Mass Balance, Reactors and Kinetics

T1 Title
T2 Some definitions
Environmental Engineering and Sustainability
In our every deliberation we must consider the impact of our decisions on the next seven
generations. Iroquois Confederacy
We see to meet the needs of the present without compromising the ability of future
generations to meet their own needs. World Commission on Environment and
Development, 1987
!ow do we do this" #athematical models provide a means of $uantifying the impacts of
our decisions.
What is a Model?
% mathematical model is an ideali&ed formulation that represents the response of a
physical system to external stimuli. Chapra 1997, p. 1
T2 'continued( )annon example
Why Model?
)onsider modeling as an alternative to !uild and measure* providing a more rational
basis for maing water $uality control decisions* such a basis to include a defensible*
credible* predictive framewor* within the larger framewor of cost+benefit analysis.
T, the bridge to nowhere
T- the bridge falling down
T. when and to what extent
Reactor Analogs
#odels in environmental engineering are based on reactor theory* with three reactor
analogs commonly employed/ the completely mixed flow reactor ')#01(* the batch
reactor and the plug flow reactor '201(.
1

T3 1eactor analogs in engineered systems
T4 1eactor analogs in natural systems
%s students to explore mass balances in their lives* e.g.
a soaing rain T5 The )ompletely+#ixed 0low 1eactor
buying a 6exus T7 The )ompletely+#ixed 0low 1eactor
Model Development
The 6aw of )onservation of #ass states that mass can neither be created nor destroyed*
but it may change form. This means that the change in mass in a control volume must
e$ual the mass entering minus the mass leaving plus or minus the mass reacting
'changing form(.
The 6aw of )onservation of #ass forms the basis for one of the most important tools in
environmental engineering + the mass !alance.
The mass balance provides a means for constructing a budget for a material 'mass( which
is no more complicated than the soaing rain or 6exus example introduced previously.
6et8s apply the principles evident in those examples to the case of chemical mass/
# # # # #
t t t in t t t out t t t reacted t t t + + + +
= +
* * *
The analysis is performed over the time period t. #oving the initial mass to the other
side and dividing by t yields/
# #
t
#
t
#
t
#
t
t t t
in t t t out t t t reacted t t t
+
+ + +

* * *
The left hand side of the e$uation is the rate of change in chemical mass* i.e.
# #
t
#
t
and as t
#
t
dm
dt
t t t +

= =

9*
The terms on the right hand side are each a mass flux '
m

* units of mass per time(* i.e. the

rate at which mass enters* exits or reacts within the system. This can then be written/
dm
dt
m m m in out reaction =

2
This is the governing e$uation for mass balances throughout environmental engineering.
It remains to identify an approach for $uantifying the terms in this e$uation.
he !ontrol "olume
We begin our exploration of the mass balance using the )#01 reactor analog.
T19 The )ompletely+#ixed 0low 1eactor
The mass balance is written for a control volume* i.e. a specific region of space which has
boundaries across which the mass flux in and mass flux out can be determined.
T11 The )ontrol :olume
The control volume for the )#01 is the entire reactor* taen to include the inlet and
outlet.
erms in the Mass Balance
There are four terms in the mass balance/
dm
dt
m m m in out reaction =

the rate of mass accumulation* mass flux in* mass flux out and the rate of mass reaction.
1ate of mass accumulation
%s mentioned earlier* it is concentration* not mass* which is of great importance in
environmental systems. 0or this reason* we write the mass balance in terms of
concentration* remembering that/
m : ) =
and substituting/
dm
dt
d :)
dt
=
b g
0or our purposes* and in most environmental applications* it can be assumed that the
volume of the reactor is constant. Thus/
dm
dt
:
d)
dt
=
;ote that the assumption of constant volume re$uires that inflow e$ual outflow.
,
#ass flux in
The mass flux in is most commonly $uantified as the product of the volumetric flow rate
'<( and the chemical concentration in the inflow ')in(/
m < ) in
in in

=
and given constant volume* <
in
= <
out
*
in
in
m " C

=
;ote the way that the units wor out in this e$uation/
g
d
m
d
g
m
=
,
,
#ass flux out
The mass flux out is calculated in a similar way/
m < ) out
out out

=

and again given constant volume* <
in
= <
out
*
out
out out
m " C =
g
again* with units/
g
d
m
d
g
m
=
,
,
>ut note that since the chemical concentration is the same anywhere in a )#01*
including at the outlet* we can refer to )out as simply )/
out m " C

=
1ate of mass reaction
This term $uantifies gains or losses of a chemical as a result of biological or chemical
reactions. )hemical reaction rates are typically expressed in terms of concentration* not
mass* as it is concentration which often drives the reaction/
-
r#n
r#n only
dC
m $
dt

=
note the dimensional character of this term/
g
d
m
g
m d
=

,
,
Some materials 'e.g. chloride( are termed conservative* i.e. they do not participate in
biological or chemical reactions. In this case* the expression for the rate of mass
accumulation ':?d)@dt( does not include a reaction term/
9 r#n
r#n only
dC
m $
dt

= =
Aur consideration of materials that do participate in such reactions evolves from the
Binetic 1ate 6aw/
n
r#n
r#n only
dC
m $ $ % C
dt

= =
where is the reaction rate coefficient and n is the reaction order.
We will consider two reaction orders* although there are others 'e.g. second order* mixed
order(/
#ero $rder/ here the rate of reaction is constant and independent of the
concentration of reactant. 0or a &ero order decay/
9 n
r#n
r#n only
dC
m $ $ % C $ % C $ %
dt

= = = =
where has units of #?:
+1
?T
+1
. Integrating the d)@dt portion of the e$uation
permits prediction of the time course of reaction/
9
* *
t
dC
% C inte&ratin& C C % t
dt
= =
and a plot of ) versus t yields a straight line with a slope* .
T12 Cxample of &ero order inetics* oxygen depletion in Dollar >ay.
.
%irst $rder/ here the rate of reaction is not constant and depends on the
concentration of reactant. 0or a first order decay/
1 n
r#n
r#n only
dC
m $ $ % C $ % C $ % C
dt

= = = =
where has units of T
+1
. Integrating the d)@dt portion of the e$uation permits
prediction of the time course of reaction/
9
* *
% t
t
dC
% C inte&ratin& C C e
dt

= =
and a plot of ln) versus t yields a straight line with a slope* .
T1, Cxample of first order inetics* radioisotope decayE half+life calculation
The magnitude of the reaction rate coefficient* * can be influenced by a variety of
environmental factors* most notably temperature. The effect of temperature on the
reaction rate coefficient is calculated using a 8theta function8/

T
T
=

29
29

The value of increases with increasing temperature with ranging from 1.99 'no
temperature effect( to F1.2 'very strong temperature effect(.
T1- Temperature and inetics
T1. Cxample of first order inetics* radioisotope decayE half+life calculation
&utting it all ogether
The original mass balance expression/
dm
dt
m m m in out reaction =

can thus be written as/
:
d)
dt
< ) < ) :
d)
dt
in
rxn only
=
F
H
G
I
K
J
3
%ssuming a first order decay 'but remembering that there is also growth and reactions of
different orders(* can be further written as/
in
dC
$ " C " C $ % C
dt
=
Steady state versus 'on(steady state
>efore trying our first application of the mass balance* we need to address a ey concept/
steady state. It can be seen from the above e$uation that changes in flow* inlet
concentration* or reactivity result in changes in chemical concentration within the reactor.
If these conditions remain constant for a sufficiently long period* they come into balance
and the concentration and mass within the control volume remain constant. This
condition is termed steady state and since concentration is not changing/
dm
dt
:
d)
dt
= =9
T13 )#01/ discuss how the G<)H and :)H terms allow the reactor to Gcatch upH.
If the flow* inlet concentration* and@or reactivity are changing* then the system is
considered non+steady state 'dynamic or time+variable( and/
dm
dt
:
d)
dt
= 9
This has important implications in solving the mass balance e$uation.
!M%R) Steady State ( !onservative
The steady+state conservative case for a )#01 with a single inlet and outlet is $uite
straightforward/
in
dC
$ " C " C $ % C
dt
=
9
in in
" C " C and C C = =
and has relatively little application. Af more interest is the case where two inlet streams
meet with a single outlet.
4
!M%R) Steady State * !onservative * Multiple Sources
)onsider the above example* but with two 'or more( inputs/
1 *1 2 *2 in in
dC
$ " C " C " C $ % C
dt
= +
Simplifying for the steady+state 'because the time it taes to mix is relatively short(*
conservative case and solving for )/
1 *1 2 *2 in in
" C " C
C
"
+
=
This particular mass balance* i.e. one for a conservative substance at steady state* is often
referred to as a mi#in& !asin calculation and is commonly employed wherever two
chemical streams Ioin together. The approach can be applied to reactive materials as
well* because the residence time of the mixing basin is so short that there is no change
due to reaction.
T14 #ixing basin example Sonora 1iver
6etHs consider the case of a river which receives a chloride input from a wastewater
treatment plant. The river has a flow '<up( of 7 m
,
?s
+1
and a chloride concentration ')up(
of 2 mg?6
+1
and the treatment plant has a flow '<in( of 1 m
,
?s
+1
and a chloride
concentration ')in( of 199 mg?6
+1
. Determine the chloride concentration in the mixing
basin.
7 2 1 199 115
11.5
7 1 19
up up in in
m!
up in
" C " C
m&
C
" " '
+
+
= = = =
+ +
The power of this approach is evident in this more difficult example dealing with
industrial wastes.
Steady State ( !onservative E+ample) !hloride in , Mile !ree-
T15 )hloride in 7 #ile )ree bacground
T17 )hloride in 7 #ile )ree + calculation
!ere* the terms available to us in the previous mixing basin calculation are not all nown.
Instead* we now the upstream flow ',.. m
,
?s
+1
( and chloride concentration '-9 mg?6
+1
(
5
and the mixing basin flow '-.2 m
,
?s
+1
( and chloride concentration '1.99 mg?6
+1
( and can
bac+calculate the input from the waste beds.
>eginning with the basin mixing basin e$uation/
up up in in
m!
up in
" C " C
C
" "
+
=
+
and given that <mb = <up J <in/
m! m! up up in in
" C " C " C =
-.2 1.99 ,.. -9 3139 =
The input flow is -.2 ,..* yielding a wastebed chloride concentration of/
3139
5* 599
9.4
in in
in
" C m&
" '

= =
To this point we have considered a conservative substance and multiple feeds in a )#0
reactor. While it might seem logical to continue with the )#0 reactive case* we will
delay that for a bit and turn our attention to the other maIor reactor analog* the plug flow
reactor.
he &lug %lo. Reactor
The plug flow reactor is typically applied to columns 'in engineered systems( and rivers
'in natural systems(. The $uantitative basis for modeling the 201 begins with a simpler
system* the batch reactor.
>atch 1eactor
T17 >atch reactor
% reactor which has no inlet our outlet is termed a batch reactor. #athematically/
:
d)
dt
< ) < ) :
d)
dt
in
rxn only
=
F
H
G
I
K
J
:
d)
dt
:
d)
dt
rxn only
=
F
H
G
I
K
J
7
d)
dt
d)
dt
rxn only
=
F
H
G
I
K
J
and for a first order decay/
d)
dt
) =
and integrating/
) ) e
t
t
=

9
)onsider the shape of the ) = K't( curve.
T29 )oncentration = f 't( in a batch reactor
2lug 0low 1eactor
Ane might thin of the a plug flow reactor as a train of batch reactors. In a 201*
complete mixing occurs in a radial direction* but there is no mixing in the axial direction.
Thus each 8plug8 of fluid is considered to be a separate entity 'mini+batch reactor( as it
flows down the pipe.
T21 Single batch reactor in a pipe
T22+,, Train of batch reactors in a pipe
)onsider the shape of the ) = f'x( curve for the train of reactors. The mass balance for a
201 with first order decay is as follows/
:
d)
dt
< ) < ) :
d)
dt
in
rxn only
=
F
H
G
I
K
J
:
d)
dt
: ) =
) ) e
t
t
=

9
The influent and effluent concentrations are related by the hydraulic retention time of the
pipe* i.e. substituting for t in the e$uation above/
19
) ) e
out in

=

and is related to the length of the pipe '6( and the fluid velocity '(/

=
6
where fluid velocity is a function of flow '<( and the cross+sectional area of the pipe '%(/
=
<
%
and thus/
=
6 %
<
and thus/
=
6 %
<
;ote that the apparent time dependence here is really a position dependence which is
governed by the velocity and downstream distance in the pipe/
t
6
=

where is the fluid velocity and 6 is the downstream distance. Thus/

) ) e
6

6
=

9

!M%R) Steady State ( /st $rder Decay
T,. )#0 1eactor
The steady state case with first order decay for a )#01 is very common in both natural
'laes( and engineered 'treatment units( systems/
in
dC
$ " C " C $ % C
dt
=
11
Lo To Water <uality
()D and *iver D)
%t steady state* the mass balance is/
9= " C " C $ % c
in
and solving for )/
C C
"
" $ %
in
=
+
Steady State ( /st $rder Decay E+ample) &ortage 0a-e reatment &lant
The 2ortage 6ae Treatment 2lant receives an inflow of 5999 m
,
?d
+1
with a pollutant
concentration of 2.9 mg?6
+1
. The first unit operation removes the pollutant according to
first order inetics with a rate constant of 9.. d
+1
. The volume of the tan is 2.99 m
,
.
)alculate the effluent pollutant concentration.
) )
<
< :
mg
6
in
=
+
=
+
= 2.9
5999
5999 2.99 9.
213
.
%nother way of looing at this application is to consider the tan si&e re$uired to effect a
particular reduction in pollutant concentration.
)alculate the tan si&e 'm
,
( re$uired to achieve a 4.M reduction in the effluent
concentration 'i.e. an effluent concentration of 3, mg?6
+1
(/

0or a reduction ) )
in
4.M 9 2. * . =
9 2. . =
+
) )
<
< :
in in
9 2. . =
+
<
< :
9 2. 92. . . + = < : <
:
<

m =

=

=
9 4. 9 4. 5999
9. 9 2.
-5999
,
. .
. .
E11ect o1 Kinetics and "olume on !ss
;ote in the steady state solution to the )#01 e$uation*
12
C C
"
" $ %
in
=
+
that the effluent concentration can be reduced through increases in : and . Why is this"
!ow can we influence these parameters"
E11ect o1 !hanges in Kinetics
%n increase in the reaction rate coefficient leads to a reduction in the effluent
concentration and improved treatment because the reaction proceeds more rapidly.
Kinetics E+ample) &ortage 0a-e reatment &lant
Some reactions* such as the conversion of ammonia to nitrate* are highly sensitive to
temperature. )alculate the M removal for the case above ': = -5*999 m
,
( for
temperatures of -N) and 29N) if = 1.95.
%t 29N)* = 9.. d
+1
* removal efficiency is 4.M and the effluent has ) = 3, mg?6
+1
* as
calculated previously.
%t -N)/
29 '- 29(
- 29
9.. 1.95 9.. 9.27 9.1.
+
% %

= = = =
5999
2.9 1,2
5999 -5999 9.1.
in
" m&
C C
" $ % '
= = =
+ +
1emoval efficiency has dropped from 4.M to -4M due to temperature impacts.
E11ect o1 !hanges in "olume
%n increase in the reactor volume leads to a reduction in the effluent concentration and
improved treatment because the waste remains in the reactor for a longer time.
2ydraulic Retention ime
The volume effect is $uantified through a concept termed the hydraulic retention time '*
units of timeE also called detention time and residence time(* i.e. the average period which
a volume of water spends within the reactor.
$
"
=
1,
Since this is the time available for reactions to proceed* influences the degree of
treatment.
2ydraulic Retention ime E+ample) &ortage 0a-e reatment &lant
In an earlier example* we increased treatment efficiency from F1.M removal to F4.M
removal by changing the tan volume from 2.99 to -5999 m,. What was the
corresponding change in hydraulic retention time"
1
1
2.99
9.,,
5999
$
d
"
= = =
2
2
-5999
3
5999
$
d
"
= = =
Increases in hydraulic retention time will result in reduced effluent concentrations and
improved treatment.
Thus we can see that )ss* i.e. the effluent concentration in a )#0 reactor at steady state*
can be influenced by retention time 'e.g. reactor volume( and inetics 'e.g. temperature(.
ime "ariable Solution
When we choose the steady state solution to be mass balance e$uation* it is assumed that*
the system will reach steady state in a time period meaningful to the
application at hand and
the inputs to the calculation will remain constant until that steady state is
reached.
6etHs examine those assumptions.
T,3 )hange from )ss*1 to )ss*2
If those conditions are not met* a time+variable solution is re$uired*
in
dC
$ " C " C $ % C
dt
=
integrating for a step change from )ss1 to )ss2 yields*
1-
) ) e ) e
t ss
t
ss
t
= +
F
H
G
I
K
J

+
F
H
G
I
K
J
+
F
H
G
I
K
J
1
1
2
1
1

6et8s loo at this e$uation in its parts and then as a whole.
T,4 Time variable response
Response ime
The decision regarding a choice between the steady+state and time variable solution is
guided by a nowledge of how long it taes to reach steady state* i.e. the response time.
1esponse time* defined as the period re$uired for a system to reach e$uilibrium 'steady
state( with a new set of inputs or inetics* is influenced by both the hydraulic residence
time and the inetics of the target substance. >ecause a system never perfectly achieves a
steady state '199M of the )ss value(* it is necessary to establish a criterion for the
response time. In practice* we say that a system is at steady state when it has covered
7.M of the distance between )ss*1 and )ss*2 'note that 79 or 77 or 77.7M could be used as
well.
1e+arranging the time variable solution*
) ) e ) e
t ss
t
ss
t
= +
F
H
G
I
K
J

+
F
H
G
I
K
J
+
F
H
G
I
K
J
1
1
2
1
1

to yield*
1
*2
*1 *2
% t
t ss
ss ss
C C
e
C C


+

and recogni&ing that the system has covered 7.M of the distance from )ss*1 to )ss*2 when
the left+hand side of the e$uation e$uals 9.9.* gives the response time expression*
7.M
ln 9.9. ,
1 1
t
% %

= =
+ +
;ote that for a conservative substance* we can say that steady state is achieved after three
retention times/
7.M
,
,
1
t

= =
1.
and that for a reactive substance it will reach steady state more $uicly. ;ow we are
prepared to select a steady state or time+variable approach.
Selection o1 SS or ime("ariable Approach
%s introduced previously the selection of an approach depends on the time necessary to
achieve steady state 'as reflected in t7.M( and the constancy of the inputs over that
interval. 6etHs loo at these factors for engineered and natural systems.
Treatment 0acilities
Cvaluation of treatment performance is conducted on a monthly or weely 'and
occasionally* daily( basis. %s can be seen in T,4*
T,4 1esponse time
the hydraulic retention times for most unit operations in water and wastewater treatment
are short and the response times are on the order of hours to days. This meets the criteria
for a steady state solution.
Inputs to treatment plants vary seasonally* but are reasonably constant over the response
time of the unit operations. %n exception to this is diurnal flows which are
accommodated with e$uali&ation basins. This also meets the criteria for a steady state
solution.
;atural Systems
Cvaluation of water $uality conditions in laes is typically considered on an annual basis.
While this would suggest that a steady state solution is valuable* the hydraulic retention
time of laes varies widely and thus so does the utility of a steady state approach/
Anondaga 6ae '9.2. yr(* 6ae Antario '5 yr(* 6ae #ichigan '1,3 yr(* 6ae Superior
'147 yr(. !ere* that application is lae and chemical 'due to inetics( specific.
Seasonal variation in inputs and inetics must also be considered. This is especially
important with respect to spring runoff and biological features and depends on the
specific case.
!omparison o1 !M%R and &%R
Cfficiency
13
)onsider the case of 20 and )#0 reactors having the same volume ':(* inflow
'<(* influent concentration ')in(* and reaction inetics '(. The 201 is more efficient in
removing the chemical and thus the 201 effluent concentration would be lower than that
for the )#01. This occurs because the influent to the )#01 is immediately mixed with
the more dilute reactor contents* reducing ) and minimi&ing the value of the reaction
term/
: )
3&4 &%R vs5 !M%R e11iciency6 Mihelcic, %igure 7(8, p5 /9,
Therefore a smaller 'and thus more economical( 20 reactor would be re$uired to meet the
same effluent standards.
Influent spies
#any pollution control systems encounter fluctuations or spies in their influent
concentrations. These spies would simply travel down a 201* but the complete mixing
in a )#01 tends to dampen the impact of spies on the effluent concentration.
3&4 &%R vs5 !M%R * sensitivity to spi-es6 Mihelcic, %igure 7(,, p5 /:;
Selection of a 1eactor
The selection of a 201 or )#01 in engineered systems is guided by efficient
utili&ation of tan volume 'favoring 201s( and sensitivity to inlet spies 'favoring
)#01s(. In natural systems* the choice is based on which best describes the lae or
river.
14