-Clapeyron equation - plot In p*

versus 1/T
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Estimation of Heat of Vaporization


(contd)
4.

Chaperon equation

5. Watson correlation estimate v at T2 from

known v
at T1
.Estimation of Heat of Fusion

m (kJ/mol) = 0.0092 Tm (K) metallic elements


= 0.0025 Tm (K) inorganic
compound
= 0.050 Tm (K) organic compound
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Class Discussion
EXAMPLE 8.4-1
EXAMPLE 8.4-2
EXAMPLE 8.4-3
EXAMPLE 8.4-4

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Psychrometric Charts
PSYCHROMETRIC chart (or HUMIDITY Chart)

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is a compilation of a large quantity of


physical property data in a single chart.
The properties are:
(a) Wet Bulb Temperature
(b) Saturation Enthalpy
(c) Moisture Content
(d) Dry Bulb Temperature
(e) Humid Volume
The Psychrometric Chart is particularly
important for Air-Water system and
normally is at Pressure of 1 atm.
Psychrometric Chart is very useful in the

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Psychrometric Charts
(contd)
To use Psychrometric Chart, you need to

know TWO values to determine the values of


the others on the chart.

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IMPORTANT TERM:
Dry-bulb temperature, T This is the air
temperature as measured by thermometer,
thermocouple, or other conventional
temperature measuring device.
Absolute humidity, ha [kg H2O(v)/kg DA]
Called moisture content placed on the
ordinate of the chart.

Psychrometric Charts
(contd)
Relative humidity, hr

Curves on the psychrometric chart correspond to


specified values of hr (100%, 90%, 80%, etc.).
The curve that form the left boundary of the chart
is 100% relative humidity (saturation curve).
Dew point, Tdp
The temperature at which humid air becomes
saturated if it is cooled at constant pressure.
Humid volume,
(m3/kg dry air)
The humid air is the volume occupied by 1 kg of
dry air plus the water vapor that accompanies it.
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Class Discussion
EXAMPLE 8.4-5

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THANK
YOU.

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