Chapter 9: Balances on Reactive Processes

Consider familiar reaction in which water is formed

from hydrogen & oxygen:
On molecular level. reaction might be depicted as follows:

Each time this reaction takes place, three chemical

bonds are broken (two between hydrogen atoms &
one between oxygen atoms) & four bonds are
formed among atoms of two water molecules
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 As it happens, more energy is released
when water molecule bonds form than it
takes to break hydrogen & oxygen
molecule bonds. For reactor temperature
to remain constant, net energy released
(about 250 kJ per mol of water formed)
must be transferred away from reactor;
otherwise it can raise reactor temperature
by several thousand degrees.
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 In any reaction between stable molecules,
energy is required to break reactant chemical
bonds & energy is released when product
bonds form. If first process absorbs less
energy than second process releases (as in
water formation reaction), reaction is
exothermic: product molecules at a given
temperature & pressure have lower internal
energies (& hence lower enthalpies) than
reactant molecules at same temperature &
pressure.
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 The net energy released- the heat of
reaction-must be transferred from reactor as
heat or work, or else system temperature
increases. In the other hand, if less energy is
released when product bonds form than it
took to break reactant bonds, reaction is
endothermic: energy must be added to
reactor as heat or work to keep temperature
from decreasing.

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 The large internal energy & enthalpy
changes commonly associated with
chemical reactions can play major roles
in design & operation of chemical
processes. If a reaction is endothermic,
energy needed to keep reactor
temperature (& hence reaction rate)
from dropping too much may cost
enough to turn a profitable process into
an unprofitable one.
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An energy balance on a reactor tells process
engineer how much heating or cooling
reactor requires in order to operate at
desired conditions. In this chapter we show
how enthalpy changes that accompany
chemical reactions are determined from
tabulated physical properties of reactants &
products & how calculated enthalpies of
reaction are incorporated in energy balances
on reactive processes
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 9.1 HEATS OF REACTION
Consider reaction between solid calcium
carbide & liquid water to form solid calcium
hydroxide & gaseous acetylene:

The expression stoichiometric quantities of reactants means

molar amounts of reactants numerically equal to their
stoichiometric coefficients. For the calcium carbide
reaction, stoichiometric quantities of reactants in SI system
of units would be 1 mol of CaC2(s) & 2 mol of H2O.

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 If stoichiometric quantities of
reactants are fed & reaction
proceeds to completion, both
reactants would be completely
consumed & stoichiometric
quantities of products would be
formed.

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9.3 FORMATION REACTIONS &
HEATS OF FORMATlON

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9.5 ENERGY BALANCES ON REACTIVE PROCESSES

9.5a General Procedures

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