Introduction to

ENVIRONMENTAL
ENGINEERING
AND SCIENCE
Third Edition

GILBERT M. MASTERS
\AT-':;l\.Tn-':;1 1

"):;'1 A

I,

xii

Preface

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The rapid expansion of the environmental field, and the increa ing awarenes
that broad mterdlsclp]mary perspectives are needed ro successfully tackle environ~ental problems, makes It particularly difficult (but also importam) to write a text
t at ISup-to-dare, readIly accessibleto a broad range of students, technically sound
and sufficiently succmct so as not to overwhelm the wallet or motivation of the
reader. To theI degree that this text fulfills these goals, it is due ro the intentional and
urunrennona mpur from If'
leagues and students In a ticul group a very open, mtelligent, and dedicated coland Eduardo Saez of'the Upamcuar, wfeAwouldlike to thank Professors Bob Arnold
mvefSltya mona for rhei itical i
.
oversight At Stanford U'
. D R
err cnnca mpur and consisrenr
.
mversIfY r. oyal K p
d
ided i
. .
and assistance with the chapte
'
I' a peru pro VI ed invaluahlr- insights
rs on air qua tty and li
h
publisher would also like to thank th f II'
c rrnare c ange. The authors and
Loyola Marymount University B e a ~wmg rev.ewers. Joseph C. Reichenberger,
Raymond W. Regan, Sr., Penn' Sta:~Ctni~ Rmmann, Anzona State University,
Montgomery Brion, University of Kentuckersuy, Keith Stolzenbach, UCLA, Gail
Umversity, Ronald R. Cohen C I d S\ Gtegory G. WIlbur, Oklahoma State
Berkeley, John Novak, Virgini~ T~cohraadAC001 of Mines, David L. Sedlak, UC
'
, an very Demo d U'
,
f .
M osr Importantly
both autho
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nc, mversiry 0 Michigan.
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aren, w 0 served as ghost~write
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rhiIS e ffart. Thei
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elf support enco
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,uragement
and
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Mass and Energy

Transfer

1.1
1.2
1.3
1.4

Gil Masters
Stanford University

CHAPTER

Introduction
Units of Measurement
Materials Balance
Energy Fundamentals
Problems

When you can measure what you are speaking about, and express it in numbers,
you know something about it; but when you cannot measure it, when you
cannot express it in numbers, your knowledge is of a meagre and unsatisfactory
kind; it may be the beginning of knowledge, but you have scarcely, in your
thoughts, advanced to the stage of science.

Wendell Ela
University of Arizona

- William Thomson, Lord Kelvin (1891)

1.1

Introduction
Although most of the chapters in this book focus on specific environmental problems, such as pollution in surface waters or degradation of air quality, there are a
number of important concepts that find application throughout the study of environmental engineering and science.
This chapter begins with a section on units of measurement. Engineers need to be
familiar with both the American units of feet, pounds, hours, and degrees Fahrenheit
as well as the more recommended International System of units. Both are used in the
practice of environmental engineering and both will be used throughout this book.
Next, two fundamental topics, which should be familiar from the study of elementary physics, are presented: the law of conservation of mass and the law of conservation of energy. These laws tell us that within any environmental system, we
theoretically should be able to account for the flow of energy and materials into, and
out of, that system. The law of conservation of mass, besides providing an important
tool for quantitatively tracking pollutants as they disperse in the environment,
reminds us that pollutants have to go somewhere, and that we should be wary of
approaches that merely transport them from one medium to another.
1

Chapter 1

Mass and Energy Transfer

1.2

Units of Measurement

Libr
Mas

In
Mas

Ir

,
In a similar way, the law of conservation of energy i al 0 an
nnal a ounrmg tool with special envrronmenrn] implications, When coupled with Other thermodr~~lcl
o goa

P~Inclples, It WIllbe useful in a number of application

in ludtng rhe
c irnate change, thermal pollution, and the di per ion of air polluranlS.

TABLE

rod"

Common Prefixes

'
Quantity
10 15
10-12
10-9
10-6
10-3
10-2
10-1
10
102
103
10'
109
1012
1015
1018
1021
1024

I~
1
Wei
T

6
Ed,
Sen

Ed;
Ser
AIl

Co
Ar
M,
M.

SeI
AI

',1

re

I
A

P
p

1
il
e
t

In the United States environm

I
' ,
the U,S, Customary System (US~~a q~a~tItles are measured and reported in both
is important to be familiar with b) ~n I t ~ InternatIonal System of Units ( IJ so II
although the U.S. system wil! b ot " n tms book, preference i given 10 I units,
, fIe
use d In some CI
-r- b
.
sion actors between the 51a d uses
rcumstances, I a le 1.1 II t conver'II
n
systems f
f
WI be encountered. A more e t '
b
or some 0 me mo r ba ic units roar
"U fie
x enSIve ta Ie of co
'
, ,
.
se u auversian Factors."
nversions 1 given In Appendix A1
In the study of environmental en inee '
"
extremely large quantities and
gl nng, It IS common ro encounrer both
roxi
b
extreme y small
Th
OXICsu stance may be meas d i
ones,
e concentration
of some
,
ure In pans per b'W
(
COUntry s rate of energy use rna be
I ron ppb), for example, whereas a
(lerawans). To describe quantitie; th measured In lhousands of billions of warts
to have a system of prefixes thaI
at may take On such exrreme values it is useful
f
accompa
h
'
,
pre ixes are presented in Table 1 2
ny t e urnrs, Some of the most important
Of te n, It" IS t h e <oncent ...
interesr U'
h
ratIon of some sub
"
SIng t e metric syslem i
'h
srance In air Or warer thar is of
b ase d' On mass
(II
n eit er medi
usua y mg Or g) velum (
IlIum,
concentrarions
may be
mol) ,W hiICh can le
d
'
e usua y 1
3
II
thar one
I
a to some confusion It
01 m ), or number
(usua y
(6.02 X 1O~0 e of any substance ha; A~ay dbe ,helpfUl ro recall from chemistry
moleCUles/mol) and has a
ga ro s number of molecules
in it
'
'd
mass equal to its molecular weighr
LIqUi S
.
ConCentrations of sub
Stances dis I d'
mass or number er u .
So ve In Water
p
nIt volume of mixture M
are usually expressed in rerms of
TABLE
. OStoften th
'
)
1.1
e umrs are milligrams (mg,

meter
kilograrn
CelSius
square rneter
Cubic meter
kilojoule
Watt

rneterlsec
meter]/sec
kilogr rnJ
a meter]

AppendIX A fora m
Ore COlllplete list.

Prefix

Symbol

femro

pICO

P
n

nano
mICro

J.L

milli

m
c
d
da
h
k
M
G
T
p
E

centi

deci
deka
hecro
kilo
mega
glga
tera
peta

exa

krn
g
'C
rn'
rn3
k

rnls
rn3/s
kg/m3

ConverslOn factor
3.2808
2.2046
1.8 (OC) + 32
10.7639
35.3147
0.9478
3.4121
2.2369
35
.3147
0.06243

uses

unirs

zetta
yotta

micrograms
(!'-g), or moles (mol) of substance per liter (L) of mixture. Ar times, they
may be expressed in grams per cubic merer (g/m ').
Alternatively,
concentrationsin
liquids are expressed as mass of subsrance per
mass of mixrure, with the most common unirs being parts per million (ppm) or parrs
per billion (ppb). To help put rhese unirs in perspecrive, 1 ppm is abour the same as
1 drop of vermouth added to 15 gallons of gin, whereas 1 ppb is abour rhe same as
one drop of pollutant in a fairly large (70 m3) back-yard swimming pool. Since mosr
concentrations
of pollutants
are very small, 1 Iirer of mixture has a mass thar is
essentially 1,000 g, so for all practical purposes, we can write
1 mgIL

1 glm3

=
3

1 !,-glL = 1 mglm

1 ppm (by weighr)

(1.1)

= 1 ppb (by weighr)

(1.2)

In unusual circumstances,
the concentration
thar rhe specific gravity of the mixture is affected,
and (1.2) may be required:

~Some Basic Units and C

Mass
Ternperature
AI
ea
Volurne
E
nergy
POwer
VelOCity
Flow rate
D .
enslty
4S.

1.2

mgll

= ppm

(by weighr)

of liquid wastes may be so high

in which case a correction to (1.1)

x specific gravity

of mixture

(1.3)

fr
Ib
OF
ft2
ft3
Btu
Btu/hr
milhr
ft3/s
Ib/fr'

EXAMPLE 1.1 Fluoridation

of Water

The fluoride concentration

in drinking water may be increased ro help prevent
rooth decay by adding sodium fluoride; however, if roo much fluoride is added,
it can cause discoloring
(mottling) of lhe teeth. The optimum dose of fluoride in
drinking warer is abour 0.053 mM (millimolelliter),
If sodium fluoride (NaF) is
purchased in 25 kg bags, how many gallons of drinking water would a bag !reat?
(Assume there is no fluoride already in lhe water.)

Chapter 1

Mass and Energy Transfer

1.2

Units of Measurement

R
T

Solution Note that the mass in the 25 kg bag is the sum of the rna s of the
sodium and the mass of the fluoride in the compound. The atomic weight of
sodium is 23.0, and fluoride is 19.0 (values are given in Appendix B), so the
molecular weight of NaF is 42.0. The ratio of sodium to fluoride atoms in aF
is 1:1. Therefore, the mass of fluoride in the bag is

x
mass F

= 25 kg

19.0 g/mol
X

42.0 g/mol

= 11.31 kg
con-

0.053 mmollL X 19.0 g/mol X 1,000 mg/g

1,000 mmollmol
= 1.01 mgfL

The mass concentration of a substance in a fluid is generically

c=m

(1.4)

'

mol-1

The mass in (1.6) is expressed as moles of gas. Also note the temperature
exptessed in kelvins (K), where
=

+ 273.15

is

(1.7)

There are a number of ways ro express pressure; in (1.6), we have used atmospheres. One
atmosphere of pressure equals 101.325 kPa (Pa is the abbreviation for Pascals). One
atmosphere is also equal to 14.7 pounds per square inch (psi), so 1 psi = 6.89 kPa.
Finally, 100 kPa is called a bar, and 100 Pa is a millibar, which is the unit of pressure
often used in meteorology,

EXAMPLE 1.2 Volume of an Ideal Gas

where m is the mass of the substance and V is the v I

._
and the results of the t
I I '
0 ume of the fluid. Using (1.4)
wo ca cu anons above the I
f
h
b
treated is

ideal gas constant = 0.082056 L arm- K-1

absolute temperature (K)

Conve~ting the m~lar .concentration to a mass concentration, the optimum

centration of fluonde III water is
F

vo ume 0 water t at can

Find the volume that 1 mole of an ideal gas would occupy at standard temperature and pressure (STP) conditions of 1 atmosphere of pressure and OC temperature. Repeat the calculation for 1 atm and 25C.

Solution

V = 11.31 kg X 106 mg/kg

1.01 mgIL X 3.785 Ugal = 2.97 X 106 gal

The bag would treat a day's supply of d - ki

the United States!
rm 109Water for about 20,000 people in

Using (1.6) at a temperature of OC (273.15 K) gives

Imol

0.082056

L'atm'K-1'mol-J
1 atm

273.15 K

22.414 L

298.15 K

22.465 L

and at 25C (298.15 K)

V

1 mol

0.082056

L atm' K-1 mol-1

1 atm

Gases
For most air pollution work it is custo

,
mary to ex

II

vo Iumetnc terms. For example th

. press po utanr concentrations
II' (ppm} i
, e concentration of

in

rru Ion ppm) ISthe volume of poll t

. _ a gaseous pollutant in parts per
u ant per million I
f
1 I
vo umes 0 the air mixture:
vo ume of gaseous pollutant
6

10 volumes of air

= 1 ppm (by volume) = 1 ppmv

PV=nRT
P = absolute pressure (atm)
V = volume (rrr')
11 = mass (mol)

mg/rn '

ppmv

1 m3 pollurant/TU''
ppmv

m3 air
X

mol wt (g/mo!)
22.414 X 10 3 m3/mol

10 mg/g

(1.5)

To help remind us that this fraction is b d

to the ppm, giving pprnv, as suggested ina;~ 5)n volume, it is common ro add a "v"
At ~Imes,conc~ntrations are expressed' .
.
or mg/m . The relationship between p
adsmass per umr volume, such as J-Lg/m3
perature and
I I'
pmvan mg/rn! d
'.
mo ecu ar weIght of the 011
_ epen d s on the pressure, ternthat relationship' .
p utant. The Ideal gas la w h eIps us esta bli15 h
where

From Example 1.2, 1 mole of an ideal gas at OC and 1 atrn occupies a volume
of 22.414 L (22.414 X 10-3 rn'}. Thus we can write

(1.6)

Of,

more simply,
3 _

mg/m

ppm v X mol wt
22.414

(at OC and 1 atm)

(1.8)

Similarly, at 25C and 1 atrn, which are the conditions that are assumed when air
quality standards are specified in the United States,
mg/m

3 _

ppmv X mol wr
24.465

(250C
at

an

d 1)
arm

(1.9)

In general, the conversion from ppm ro mg/rn:' is given by

3

mg/m

ppm v X mol wt
22.414

P(atm)

273.15 K
X

T(K)

1 atm

(1.10)

Chapter 1

1.3

Mass and Energy Transfer

The U.S. Air Quality Standard for carbon monoxide (based on an 8-hour measurement) is 9.0 ppmv. Express this standard as a percent by volume as well as in
rng/nr' at 1 arm and 25'C.

..........

Accumulation

Inputs~
Reactions: Decay

and generation

Solution

Within a million volumes of this air there are 9.0 volume of CO, no
matter whar the temperature or pressure (this is the advantage of rhe ppmv units).
Hence, the percentage by volume is simply

9.0
1

x 10

100

0.0009%

To find the concentration in mg/rrr', we need the molecular weight of CO, which
tS 28 (the atomic weights of C and 0 are 12 and 16, respectively). Using (1.9) gives
CO = 9.0 x 28 _
3
24.465
- 10.3 mg/m
Actually, the standard for CO is usually rounded and listed as 10 mg/rrr',

The fact that 1 mole of every ide a I gas Occupies

ies th
t e same volume (under the
same temperature and pressure co dition)
id
I'
,
n I Ion provi es several other interpretations
of
vo umetnc concentrations expressed as ppmv. For ell
'1
I
f
pollutant per million volumes of air whi h '
. xamp e, ppmv IS vo ume 0
rant per million moles f ' S' '1'1
IC IS equivalenr to saying 1 mole of polluo air, irnuarty smcee hi'
f
molecules 1 ppmv also Cd'
ac mo e contains the same number 0
,
orrespon s 10 1 mol
I f
II
of air.
ecu e 0 po utanr per million molecules
1ppmv = 1 mol of pollutant
10 mol of air

Control volume \
boundary

EXAMPLE 1.3 Converting ppmv to mg/m'

percent CO

Materials Balance

1 molecule of pollutant
106

I
I
.
rna ecu es of air

(1.11)

1.3 I Materials Balance

Everything has to go somewhere is a sim I
mental engineering principles Mo
p e way to express one of the most funda'
.
re preCisely th If'
t h at w h en chemical reactions tak
I
,e
.aw 0 conservauo of mass says
'I nuc ear reactions masse p ace,
matter IS ith
(th aug h In
b
nett er created nor destroye d
'
'
can
e
convert
d
a IIows us to do IS track materials f
e to energy). What this concept
irh
b J
' or example poll utants, from one place to another
WI mass a ance equations Thi ,
II'
.
IS ISone of the m
id
po . urants 10 the environment and'
h basi
ost WI ely used tools in analyzing
b
d
d '
IS t e asis for
f
e intro uce 10 later chapters.
many a the approaches
that will
The first step in a mass b I
h a ance analys'
def
s~ace t at IS to be analyzed. This is often
;~ ~s ~ efine the particular
region in
t e ~ontrol volume might include anything ~a e t e COntrol volume. As examples,
m
nb~mg tank, to an entire coal-fired po
rlo a glass of water or simple chemical
asm above a cit
hI'
wer P ant a lak
'
y, Or t e g abe Itself B '
.'
e, a stretch of stream an air
. Y P1ctunng an .
.
'
Imagmary boundary
around

FIGURE 1.1

--t-+- Outputs

A materials balance diagram.

the region, as is suggested in Figure 1.1, we can then begin to quantify the flow of
materials across the boundary as well as the accumulation
and reaction of materials
within the region.
A substance that enters the control volume has four possible fates. Some of it
may leave the region unchanged,
some of it may accumulate
within the boundary,
and some of it may be converted to some other substance (e.g., entering CO may be
oxidized to CO2 within the region). There is also the possibility that more substance
may be produced (e.g., CO may be produced by cigarette smoking within the control volume of a room). Often, the conversion and production
processes that may
occur are lumped into a single category termed reactions. Thus, using Figure 1.1 as
a guide, the following materials balance equation can be written for each substance
of interest:
ACCUmulation)
rate

= (Input)

rate

_ (output)
rate

(Reaction)
rate

(1.12)

The reaction rate may be positive if generation of the substance is faster than its
decay, or negative if it is decaying faster than it is being produced. Likewise, the accumulation
rate may be positive or negative. The reaction term in (1.12) does not
imply a violation of the law of conservation
of mass. Atoms are conserved, but there
is no similar constraint on the chemical compounds,
which may chemically change
from one substance into another. It is also important
to notice that each term in
(1.12) quantifies a mass rate of change (e.g., mg/s, lb/hr) and not a mass. Strictly, then,
it is a mass rate balance rather than a mass balance, and (1.12) denotes that the rate
of mass accumulation
is equal to the difference between the rate the mass enters and
leaves plus the net rate that the mass reacts within the defined control volume.
Frequently, (1.12) can be simplified. The most common simplification
results
when steady state or equilibrium conditions
can be assumed. Equilibrium
simply
means that there is no accumulation
of mass with time; the system has had its inputs
held constant for a long enough time that any transients have had a chance to die out.
Pollutant concentrations
are constant. Hence the accumulation rate term in (1.12) is
set equal to zero, and problems can usually be solved using just simple algebra.
A second simplification
to (1.12) results when a substance is conserved within

the region in question, meaning there is no reaction occurring-no radioactive

decomposition,
or chemical decay or generation. For such conservathe reaction rate in (1.12) is O. Examples of substances that are typ-

decay, bacterial
tive substances,
ically modeled
heavy metals in

as conservative
include total dissolved solids in a body of water,
soils, and carbon dioxide in air. Radioactive
radon gas in a home or

Chapter

1.3

Mass and Energy Transfer

Stream ~

.:

--"\

,/ Accumulmion
I
r

\\"

Control volume \
boundary

e,

0 \ 1 C m'
:~Mixlure

C,~20,OmglL

----

Cm =1'

Reaction = 0 "
Wastes ~Qw'

Materials Balance

Q= flow rate
C = concentration
of pollutant

FIGURE 1.2 A steady-state conservative system. Pollutants enter and leave [he region
the same rate.

at

FIGURE 1.3
decomposing organic wastes in a lake are examples of nonconservarive substances,
Often problems involving nonconservative substances can be simplified when rhe
reaction rate ISsmall enough to be ignored,

Steady-State

Conservative Systems

Next the mass balance equation

problem's conditions
~

The simplest systems to analyze are those in which steady state can be assumed (so
the accumulation
rate equals 0)' and th e su b stance in
' question
" IS conservative, (so the
.
reaction rate equals 0), In these cases, (1.12) simplifies to the following:
Input rate ~ Output rate

Sketch of system, variables, and quantities for a stream and tributary

mixing example.

(Input)
rate

~=

and pollutant concentratio C Th

,waste
stream With flow rate Qw
n W'
e output IS a rni t
' h fl
Q m an d
pollutant concentration C If h
11
'
x ure Wit
ow rate
rnt e po utant
IS c
'
d if
steady state conditions then a
b I
onservanve, an 1 we assume
following:
,mass
a ance based on (1.13) allows us to wrire the

,
C,Q, + CwQw ec CmQm
(1.14)
The followmg example illustrates th
f hi
,
provides a general algorithm for d e use 0 t ISequation. MOte importantly, it also
omg mass balance problems,
EXAMPLE 1.4 Two Polluted Streams
A stream flowing at 10,0 m3/s has
ib
utaryfeed'
,
, ,
3
Th'e stream s concentration of chi a tn
id
mg inro It WItha flow of 5,0 ra'!.
the, tributary chloride concentrat:~ ~ 1~.t~e~m of the junction is 20,0 mg/L, and
vanve substance and assuming
I
' gIL, Treatmg chlonde as a conserdo,
hi '
comp ete mlxmg f h
vnstream conde concentration,
0 t e two streams, find the
SolutIon
The first step in s I '
I
id ify
0 vmg a mass b I
em, I ent
the "region" or control volu a ance problem is to sketch the probthe variables as has been done in Figu 1~ef that we Want to analyze, and label
re , or thISproblem.

(Output)
rate

+~

The simplified (1.12) is then written in terms of the variables in the sketch

o=

(1.13)

con'
hown i
,Consider
d ithithe steady-state,servatlve
system sown
m Figure 1,2, The system
contame
Wit m the boundaries mi ht b I k
'
ai b
'
g
e a a e, a section of a free flowing stream,
Or th e mass 0 f air
a ave a cay One'
h
.
for instance) with
fl
'
input to t e system ISa stream (of water or air,
I a ow ' rate "Q (vol urne I'time ) an d pollutant concentration C
(mass Ivo Iume ). Th e other mput
IS assumed to be a
.
S

(1.12) is written and simplified to match the

C,Q, + CwQw - CmQm

The next step is to rearrange the expression to solve for the variable of interestin this case, the chloride concentration downstream of the junction, Crn' Note
that since the mixture's flow is the sum of the two stream flows, Q, + Qw can be
su bstituted for Qm in this expression,
C

C,Q, + CwQw

Qrn

C,Q, + CwQw

= --,"""-_--"-"'c:'

Q,

+ Qw

The final step is to substitute the appropriate values for the known quantities into
the expression, which brings us to a question of units, The units given for Care
mg/L, and the units for Q are m3/s, Taking the product of concentrations and
flow rates yields mixed units of mg/L> m3/s, which we could simplify by applying
the conversion factor of 103 L = 1m '. However, if we did so, we should have to
reapply that same conversion factor to get the mixture concentration back into
the desired units of mg/L. In problems of this sort, it is much easier to simply
leave the mixed units in the expression, even though they may look awkward at
first, and let them work themselves out in the calculation, The downstream concentration of chloride is thus
(20.0

+ 40,0 X 5,0) rng/L: m3/s

(10,0 + 5,0) m3/s

10,0

= '----.:......-------oc.:.-.:::...-- = 26,7 mgIL

C
m

This stream mixing problem is relatively simple, whatever the approach used,
Drawing the system, labeling rhe variables and parameters, writing and simplifying the mass balance equation, and then solving it for the variable of interest is
the same approach that will be used ro solve much more complex mass balance
problems later in this chapter and later in the book,

- - --~---~----

10

Chapter 1

-.

.-

--

--~~~-'--~--

--====-- ----

----

1.3

Mass and EnergyTransfer

11

Materials Balance

1
I

Batch Systems with Nonconservative Pollutants

200

The simplest system with a nonconservative pollutant is a batch system, By definition, there is no contaminant flow into or out of a batch system, yet the ontaminants in the system undergo chemical, biological, or nuclear reaction
fa r enough
that they must be treated as nonconservative substances. A batch system (reactor)
assumes that its contents are homogeneously distributed and is often referred ro as a
completely mixed batch reactor (CMBR). The bacterial concentration
in a closed
water storage tank may be considered a nonconservative pollutant in a batch reactor because it will change with time even though no water is fed into or withdrawn
from the tank. Similarly, the concentration of carbon dioxide in a poorly ventilated
room can be modeled as a nonconservative batch system because the concentration
of carbon dioxide increases as people in the room breathe. For a batch reactor (1.12)
simplifies to
'
Accumulation

rate ~ Reaction rate

(1.15)

As discussed before, the reaction rate is the sum of the rates of decay, which
are negative, and the rates of generation, which are positive. Although the rates of
reacnon can exhibit many dependencies and complex relationships
most nuclear,
chemical , and biocherni
.
, ' zero-, [irst-,
.
. rca I reactiIon rates can b e approximated
as either

or second-order reactton rates. In a zero-order reaction, the rate of reaction

the substance IS not dep dent
h
en
On t e amount
expressed as

r(C) ~ k (generation)

or

f h
ate
substance

present

r(C) ~ -k (decay)

r(C) of
'
,
and can be
(1.16)

where k is a reaction rate coefficie

hi h h
h
.
I
I
as t e uruts of mass' volume. time(e.g., mg . L-I . s-I ). The rate of evnt, W ic
ti
f
f
reaction beca
th
f I
apoea Ion a water rom a bucket is a zero-order
use e rate a ass of the
'
d
f
water in the bucket bu- :
I d
water IS not ependent on the amount 0
water exposed to the Ut ISon y ependenr on the nearly constant surface area of the
air,
Using (1.15) and (1.16), the mass b I
'
stance in a batch reactor is
a ance for the zero-order reacnon of a sub-

dC
V~ -Vk
dt
The equation is written as a zero-orde d
fight-hand side of the'
r ecay, denoted by the negative sign on the
,
equanon, So that each t
in th
recr umts of massltirne both th
I ' errn m t e mass balance has the corhi'
e accumu anon
d
'
t e vo ume of the batch reactor. Al h
h i an reaction terms are multiplied by
dl. appears by dividing both side ~ ~g
10 a batch sYStem, the volume
coefficient
initial balance equation because s y h ' It IS worth remembering its presence in the
diff
. I'
10 ot er system
.
I erenna equanon, the variabl
s It may not cancel out. To solve the
es are separated and inr egrate d as
C

JdC~
which yields

Co

-kJdt
0

C - Co ~ -kt

(1.171

Decay
c

150

'"g

100
~
u
e

c
0

50
0

Production

20

-k

40

60

100

80

Time

FIGURE 1.4
kinetics.

Concentration of a substance reacting in a batch system with zero-order

Solving for concentration

gives us

C ~ Co - kt

(1.18)

where Co is the initial concentration.

Using (1.18) and its analog for a zero-order
generation
reaction, Figure 1.4 shows how the concentration
of a substance will
change with time, if it is reacting (either being generated or destroyed) with zeroorder kinetics.
For all nonconservative
pollutants
undergoing
a reaction other than zeroorder, the rate of the reaction is dependent
on the concentration
of the pollutant
present. Although decay and generation rates may be any order, the most commonly

encountered reaction rate for generation is zero-order, whereas for decay it is firstorder. The first-order

riC)

reaction
=

rate is

kC (generation)

or

riC) ~ -kC

(decay)

(1.19)

where k is still a reaction rate constant, but now has the units of reciprocal time
(time-I). Radioactive
decay of radon gas follows first-order
decay-the
mass that
decays per given time is directly proportional
ro the mass that is originally present.
Using (1.15) and (1.19), rhe mass balance for a pollutant
undergoing
first-order
decay in a batch reacror is

dC
Vdt

-VkC

This equation can be integrated

by separation
of variables
(1.17). When solved for concencration,
it yields

and solved similarly

ro

(1.20)

That is, assuming a first-order reaction, the concentration of the substance in

question decays exponentially.
This exponential
function will appear so often in
this text that it will be reintroduced
and explored
more fully in Chapter
3,
"Mathematics
of Growth."
The first-order
rime dependence
of a nonconservative
pollutanc's concentration
in a batch system can be seen in Figure 1.5.
Although not nearly as common as first-order
processes, sometimes
a substance will decay or be generated by a second-order
process. For instance, hydroxyl

12

Chapter 1

-- -~

-----

~.

-~

--

----~------

-~

1.3

Mass and Energy Transfer

200~----------------,

150

"

150

.~
c

.~
b

100

Production

100

50

20

40

60

80

50 I\-

I~Y
a
a

100

Production

./
20

40

Time

FIGURE 1.5
kinetics.

FIGURE 1.6
kinetics.

Concentration of a substance reacting in a batch system with first-order

IS

r(C)

kC (generation)

or

r(C)

-kC2 (decay)

(1.21)

where k is nOW a reaction rate constant with units of (I

.
-I."
-I)
Agam substit ti
(121)"
vo ume mass
time
'
d d I ~ mg f'
into (1.15), we have the differential equation for the
secon -or er ecay

a nonconservative substance in a batch reactor

V

dC

dt

of a substance reacting in a batch system with second-order

purposes,

its rate can be approximated

Figure 1.6 shows how the cOncentration of

decays or is produced by a second- d
,a substance changes with time if it
10

a batch reactor.

Zero-order,
Zero-order,

decay rate

generation

rate

First-order, decay rate

Steady-State Systems with Nonconserv ti

a ive Pollutants

o=

Input rate - Ou

as either zero-, first-, or second-

(1.22)

1 + Cokt

or er reacnon

Concentration

order, Just as for the batch reactor, for a CSTR, we assume the substance is
uniformly distributed throughout a volume V, so the total amount of substance
is CV, The total rate of reaction of the amount of a nonconservative substance is
thus d(CV)/dt = V dC/dt = Vr(C) , So summarizing (1.16), (1.19), and (1.21), we
can write the reaction rate expressions for a nonconservative substance:

-VkC2

C = _-,Co,--

servative, then (1.12) becomes

100

two orher ideal reactors, In the first, the substances within the system are still
homogeneously mixed as in a batch reactor, Such a system is variously termed a
continuously stirred tank reactor (CSTR), a perfectly mixed flow reactor, and a
complete mix box modeL The water in a shallow pond with an inlet and outlet is
typically modeled as a CSTR as is the air within a well-ventilated room, The key
concept is that the concentration, C, within the CSTR container is uniform throughout, We'll give examples of CSTR behavior first and later discuss the other ideal
reactor model that is often used, the plug flow reactor (PFR),
The reaction rate term in the right-hand side of (1.23) can denote either a
substance's decay or generation (by making it positive or negative) and, for most environmental

which can be integrated and then solved f h

'
or t e COncentratiOnto yield

If we assume that steady-state conditions

80

60
Time

radical reactions with volatile organic pollutants is a key step in smog generation,
However, If two hydroxyl radicals collide and react, they form a much less potent
hydrogen peroxide molecule, This is a second-order reaction, since two hydroxyl
radicals are consumed for each hydrogen peroxide produced, The second-order
reaction rate

13

Materials Balance

200

Decay

-----

"I
prevai and treat the pollutants as noncon-

tpur rate + Reaction rate

(1.23)
Thebatch reactor, which has just b
di
system With a nonconservative substan ee~ Iscussed, can't describe a steady-state
Although there are an infinite number ofc~th~~ausenow there is input and output,
ploymg two other types of ideal reactors II pOSSIbletypes of reactors simply emronmental processes, The type of m' , a ows us to model a great number of enviIXmg III the s
' ,
ystem dlsltnguishes between the

First-order,

generation

rate

Second-order, decay rate

Second-order,

generation

rate

= - Vk

(1.24)

= Vk

(1.25)

= -VkC

(1.26)

= VkC

(1.27)

-VkC2

(1.28)

= VkC2

(1.29)

Thus, for example, to model a CSTR containing a substance that is decaying with a
second-order rate, we combine (1.23) with (1.28) to get a final, simple, and useful
expression for the mass balance involving a nonconservative pollutant in a steadystate, CSTR system:
Input rate

Output rate + kC2V

(1.30)

1.3

EXAMPLE 1.5 A Polluted Lake

l

Consider a 10 X 106 m3 lake fed by a polluted stream having a flow rate of

5.0 m3/s and pollutant concentration equal to 10.0 mgiL (Figure 1.7). There is
also a sewage outfall that discharges 0.5 m3/s of wastewater having a pollutant
concentration of 100 mg/L. The stream and sewage wastes have a de ay rate coefficienr of 0.20/day. Assuming the pollutant is completely mixed in the lake and
assuming no evaporation or other water losses or gains, find the steady- tare
pollutant concentration in the lake.

Idealized models involving nonconservative

15

Materials Balance

pollutants

in completely mixed,

steady-state systems are used to analyze a variety of commonly

encountered water

pollution problems such as the one shown in the previous example. The same simple
models can be applied to certain problems involving air quality, as the following
example demonstrates.
EXAMPLE 1.6 A Smoky Bar

Solution

We can conveniently use the lake in Figure 1.7 as our control volume.
Assuming that complete and instantaneous mixing occurs in the lake-it acts as a
CSTR-lmphes that the concentration in the lake, C, is the same as the concenrranon of the mix leaving the lake C The units (day" I) f h d
.
ffi
'.
...'
m0 t e ecay reaction
coe ficient indicates this IS a first-order reaction. Using (1.23) and (1.26):
Input rate = Output rate
We can find each term as follows:

+ kCY

(1.31)

A bar with volume 500 m3 has 50 smokers in it, each smoking 2 cigarettes per
hour (see Figure 1.8). An individual cigarette emits, among other things, about
1.4 mg of formaldehyde (HCHO). Formaldehyde converts to carbon dioxide
with a reaction rate coefficient k = 0.40/hr. Fresh air enters the bar at the rate
of 1,000 m3/hr, and stale air leaves at the same rate. Assuming complete mixing,
estimate the steady-state concentration of formaldehyde in the air. At 25"C and
1 arm of pressure, how does the result compare with the threshold for eye irritation of 0.05 ppm?

There are two input sources, so the total input rate is

Input rate =
The output rate is

Solution

The bar's building acts as a CSTR reactor, and the complete mixing
inside means the concentration of formaldehyde C in the bar is the same as the
concentration in the air leaving the bar. Since the formaldehyde concentration in
fresh air can be considered 0, the input rate in (1.23) is also O. Our mass balance
equation is then

Q ssw
C + Q Cw

Output rate = QmCm =

(Q, + Qw)C

(1.31) then becomes

o,c, = (Q,

Q,C, +
And rearranging to solve for C ,

Output rate

+ Qw)C + kCY

10.0 mgIL + 05 31
. m s

+ 0.5) m3/s +

(5.0
S0,

Reaction rate

(1.32)

However, both a generation term (the cigarette smoking) and a decay term (the
conversion of formaldehyde to carbon dioxide) are contributing to the reaction
rate. If we call the generation rate, G, we can write

C = Q,C, + QwCw
Q, + Qw + kY
_ 5.0 m3/s
-

G
X

100.0 mg/L

50 smokers

2 cigslhr

1.4 mg/cig

140 mg/hr

We can then express (1.32) in terms of the problem's variables and (1.26) as

0.20/d X 10.0 X 106 m3

24 hrld X 3600 slhr

QC

G - kCY

so
C

=..!QQ.._

28.65 - 3.5 mgIL

---;;...,-_14-'0~m-"'.g/_:hr---___;_
1,000 m3/hr + (0.40/hr) X 500 m3

= __

Q + kV
Outfall

Incoming

_sl_"_Ufl_'

Qt= 5.0 m3/s

C, = 10.0 mglL

14

.-/

FIGURE 1,7

---.;:
Lake \

(r

m3/s
Cw = 100.0 mg/L

Qw=0.5

0.1l7mg/m3

Oasis
Indoor concentration

V:::: 500 m3
Q = 1,000 m3/hr

,-,J
~

'\..~

V=10.OxlO'm3
k= 0.20/day

C=?

Outgoing

ff---Cm=?
Qm=?

A lakewith a

nonconservative pollutant,

-t--

Fresh air
140 mglhr

!l

FIGURE 1.8

kO.40/hr

Tobacco smoke in a bar.

Q = 1,000 m3/hr
C=?

16

Chapter 1

1.3

Mass and Energy Transfer

Materials Balance

17

We will use (1.9) to convert mg/rrr' to ppm. The molecular weight of formaldehyde
Lake

is 30, so

HCHO

C (mg/rrr')

iff

24.465

0.117

mol wt

Q = 700 m3/rnin

24.465 _ 0095
-.
ppm
30

.....-3

Q = 7(J() m /min

.--;

This is nearly double the 0.05 ppm threshold for eye irritation.

t = tl = V/Q
whderQelis thhefllendgtfhl
of the PFR, v is the fluid velocity, V is the PFR control
an
IS t e
ill
owrate,

r---

c=?

Besides a CSTR, the other type of ideal reactor that is often useful to model
pollutants as they flow through a system is a plug flow reactor (PFR). A PFR can be
visualized as a long pipe or channel in which there is no mixing of the pollutant
along its length between the inlet and outlet. A PFR could also be seen as a conveyor
belt carrying a single-file line of bottles in which reactions can happen within each
bottle, but there is no mixing of the contents of oue bottle with another. The behavior of a pollutant being carried in a river or in the jet stream in the Earth's upper
atmosphere could be usefully represented as a PFR system. The key difference between a PFR and CSTR is that in a PFR, there is no mixing of one parcel of fluid
with other parcels in front or in back of it in the control volume, whereas in a
CSTR, all of the fluid in the container is continuously and completely mixed. (1.23)
applies to both a CSTR and PFR at steady state, but for a PFR, we cannot make the
simplification that the concentration everywhere in the control volume and in the
fluid leaving the region is the same, as we did in the CSTR examples. The pollutant
concentration in a parcel of fluid changes as the parcel progresses through the PFR.
Intuitively, it can then be seen that a PFR acts like a conveyor belt of differentially
thin batch reactors translating through the control volume. When the pollutant enters the PFR at concenrranon, Co, then it will take a given time t to move the length
of the control volume and will leave the PFR with a concentra;i~n just as it would if
It had been 1B a batch reactor for that period of time. Thus, a substance decaying
With a zero-, firsr-, or second-order rate will leave a PFR with a concentration
given
by (1.18)~ (1.20), and (1.22), respectively, with the understanding
that t in each
equation IS the residence time of the fluid in the co t I I
d i
b
n ro vo ume an IS gIven y

(1.33)

L=4.

75 \<In

Co = 7 fishlm3

:::=---I

A=20m'

Ocean

FIGURE 1.9

Birds fishing along a salmon srream.

Solution First we draw a figure depicting the stream as the control volume and
the variables (Figure 1.9).
Since the birds eat the salmon at a steady rate that is not dependent on the
concentration
of salmon in the stream, the rate of salmon consumption
is zeroorder. So,

k = 10,000 fish km~l. hr~l = 0.50 fish. m~3. hr~l

20 m2
For a steady-state

1,000 m/km

PFR, (1.23) becomes

C
The residence

time, t, of the stream

(1.18),

Co - kt

can be calculared

using (1.33) as

t = ~ = 4.75 km X 20 m X 1,000 m/km = 2.26 hr

Q
700 m3/min X 60 minlhr
and the concentration

of fish reaching

the ocean is

C = 7 fish/m3 - 0.50 fish- m~3. ht~l

2.26 hr

5.9 fish/m3

volume,

EXAMPLE 1.7 Young Salmon Migration

Step Function Response

So far, we have computed

~~::~e:r~~~~oe~:i~geaagUlllkS,eaglehs,and Other birds mass along a 4.75 km stretch

aetoteoceanto
h the f
h
migrate downstream to the e The hi
catc t e mgerhng salmon as t ey
surne 10,000 fingerlings per ~il:met~r ~;ds are efficient fishermen and will conber of the salmon in the stream I
h stream each hour regardless of the numbirds are only limited by how f' nhot er words, there are enough salmon; the
ast t ey can cat h
d'
,
average Ctoss-sectional area is 20 2
d h
c an eat the fish. The stream s
stream's tlow rate of 700 m3/m'I mlf'han t e salmon move downstream
with the
.
n. t ere are 7 f
I'
3
termg the stream what is the co
'
inger lOgs per m in the water enbi
'
ncentratlon of I
h
h
t h e irds are feeding?
sa man t at reach the ocean w en

steady-state

concentrations

in environmental

systems that

are contaminated with either conservative or nonconservative pollutants. Let us

now extend the analysis to include conditions that are not steady state. Quite often,
we will be interested in how the concentration
will change with time when there is a
sudden change in the amount of pollution entering the system. This is known as the
step function response of the system.
In Figure 1.10, the environmental system to be modeled has been drawn as if it
were a box of volume V that has flow rate Q in and out of the box.
Let us assume the contents
of the box are at all times completely
mixed
(a CSTR model) so that the pollutant concentration
C in the box is the same as the
concentration
leaving the box. The total mass of pollutant in the box is therefore

18

Chapter 1

1.3

Mass and Energy Transfer

Materials Balance

19

then
Flow

Flow in

OUt

dy

dC

dt

dt

(1.39)

Q.C

Control volume V
Concentration C

Q,C,

so (1.37) becomes

Decay coefficient kd
Generation coefficient kg

dy

(1.40)

dt
FIGURE 1.10

A box model for a transient analysis.

This is a differential

VC, and the rate of accumulation of pollutant in the box is VdC/dt. Ler u designate
rhe concentration of pollutant entering the box as C,. We'll also a ume there are
both production and decay components of the reaction rare and de ignare the decay
coefficient kd and the generation coefficient kg. However, as is mo t common, the
decay will be first-order, so kb units are time-I, whereas the generation
is zeroorder, so kg's units are mass' volume -1. time-I From (1.12), we can write
ACCUmulation)

(Input)

rate

_ (Output)

rate

equation,

which we can solve by separating

where Yo is the value of y at t =

where

(1.42)

in the box at time t = 0, then from (1.38) we get

Yo

Substituting

(rrr')

of those

to (1.34)

Coo = QCi + kgV

Q + kdV

(1.43)

Co - Coo

C - Coo = (Co - Coo)e-(kd+~)t

in the box and exiting waste stream (g/rrr')

C, : concentranon of pollutants entering the box (g/rrr')
Q - the total flow rate in and out of the box (m3/hr)
kd = decay rate coefficienr (hr-I)
kg = production rate coefficient (g. m . hr -1)
The units given in the, preceding list ate rep'resentatrve
encountered; any consistent set will do.

(1.38) and (1.43) into (1.42) yields

C = concentration

An easy way to find the steady-state solution

gives

rate
(1.34)

dC/dt = 0, which Yields

O. Integrating

y = yoe-(kd+~)t

If Co is the concentration

v = box volume

Solving for the concentration

in the box, writing
expressing the exponential
as exp( ) gives

that

mig h t be

is simply

to set

C(t)

= Coo

it as a function

(Co - Coo)exp[ -(

Equation (1.45) should make some sense. At time t = 0, the exponential

equals 1 and C = Co. At t = 00, the exponential
term equals 0, and
Equation (1.45) is plotted in Figure 1.11.

c"" - -- - - -- --- - -- - -- - ----.-

-- --- - -- - --= .::Q;;-C-,:-i +-ck-;,,-v

hi h

_ QC'+kgV)
Q + kdV

~~ = -( ~
One way to solve this differential

'.
equation

kd)-

(1.371

(C - Coo)

to make a c h ange
Y = C - Coo

Q+kdV

(1.361

o
Time,

1S

of time Cit), and

+ ~)]

kd

w IC , usmg (1.35) ) can be rewntten

.
as

(1.44 )

(1.35)

where Coo is the concentration in the b

'
h
is with the concentration b f
'
ox at time t = DC. Our concern now, thoug ,
Rearranging (1.34) gives
e ore It reaches steady state, so we must solve (1.34),

~~=-(~+k}(C

to give

(1.41)

(Reaction)

rate

the variables

0f

vari ble . If we let

vana

(1.381

FIGURE 1.11

Step function response for the CSTR box model.

(1.45)

function
C = Coo.

20

Chapter

Mass and Energy Transfer

1.4

EXAMPLE 1.8 The Smoky Bar Revisited

The bar in Example 1.6 had volume 500 m3 with fre hair enrermg at rhe rate of
3
1,000 m /hr. Suppose when the bar opens at 5 P.M., rhe air i lean. If formaldehyde, with decay rate kd = OAO/hr, is emitted from cigarette smoke ar the constant
rate of 140 mg/hr starting at 5 P.M., what would the concentration
be at 6 P.\I.?

Solution

In this case, Q

= 1,000 m%r,

= 500 m3,

C; = 0, and kd = OAO/hr. The steady-state concentration

kg,

kd

= QC; + kgV =
G
=
Q + kdV
Q + kdV
= 0.117mg/m3

Q,C,

The steady-state

OAO/hr

eXP[-(kd

concentration

X 10.0

QC,

- --:::---=--:"-:-::

+ kdV

43.2

+ 1,000/500)t]}

is

108mglday

from (1.35)

X 107

rrr'

in the lake one week after the drop in

= Coo

C(7days)

= 1.8

+ (3.5 - 1.8)exp[-(0.2/day

C(7days)

~ 2.1mg/L

(Co - Coo)exp[ -( kd

~)t]
4

+ ~}]}

0.117!1 - exp[-(OAO

43.2

stream

1.8mglL

Using (lAS), we can find the concentration

pollution from the outfall:

C(t)

X 103mglm3

43.2 X 108 mg/day

X 104 m3/day + 0.20/day

= 1.8 X 103mglm3

500 m3

the lake from the incoming

can be obtained

140 mglhr,

This agrees with the result obtained in Example 1.6. To find the concentration at
any nrne after 5 P.M., we can apply (1045) with Co = O.

C(t) = Coo{l-

is entering

X 104m3/day

= 43.2

140 mg/hr
1,000 m3/hr

10.0 X 103 mg/m '

The total rate at which pollution

i found u ing (1.35):

21

= 0.20/day

00

Coo

C, = 10.0 mgIL

Energy Fundamentals

+ 43.2

X 10 ;\da
10 X 10 m

7days]

at 6 P.M., t = I hr, so
Figure 1.12 shows the decrease
C(lhr)

= 0.117[1 - exp(-2A

X l)J

0.106mglm3

in contaminant

concentration

3
,51'--'"

for this example.

3
To further demonstrate the use f (14
.
Example 1 5 This tim
'II
o.
5), let us reconsider the lake analyzed m
. .
I e we WI assume th
h
fl"
the lake, so its contribution t h I ke' at t e out a I suddenly stops draining mID
ate
a e s pollutIOn stops.

2.1 -~-----------~_~~~~~
~ 1.8 -------~

~
EXAMPLE 1.9 A Sudden Deer

.
ease in Pollutants Discharged

Solution

For this siruation

Co = 3.5 mg/L

V = 10
Q=Q

,-

106 m3

-503

. m /s X

3 600 sib
'

r X 24 hr/day

43.2 X 104 m3/day

o '-------=-~-------o

inro a Lake

Consider the 10 X 106 rrr' I k

I
.
tions given, was found to h a e ana yzed in Example 1.5 which under a condi,
ave a steady- t
II'
'
The POllutIOn is nonconse
.
. s ate po unon concentration
of 3.5 mg/L.
Suppose the condition of thelVlatklveWdlthreaction-rate constant
kd = 0.20/day.
, . d id
a e IS eemed
I
It IS eCI ed to completel di
h
unacceptable. To solve the prob em,
y Ivert t e sewa
f II
' .
as a SOurce of pollution Tbe :
.
ge out a from the lake e1iminatmg It
.
.
e mcommg t
'I'd
concenrrallon C = 100
gIL's
ream sn I has flow Q = 5 0 m3/s an
s.
m
With
h
'
.
flow Q is also 5.0 m3/s Ass',
t e sewage outfall removed
the outgoing
.
f
.
ummg co mp I'
,
tlon 0 POliutanr in the lake
k
ete-mlx conditions
find the concenrrastead
one wee afte h d"
, I
y-state concentration.
r t e Iversion, and find the new flna

7 days

Time,t

FIGURE 1.12

The contaminant

concentration

profile for Example 1.9.

1.4 I Energy Fundamentals

Just as we are able to use tbe law of conservation
of mass to write mass balance
equations that are fundamental
to understanding
and analyzing the flow of materials, we can use the first law of thermodynamics to write energy balance equations
that will help us analyze energy flows.
One definition of energy is that it is the capacity for doing work, where work
can be described by the product of force and the displacement
of an object caused by
that force. A simple interpretation
of the second law of thermodynamics
suggests
that when work is done, there will always be some inefficiency, that is, some portion
of the energy put into the process will end up as waste heat. How that waste heat

22

Chapter 1

1.4

Mass and Energy Transfer

affects the environment is an important consideration in the study of environmental

engineering and science.

Another important term to be familiar with is power. Power I the rate of

doing work. It has units of energy per unit of time. In Sl units, power i given in
joules per second (Jisl or kilojoules per second (kj/s}, To honor the Scottish engineer
James Watt, who developed the reciprocating steam engine, the joule per second has
been named the wart (1 Jls = 1 W = 3,412 Btu/hr).

The First Law of Thermodynamics

The first law of thermodynamics says, simply, that energy can neither be created nor
destroyed. Energy may change forms in any given process, as when chemical energy in
a fuel is converted to heat and electricity in a power plant or when the potential energy
of water behind a dam is converted to mechanical energy as it spins a turbine in a hydroelectric plant. No matter what is happening, the first law says we should be able to
account for every bit of energy as it takes part in the process under study, so that in the
end, we have just as much as we had in the beginning. With proper accounting, even
nuclear reactions involving conversion of mass to energy can be treated.
To apply the first law, it is necessary to define the system being studied, much
aswas done in the analysis of mass flows. The system (control volume) can be anything thar we want to draw an imaginary boundary around; it can be an automobile
engme, or a nuclear power plant, or a volume of gas emitted from a smokestack.
Later when we explore the topic of global temperature equilibrium, the system will
be the Earth Itself. After a boundary has been defined the rest of the universe becomes the surroundings. Just because a boundary has 'been defined, however, does
not mean that energy andlor matenals cannot flow across that boundary. Systems in
which both energy and matter can flow across the boundary are referred to as opell
systems,. whereas those III which energy is allowed to f1ow across t h e b Dun d ar y, but
matter ISnot, are called closed systems.
Sinfcedenergyis conserved, we can write the following for whatever system we
h ave d e me :

:~::i~;e~::ndarY)

as heat and work

+ (~~:~:;ergy

) _ (T~tal energy)
mass
leavi
eavmg system

entering system

(Net Change)
of energy

(1.46)

In

the system

(1,471

23

.
In many applications of (1.46), the net energy added to a system will cause an
increase m temperature. Waste heat from a power plant, for example, will raise the
temperature of cooling water drawn into its condenser. The amount of energy needed
to raise the temperature of a unit mass of a substance by 1 degree is called the specific
heat. The specific heat of water is the basis for two important units of energy, namely
the British thermal unit (Btu), which is defined to be the energy required to raise 1 Ib
of water b~ 1F, and the kilocalorie, which is the energy required to raise 1 kg of
water by 1 C. In the definitions Just gIven, the assumed temperature of the water is
15C (59F). Since kilocalories are no longer a preferred energy unit, values of specific heat in the SI system are given in kJlkgOC, where 1 kcal/kg'tC = 1 Btu/lb'T =
4.184 kJ/kgC.
For most applications, the specific heat of a liquid or solid can be treated as a
simple quantity that varies slightly with temperature. For gases, on the other hand
the concept of specific heat is complicated by the fact that some of the heat energy
absorbed by a gas may cause an increase in temperature, and some may cause the
gas to expand, doing work on its environment. That means it takes more energy to
raise the temperature of a gas that is allowed to expand than the amount needed if
the gas is kept at constant volume. The specific heat at constant volume c, is used
when a gas does not change volume as it is heated or cooled, or if the volume is allowed to vary but is brought back to its starting value at the end of the process.
Similarly, the specific heat at constant pressure cp applies for systems that do not
change pressure. For incompressible substances, that is, liquids and solids under the
usual circumstances,

c, ~nd.cp are identical. For gases, cp is greater than Cv'

The added complications associated with systems that change pressure and
volume are most easily handled by introducing another thermodynamic property of
a substance called enthalpy. The enthalpy H of a substance is defined as
H

+ PV

(1,48)

where U is its internal energy, P is its pressure, and V is its volume. The enthalpy of
a unit mass of a substance depends only on its temperature. It has energy units (kJ or
Btu) and historically was referred to as a system's "heat content." Since heat is correctly defined only in terms of energy transfer across a system's boundaries heat
content is a somewhat misleading descriptor and is not used much anymore. '
.
When a process occurs without a change of volume, the relationship between
Internal energy and temperature change is given by
!!.U=mc,!!.T

For closed systems there is no move

f
and third term drop out of th
ment a mass across the boundary, so the second
e equation The ac
I'
f
db
the right side of (1 46) m
h . , cumu anon a energy represente
Y
.
ay cause c anges 10 the b
bl
f
f
energy, such as kinetic and pot 'I
'
a serva e, macroscopic arms a
.
entia energies or mi
. f
I d
the
atorruc and molecular srruct
f h
'
ICroscoplc arms re ate ro
.
ure ate
system Th
.
,
f
include rhe kinetic energies of
I I
.
ose microscopic forms a energy
. b
rna ecu es and the
.
,
h f
S
acting erween molecules b tw
,energIes
associated with t e orce
' e een atoms With'
I I
Th
sum 0f those microscopic for
f
,Ill
rna ecu es, and within atomse
is represented by the symbol ~\Oh energy IScalled the system's internal energy and
d escnibed t h en as the sum of' . .e total energy E th at a su b stance possesses can be
ItS IOtemal energy U',1lS k inetic energy KE, an d ItS
.
potentia, I energy PE:

E = U + KE + PE

Energy Fundamentals

(1.49)

The analogous equation for changes that occur under constant

enthalpy
!!. H = m cp!!. T

pressure involves
(1.50)

For many environmental systems, the substances being heated are solids or
liquids for which c, = cp = c and A U = !!.H. We can write the following equation
for the energy needed to raise the temperarure of mass m by an amount !!. T:
Change in stored energy

m c S'T

(1.51)

Table 1.3 provides some examples of specific heat for several selected substances. It is worth noting that water has by far the highest specific heat of the
substances listed; in fact, it is higher than almost all common substances. As will be

1.4

24

Chapter 1

25

Energy Fundamentals

Mass and Energy Transfer

There are two key assumptions
implicit in (1.51). First, the specific heat is
assumed to be constant over the temperature
range in question, although in actuality
it does vary slightly. Second, (1.51) assumes that there is no change of phase as
would occur if the substance were to freeze or melt (liquid-solid phase change) or
evaporate or condense (liquid-gas phase change).
When a substance changes phase, energy is absorbed or released without a
change in temperature.
The energy required to cause a phase change of a unit mass
from solid to liquid (melting) at the same pressure is called the latent heat of fusion
or, more correctly, the enthalpy of fusion. Similarly, the energy required to change
phase from liquid to vapor at constant pressure is called the latent heat of vaporization or the enthalpy of vaporization. For example, 333 k] will melt 1 kg of ice
(144 Bru/lb}, whereas 2,257 k] are required to convert 1 kg of water at 100'C to
steam (970 Btu/lb}, When steam condenses
or when water freezes, those same
amounts of energy are released. When a substance changes temperature
as heat is
added, the process is referred to as sensible heating. When the addition of heat
causes a phase change, as is the case when ice is melting or water is boiling, the
addition is called latent heat. To account for the latent heat stored in a substance, we
can include the following in our energy balance:

TABLE 1.3
Specific

Heat Capacity

c of Selected

Substances

(kcaVkgOC,Btu/lb'F)
1.00
0.24
0.22
0~9
0,20
0.50
0.48
0.45

Water (15C)
Air
Aluminum
Copper
Dry soil
Ice
Steam (100C)'
Water vapor (20'C)'
"Constant

(kj/kg'C)
4.18
1.01
0.92
039
0.84
2.09
2.01
1.88

pressure values.

noted in Chapter 5, this is one of water's very unusual properties

responsible for the major effect the oceans have on moderating
tions of coastal areas.

and is in large part

temperature
varia-

Energy released
EXAMPLE 1.10

A Water Heater

in phase change

I--------Latent
100 --------------

Boiling water

from the tank during

i~~,~h~ge
i~1e~;~g~ stored corresponds to the water warming from 50'F to
. smg .
a ong With the fact that water weighs 8.34 lb/gal gives
Change in stored energy ~ rn cAT
X (140

Setting the energy input equal to th

h
'.
units using Table 1.1 yields
e c ange 10 Internal energy

- 50)'F

Melting ice
latent
heat of
fusion

~A~t..:~,-I~.7~6~h~r~

Water 4. 18

kJre

333 kJ

1
'2.1

~
kWC Ice
Heat added to I kg of ice (kJ)

.
and converting

5At kWhr X 3412 B u!k

,
t
Whr ~ 30 X 103 Btu
~~--~~-

-,

o I,
X 1 Btu/lb'F

Steam 2.0 kJjOC

Energy output ~ 0

~ 40 gal X 8.34lb/gal
~ 30 X 103Btu

(1.52)

heatofvaporization,
2,257kJ------1111/

Energy input ~ 5 kW X At hrs ~ SAt kWhr

Assuming no losses from the tank and no water withdrawn
the heating penod, there is no energy output:

~ mL

where m is the mass and L is the latent heat of fusion or vaporization.

Figure 1.13 illustrates the concepts of latent heat and specific heat for water as
it passes through its three phases from ice, to water, to steam.
Values of specific heat, heats of vaporization
and fusion, and density for water
are given in Table 1.4 for both SI and USCS units. An additional
entry has been
included in the table that shows the heat of vaporization
for water at 15'C. This is
a useful number that can be used to estimate the amount of energy required to cause

How long would it take to heat the water in a 40-gallon electric water heater
from 50'F to 140'F if the heating element delivers 5 kW? Assume all of the electrical energy is converted to heat in the water, neglect the energy required to raise
the temperature of the tank itself, and neglect any heat losses from the tank to the
environment.
Solution.
The first thing to note is that the electric input is expressed in kilowatts, which IS a measure of the rate of energy input (i.e., power). To get total
energy delivered to the water,. we must multiply rate by time. Letting t.t be the
number of hours that the heating element is on gives

or absorbed

___

FIGURE 1.13 Heat needed to convert 1 kg of ice to steam. To change the temperature of 1 kg of ice,
2.1 kJ/'C are needed. To completely melt that ice requires another 333 k] (heat of fusion). Raising the
temperature of that water requires 4.184 k]rC, and converting it to steam requires another 2,257 k]
(latent heat of vaporization). Raising the temperature of 1 kg of steam (at atmospheric pressure)
requires another 2.0 kJ/'C.

26

Chapter 1

1.4

Mass and Energy Transfer

TABLE1.4

Important Physical Properties of Water

Property
Specific heat (15'C)
Heat of vaporization (100'C)
Heat of vaporization (15'C)
Heat of fusion
Density (at 4'C)

51 Units
4.184 kJlkg'C
2,257 kJlkg
2,465 kj/kg
333 kJlkg
1,000 kg/m3

nilS

1.00 BruJlb"F
9 2 BruJlb
1,060 Brullb
1-14 BruJlb
62.4 Iblft-' ( .341b1g>!

surface water on the Earth to evaporate. The value of 15 ha been picked a the
starting temperature sincethat is approximately the currenr average urface temperature of the globe.
One way to demonstrate the concept of the heat of vaporization \ hile at the
same time Introducingan important component of the global energy balance that
WIll be encountered in Chapter 8, is to estimate the energy required ro power the
global hydrologiccycle.

Energy Fundamentals

27

Many practical environmental engineering problems involve the flow of borh

matter and energy across system boundaries (open sysrems). For example, it is common for a hot liquid, usually water, to be used to deliver hear to a pollution conrrol
process or, the opposite, for warer to be used as a coolant to remove heat from a
process. In such cases, there are energy flow rates and fluid flow rates, and (1.51)
needs to be modified as follows:
Rate of change of stored energy

m c~T

(1.53)

where
is the mass flow rate across the system boundary, given by the product of
fluid flow rate and density, and ~ T is the change in temperature of the fluid that is
carrying the heat to, or away from, the process. For example, if water is being used
to cool a steam power planr, then
would be the mass flow rate of coolanr, and ~ T
would be the increase in temperature of the cooling water as it passes through the
steam plant's condenser. Typical units for energy rates include watts, Btu/hr, or kj/s,
whereas mass flow rates might typically be in kg/s or lb/hr.
The use of a local river for power plant cooling is common, and the following
example illustrates the approach that can be taken to compute the increase in river
temperature that results. Some of the environmenral impacts of this thermal pollution will be explored in Chapter 5.

EXAMPLE 1.12 Thermal Pollution of a River

A coal-fired power plant converts one-third of the coal's energy inro electrical
energy. The electrical power output of the planr is 1,000 MW. The other twothirds of the energy content of the fuel is rejected to the environment as waste
heat. About 15 percenr of the waste heat goes up the smokestack, and the other
85 percenr is taken away by cooling water that is drawn from a nearby river. The
river has an upstream flow of 100.0 m3/s and a temperature of 20.0C.
a. If the cooling water is only allowed to rise in temperature
flow rate from the stream would be required?
b. What would be the river temperature
ing water?

by 10.0C, what

just after it receives the heated cool-

Solution

Since 1,000 MW represents one-third of the power delivered to the

planr by fuel, the total rate at which energy enrers the power planr is
Input power =
ay yr X 24hr/day X 3600s/h
= 78.0 W/m2
14
2
which is equivalent t I
'
r X 5.10 X 10 m
the Ea h'
f
a a most half of th 168
2
'k'1l8
.
rt s Sur ace (see Fig
8
e
W/m of incoming sunlight srn I
14
quired to raise the watet va~:~ hi ).It might also be noted that the energy~'

Ii

~gh~ble compared to the heat ~; into the atmosphere after it has evaporated
t IS C apter).
vapomation (see Problem 1.27 at the end 0

------

Output power
Effici
lCleney

1,000MW,
1/3

= 3,000 MW,

Notice the subscript on the input and output power in the preceding equation. To
help keep track of the various forms of energy, it is common to use MW, for
thermal power and MW, for electrical power.
Total losses to the cooling water and stack are therefore 3,000 MW - 1,000 MW
2,000 MW. Of that 2,000 MW,
Stack losses

0.15

2,000 MW,

300 MW,

'iiiiiiiiii

28

Cha prer 1

1.4

Mass and Energy Transfer

Energy Fundamentals

29

Hot reservoir

Stack heat
JOOMW,

Th

Qc Waste heat
Cold reservoir
T,

Qs = 100.0 m3/s
T~= 20.0 -c

Q = IOO.Om"
T =2~.1 C

Stream ........

Coolingwaterenergybalancefor the 33.3 percent efficient, 1,000 ~lW,

powerplant in Example1.12.

FIGURE 1.14

and
Coolant losses = 0.85

2,000 MW, = 1,700 MW,

a. Finding the cooling water needed to remove 1 700 MW with a temperature .increase sr of 1O.0'C will require the u~e of (1.53) along with the
specific heat of water,4,184 Jlkg'C,given in Table 1.4:
Rate of change in internal energy = til c !l. T
1 700 MW = . k"1
,
,m
"'s X 4,184J/kg'C

til =
4,184

1,700
10.0

X 10-6

X 10.0'C X 1 MW/(106J/s)

40.6

X 10

kgls

or, since 1,000 kg equals 1 3 f

b T f d h
m 0 water, the low rate is 40.6 m3/s.
.
0 in t e new temperatureof th
.
MW
being released into the ri
hi e fiver,we can use (1.53) with 1,700
,
3
e fiver,w ich again has a flow rate of 100.0 m /s.
Rate of change in internal en
_.
ergy - mc!l.T

FIGURE 1.15

Definition of terms for a Carnot engine.

to work with 100 percent efficiency. There will always be "losses" (although, by the
first law, the energy is not lost, it is merely converted into the lower quality, less useful form of low-temperature heat).
The steam-electric plant just described is an example of a heat engine, a device
studied at some length in thermodynamics. One way to view the steam plant is that
it is a machine that takes heat from a high-temperature source (the burning fuel),
converts some of it into work (the electrical output), and rejects the remainder into
a low-temperature reservoir (the river and the atmosphere). It turns out that the
maximum efficiency that our steam plant can possibly have depends on how high
the source temperature is and how low the temperature is of the reservoir accepting
the rejected heat. It is analogous to trying to run a turbine using water that lows
from a higher elevation to a lower one. The greater the difference in elevation, the
more power can be extracted.
Figure 1.15 shows a theoretical heat engine operating between two heat reservoirs, one at temperature Th and one at TO" An amount of heat energy Qh is transferred from the hot reservoir to the heat engine. The engine does work Wand rejects
an amount of waste heat Qc to the cold reservoir.
The efficiency of this engine is the ratio of the work delivered by the engine to
the amount of heat energy taken from the hot reservoir:
.
W
E fflClency1)
= Qh

1,700MW X (1 X 106J/S)
!l.T=
MW
100.00 m3/s X 103 k'{/ 3
= 4.1 'C
so the temperature of the ri
.
m X 4,184 ]lkg'C
The results of the cal la fiverwill be elevated by 4.1 'C making it 24.1'C.
------..:.=.:::.::::...'~~~cu~at~lo~n~s~I~US~t~pe~rf~o~rm~ed~a~re~sh~oiw~n~i~n~F~,~g~u~r~ei1~.l~~

The Second Law of Ther

d
rno ynamics

In Example 1.12, you will notice th

.
.
contained m the coal actually w at a relatively modest fraction of the fuel enetg)
ahnda rather large amOUntof t~: 7nvlerted to the desired output elecreical power,
t e enVlfonment Th
ue energy e d d
'
. ed to
b
.
e second law of h
n e up as waste heat reJecr
e some waste heat; that is, it is imp tbelrmodynamics says that there will alwaY'
~eto&
~
lllliiiii
_iiiiii_==-__
Visea machine that can convert

(1.54)

The most efficient heat engine that could possibly operate between the two
heat reservoirs is called a Carnot engine after the French engineer Sadi Carnor, who
first developed the explanation in the 1820s. Analysis of Carnot engines shows that
the most efficient engine possible, operating between two temperatures, Th and To
has an efficiency of

TJmax

(1.55)

where these are absolute remperatures measured using either rhe Kelvin scale or
Rankine scale. Conversions from Celsius to Kelvin, and Fahrenheit to Rankine are
K
R

=
=

'C
'F

+ 273.15
+ 459.67

(1.56)
(1.57)

30

Chapter 1

1.4

Mass and Energy Transfer

Energy Fundamenrals

31

requiring less water, involves the use of cooling towers that transfer the heat directly
into the atmosphere
rather than into a receiving body of water. In either case, the rejected heat is released into the environment.
In terms of the heat engine concept
shown in Figure 1.15, the cold reservoir temperature
is thus determined
by the tem-

perature of the environment.

Steam-"

.....-Fuel
__

L----.J

Cool water

In

Let us estimate the maximum possible efficiency that a thermal power plant
such as that diagrammed
in Figure 1.16 can have. A reasonable estimate of Th might
be the temperature
of the steam from the boiler, which is typically around 600C.
For To we might use an ambient temperature
of about 20C. Using these values in
(1.55) and remembering
to convert temperatures
to the absolute scale, gives

Cooling water

Boiler
feed pump

Air

FIGURE 1.16

U:~~;:::=::::,;::;w~annater
YO

QUI

Condenser

A fuel-fired,steam-electric power plant,

, One immediate observation that can be made from (1.55) is that the maximum
possible
heat engine efficiency increases
increases as
as trh e temperature
,
of the hot reserves'
increases or the temperature f th
Id
'
,
'
f , I hoe
co reservoir decreases. In fact since neirher inmire y at temperatures,r no a bso Iute zero temperatures are possible' we must cooI d t h at no real engine ha 100
cue
,
s
percent eff'iciency
which is )'ust a 'fresrarement 0
h
t e second Iaw.
'
Equation (1.55) can help us un derstan d t he
seemi
, '
e seemingly
low efficiency
a f t herrna 1 power p Iants such as the a di
"
'
burned in a firing ch b
ne iagramma] 10 Figure 1.16. In this plant, fuel IS
am er surrounded bib'
"
hr h
this boiler tubing is c
d hi
y meta tu mg. Water Circulating t oug
onverte to igh p
hi h
'
h
conversion of chemical t h
I - ressure, Ig -temperarure steam. Dunng t IS
a t erma ener
I
h
due to incomplete c b '
gy, asses on t e order of 10 percent occur
am usnon and 10
fh
h II
consider local and regional'
II' ss a eat up the smokestack.
Later, we s a
their possible role in glob Iarr po, unon effects caused by these emissions as well as

a warmmg.

The steam produced in th b 'I

ways similar to a child'
, h all er then enters a steam turbine which is in some
s pmw eel. Th hi h
"
through the turbine blad
'
e Ig -pressure steam expands as It passes
,
es, causmg a sh ft h '
to
spm. Although therurb'
'P'
a t at IS connected to the generator
bimes have many stages me
10 igure 1 16'
h
'
with
.. , ISS own as a single unit in actualtty, tur,
I steam eXIlmg
'd
lIy
expan d 109 and COoling as 't
T
one stage and entering another, gra ua
"
,
I goes. he g
f
Spmnmg shaft IOta electrical
enerator converts the rotational
energy a a
b u tiion, A we II'-deSIgned t b' power that goes out onto transmission
",
lines fat d'"
IStrt
h
ur me may h
w ereas the generator may h
ave an efficiency that approaches
90 percent,
Th
ave a convers
If
e spent steam from th
'
Ion e IClency even higher than that.
state as it is cooled in the conde turbme undergoes a phase change back to the liquid
helps pull
h
enser. ThIS ph
h
hal
steam t rough the t b'
ase c ange creates a partial vacuum t
condensed steam is then pump~~ ~n\ thereby increasing the turbine efficiencY. The
The heat released when the ac to the boiler to be reheated.
that clhrculates through the conden steaurncondenses is transferred
to cooling wale!
rtver, eated in th
ser. sually
I'
I ke al
e condenser ad'
coo mg water is drawn from a a
once-through cooling. A rna' n teturned to that body of water which is called

re expensive a

pproach,

which

'of

has the advantage

= 1 -

TJmox

(20
(600

273)

+ 273)

= 0.66

= 66 percent

New fossil fuel-fired power plants have efficiencies around 40 percent. Nuclear
plants have materials constraints that force them to operate at somewhat lower temperatures than fossil plants, which results in efficiencies of around 33 percent, The
average efficiency of all thermal plants actually in use in the United States, including
new and old (less efficient) plants, fossil and nuclear, is close to 33 percent. That
suggests the following convenient rule of thumb:

For every 3 units of energy entering the average thermal power plant,
approximately 1 unit is converted to electricity and 2 units are rejected
to the environment as waste heat.
The following example uses this rule of thumb for power plant efficiency combined with other emission factors to develop a mass and energy balance for a typical
coal-fired power plant.

EXAMPLE 1.13

Mass and Energy Balance

for a Coal-Fired

Power Plant

Typical coal burned in power plants in the United States has an energy content of
approximately
24 kJ/g and an average carbon content of about 62 percent, For
almost all new coal plants, Clean Air Act emission standards
limit sulfur emissions to 260 g of sulfur dioxide (S02) per million k] of heat input to the plant
(130 g of elemental sulfur per 106 kJ). They also restrict particulate
emissions to
13 g/106 k]. Suppose the average plant burns fuel with 2 percent sulfur content
and 10 percent unburnable
minerals called ash, About 70 percent of the ash is
released as fly ash, and about 30 percent settles out of the firing chamber and is
collected as bottom ash. Assume this is a typical coal plant with 3 units of heat
energy required to deliver 1 unit of electrical energy.
a. Per kilowatt-hour
of electrical energy produced, find the emissions of 502,
particulates,
and carbon (assume all of the carbon in the coal is released to
the atmosphere).
b. How efficient

must the sulfur emission

control

system be to meet the sulfur

emission limitations?
c. How efficient must the particulate

emission limits?

control

system be to meet the particulate

1.4

32

Chapter 1

Energy Fundamentals

33

Mass and Energy Transfer

Solution
a. We first need the heat input to the plant. Becau e

To atmosphere
1.4 g S (2.8 g S02)
0.14gfl yash
280 g C

I kWhr electricity
(3,600 kJ)

3 kWhr of hear are

)))1 ,080 kJ

required for each 1 kWhr of electricity delivered,

Heat input
= 3 kWhr heat X 1 k]/s X
kWhr electricity
kW'

3 600 slhr = 10 00 k]

(including: 280 g C
45 gash, 9 g S)

..
130 gS
S emissions = -6X10,800 k]lkWhr
10 k]

1~ g
10 k]

10,800 k]lkWhr

per kWhr

since the coal is 62 percent carbon

0.62 gC
g coal

450 gcoal
kWhr

31.36 gash

280 g C/kWhr

b. Burning 450g coal containing 2 percent sulfur will release 0.02 X 450 =
9.0 g of S. Smce the allowable emissions are 1.4 g, the removal efficiency
must be

FIGURE 1.17

Energy and mass balance for a coal-fired power plant generating 1 kWhr
of electricity (see Example 1.13).

The Carnot efficiency limitation provides insight into the likely performance
of other types of thermal power plants in addition to the steam plants just described.
For example, there have been many proposals to build power plants that would take
advantage of the temperature
difference between the relatively warm surface waters
of the ocean and the rather frigid waters found below. In some locations, the sun
heats the ocean's top layer to as much as 30C, whereas several hundred meters
down, the temperature
is a constant 4 or 5C. Power plants, called ocean thermal
energy conversion (OTEC) systems, could be designed to operate on these small
temperature
differences in the ocean; however, as the following example shows, they
would be inefficient.

EXAMPLE 1.14
S removal efficiency

1 - ~:~

0.85

85 percent

OTEC

Using (1.55), we find

= 31.5 g fly ash/kWhr

- 1
0.14
y - 31.5 = 0.995

In Chapter 7, we will see how th

'1n",

so controls

30C and 5C. What would be the

generating
station operating
with

these temperatures?

SolutIon

Fly ash generated = 0.70 X 0.10 X 450 g coallkWhr

The allowable particular

.
.
must be installed th the ~ttferlls restricted to 0.14 glkWhr,
a ave teo
lOWing removal efficiency:

System Efficiency

Consider an OTEC system operating between

maximum
possible efficiency for an electric

c. Sflince 10percent of the coal is ash, and 70 percent of that is fly ash the total
y as h generated Will be
'

Particulate removal efficienc

7.6 I:>0 S
to disposal

0.14 glkWhr

.
10,800 k]lkWhr
Coal Input =
= 450 g coallk Whr
24 k]lg coal

"
C ar b on emissions

L-

9 g S

6 120 kJ to cooling water

To find carbon emissions, first find the amount of coal burned

Therefore,

280 g C
31.5 g fly ash

85% S,
99.5%
particulate
removal

13.5 g bottom ash

= 1.40 g IkWhr

The molecular weight of S02 is 32 + 2 X 16 = 64, half of which is sulfur.

Thus, 1.4 g of S corresponds to 2.8 g of S02, so 2.8 g SO/kWhr
would be
emitred. Particulate emissions need to be limited to:

33.3%
efficient
power
plant

450 g coal

The sulfur emissions are thus restricted to

Particulate emissions

3 kWhr
(10,800 kJ)

An even lower efficiency,

1 -

(5
(30

estimated

273)

+ 273) = 0.08 = 8 percent

at 2 to 3 percent

for a real plant,

would

be

expected.
= 99.5 percent

'.
ese emiSSIOncontrol systems work.

"
The complete mass and ener
b I.
.
Figure 1.17. In this diagram it h r b a ance for this coal plant is diagrammed
In
.
, I as een assum d h 8
h t
IS removed by cooling water
d h
. e t at 5 percent of the waste ea
(corresponding to the conditi~:;
. t e remaining 15 percent is lost in stack gases
given In Example 1.12).

Conductive and Convective Heat Transfer

When
hotter

two objects are at different temperatures,

heat will be transferred
from the
object to the colder one. That heat transfer can be by conduction, by
convection, or by radiation, which can take place even in the absence of any physical medium between the objects.

1.4
34

Chapter 1

35

Energy Fundamentals

Mass and Energy Transfer

Radiation

As the following example illustrates, improving the efficiency with which we

use energy can save money as well as reduce emissions of pollutants associated with
energy consumption. This important connection between energy efficiency and
pollution control has in the past been overlooked and underappreciated. However,
as will be described in Chapter 7, that situation has been changing. The 1990
Amendments to the Clean Air Act, for example, provide S02 emission credits for
energy efficiency projects.
EXAMPLE 1.15 Reducing Pollution by Adding Ceiling Insulation

T,

FIGURE 1.18

Heat transfer througha simplewall.

Conductive heat transfer is usually associated with solids, as one molecule

vibrates the next in the lattice. The rate of heat transfer in a solid is proportional
to the thermal conductivity of the material. Metals tend to be good thermal conductors, which makes them very useful when high heat-transfer rates are desired. Other
materials are much less so, with some being particularly poor thermal conductors,
which makes them potentially useful as thermal insulation.
Convective heat transfer occurs when a fluid at one temperature comes in contact ~ith a substance a~ another temperature. For example, warm air in a house in
the wmter that comes m contact with a cool wall surface will transfer heat to the
,:,all. As that warm air loses some of its heat, it becomes cooler and denser, and it will
sink and be replaced by more warm air from the interior of the room. Thus there is
a continuous movement of air around the room and with it a transference of heat
from the warm room air to the cool wall. The cool wall, in turn, conducts heat to the
cold exrenor surface of the house where outside air removes the heat by convection.
Figure 1.18 Illustrates the two processes of convection and conduction
through a hypothetical wall. In addition, there is radiative heat transfer from objects
m the room to the wall, and from the wall to the ambient Outside. lt is conventional
practice to combine all three processes into a sin I
II h
f
cess
thar is characterized by the following simple
g e, overa
eat-trans er pro
equanon.
A(T - T)
q =
'R 0
(1.58)
where

heat transfer rate through the wall (W) (B /hr)

A = wall area (m2)or (ft2)
or tu r
Ti = air temperature on one side of the
II ('C
T bi
.
wa
) or ('F)
o ::: am lent air temperature ('C) or ('F)
R - overall thermal resistance 1m2_'crw)
(h 2
Or r-ft -'F/Btu}
The overall thermal resistance R is called the _
.,
hardware store, It will be designated as h R value. If you buy insulation at the
system (hr-fr-'FlBtu). For example 3~-' a~mg an R-value in the American unIt
marked R-ll, whereas 6 inches of h
me -thick fiberglass insulation is usually
t e same material is R-19.

A home with 1,500 ftl of poorly insulated ceiling is located in an area with an
8-month heating season during which time the outdoor temperature averages
40'F while the inside temperature is kept at 70'F (this could be Chicago, for
example). lt has been proposed to the owner that $1,000 be spent to add more insulation to the ceiling, raising its total R-value from 11 to 40 (fc2-'F-hriBtu). The
house is heated with electricity that costs 8 cents/kWhr.
a. How much money would the owner expect to save each year, and how long
would it take for the energy savings to pay for the cost of insulation?
b. Suppose 1 million homes served by coal plants like the one analyzed in
Example 1.13 could achieve similar energy savings. Estimate the annual reduction in S02> particulate, and carbon emissions that would be realized.
Solution
a. Using (1.58) to find the heat loss rate with the existing insulation gives
= A(Ti

To}

= 1,500 ft2

X (70 - 40)'F = 4,090 Btu/hr

11 (ftl-'F-hriBtu)

After adding the insulation, the new heat loss rate will be
l
= A(Ti - To) = 1,500 ft X (70 - 40)'F = 1,125 Btu/hr
q
R
40 (ftl-'F-hr/Btu)
The annual energy savings can be found by multiplying the rate at which energy is being saved by the number of hours in the heating season. If we assume
the electric heating system in the house is 100 percent efficient at converting
electricity to heat (reasonable) and that it delivers all of that heat to the spaces
that need heat (less reasonable, especially if there are heating ducts, which
tend to leak), then we can use the conversion 3,412 Btu = 1 kWhr.
Energy saved

=
=

(4,090 - 1,125) Btu/hr

3,412 Btu/kWhr
5,005 kWhr/yr

24 hr/day

30 day/mo

8 mo/yr

The annual savings in dollars would be

Dollar savings

5,005 kWhr/yr

$0.08/kWhr

$400/yr

Since the estimated cost of adding extra insulation is $1,000, the reduction
in electricity bills would pay for this investment in about 2" heating seasons.

36

Chapter 1

1.4

Mass and Energy Transfer

1Microwave

b. One million such houses would save a total of 5 billion kWhr/yr (nearly
the entire annual output of a typical 1,000 MW, power plant). U ing the
emission factors derived in Example 1.13, the reduction in air emi ions

1000 urn
100

would be
Carbon reduction

=
=

X 5 X 109kWhrlyr

280gC/kWhr

urn

X lO-Jkglg

1,400 X 106 kg/yr

l~m

X 5 X 109kWhrlyr

SOz reduction = 2.8gS0z/kWhr

=
=

X lO-Jkg/g

Wavelength

[/

X 5 X 109kWhr/yr

0.7

Red

0,6

Orange
Yellow

Visible

14 X 106kg/yr

Particulate reduction = 0.14g/kWhr

37

Energy Fundamentals

0,5
X lO-Jkglg

om

urn

Green

Blue

Ultraviolet
0.4

0.7 X 106 kg/yr

Violet

0.001 urn
0.000]

Radiant Heat Transfer

Heat transfer by thermal radiation is the third way that one object can warm another.
Unlike conduction and convection , ra diiant energy IStransported by electromagnetIC '
waves and does not require
a m e dirum to carry t h e energy. As 'IS the case for other
,
forms of electromagnetic
phenomen
. .
a, sue h as fa di10 waves, x-rays and gamma rays,
th
ermal
radiation
can
be
described
ith er 111
' terms of wavelengths ' or using the par,I
f
eit
ttcI

e nature

. terms of discrete photons ' of energy, All

'electromagneti c ra diration, 111

::~~~~:t~n~;I~hwa~es
elf

travel at tdhehspeed of light. They can be described

requency, an t e two are related as follows:

where

Av

by their

(1.59)

c = speed of light (3 X 108 mls)

A = wavelength (rn)
v = frequency (hertz , r.e,
'
eye Ies per second)
When radiant energy is described'
frequency and energy is given by

111

where

E
h

= energy of a photon (J)

= Planck's constant 16.6 X

terms of photons, the relationship

hu

between
(1.60)

urn

X-rays

FIGURE 1.19
A portion of the electromagnetic spectrum. The wavelengths of greatest
interest for this text are in the range of about 0.1 JLm to 100 ,urn.

emitted, is to compare it to a theoretical abstraction

called a blackbody. A blackbody is defined as a perfect emitter as well as a perfect absorber. As a perfect emitter, it radiates more energy per unit of surface area than any real object at the same
temperature.
As a perfect absorber, it absorbs all radiation that impinges upon it;
that is, none is reflected, and none is transmitted
through it. Actual objects do not
emit as much radiation as this hypothetical
blackbody, but most are close to this theoretical limit. The ratio of the amount of radiation an actual object would emit to
the amount that a blackbody would emit at the same temperature
is known as the
emissivity, e. The emissivity of desert sand, dry ground, and most woodlands is estimated to be approximately
0.90, whereas water, wet sand, and ice all have estimated
emissivities of roughly 0.95. A human body, no matter what pigmentation,
has an
emissivity of around 0.96.
The wavelengths
radiated
described

by a blackbody

depend

on its temperature,

as

by Planck's law:

10-34 [-s)

Equation (1.60) points Out that hi h f

hi h
Ig er- reque
Ig er energy Content which
k
h
ncy, s h arter-wavelength
photons have
,
,
maestemp'l
I
t ungs are exposed to them.
otentla ly more dangerous when living

(1.61)

where

In this book the most I'

. Ch
'
mportant ap licari
,
111
apter 8 when the effects of
' p catIon of radiant heat transfer will come
the stratospheric Ozone layer will V~[)~uS gases on global climate and depletion of

EA
T
A
C,

power of a blackbody (W/mz-JLm)

temperature
of the body (K)
= wavelength
(JLm)
= 3.74 X 108 W-f.Lm4/mz
Cz = 1.44 X 104 JLm-K

tha.: context are roughly in the rang: o/:~~sed. The wavelengths of importance
in
6
10
m, also called 1 micton) F
ut O.llLm up to about 100 JLm (llLm IS
electromagneti~ spectrum.
. Or perspective, Figure 1.19 shows a portion of the
. Every object emits thermal
di .
radiation
I bi
ra ianon Th
I
h
a rea a JeCt emits as well
.
e usua way to describe how muc
,
as Other ch
'.
h
aractenstles of the wavelengt s

bodies

= emissive

= absolute

Figure 1.20 is a plot of the emissive power of radiation emitted from blackat various temperatures.
Curves such as these, which show the spectrum of

38

Chapter 1

1.4

Mass and Energy Transfer

2400
70

350 K

'. Iet
Ultravio

Visible

7%

47%

60

7-

50

40
30

~ 20
10
0

10

}
?c

1200

,,

800

E ~

O'AT4

(1.621

\
,\

1\

I
I

The spectral emissivepower of a blackbody with various remperarures.

wavelengths emitted, have as their vertical axis an amount of power per unitwavelength, The way to interpret such spectral diagrams is to realize that the area
under the curve between any two wavelengths is equal to the power radiated by the
object within that band of wavelengths. Hence the total area under the curve is
equal to the total power radiated. Objects at higher temperatures emir more powet
and, as the figure suggests, their peak intensity occurs at shorter wavelengths.
Extraterrestrial solar radiation (just outside the Earth's atmosphere) shows
spectral characteristics that are well approximated by blackbody radiation. Although
the temperature deep within the sun is many millions 01 degrees, its effecrive surface
temperature ISabout 5,800 K. Figure 1.21 shows the close match between rhe actual
solar spectrum and that of a 5,800-K blackbody.
As has already been mentioned, the area under a spectral curve between any
two wavelengths IS the total power radiated by those wavelengrhs. For the solar
spectrum of Figure 1.21, the area under the curve between 0.38 and 0.78 jLm (the
wavelengths visible to the human eye) is 47 percenr 0 It h e tora I area. Thar
at iIS, 47 pet
cent 0f t h e so Iar energy striking th
id f
..
.
f h
e OutSI e a Our atmosphere is in the visible parnon 0 t e spectrum The ultr . I
d h
inf
d
I
h:
. avio et range conrains 7 percent of the energy an t e
I rare wave engt s delive th
. .
,
h
.
r e remammg 46 percent. The total area under t e
I
so ar spectrum curve IScalled th
I
2 A
'11 b h
.
e so ar constant, and it is estimated to be 1 372 wattS
per m. s WI e sown m Chapt 8 hi'
I'
..
h
I
er , t e so ar constant plays an important ro e 10
d etermmmg
t e sur ace temperature of the Earth
The equation describing Plan k' I (
..
.
especially for calculations involvinc h aw 1.61) IS somewhat tricky to maDlpulate,
arion equations howeve
g h e area under a spectral curve. Two other radl'
,
r, are sttalg tfor
d did
The
first, known as the Stelan-B It
I war an are 0 ten all that is neede .
I'
a zmann
awof diati
.
Y
emitted by a blackbody . h
f
ra tatuvn, gives the total radiant energ
Wit sur ace are A d b I
a an a so ute temperature T:

I
I

Wavelength A (urn)
FIGURE 1.20

I'.

1600

-z

30

20

Tnfrared
46%

iI-

7-

250 K

~
5,800-K

Blackbody

/j
0.2

- Extraterrestrial solar flux

'~

I
I
I
I

400

0
0.0

'

0.4

0.6

0.8

1.0

1.2

Wavelength

1.4

- -2.0

2.2

2.4

A (urn)

Wavelength

A. (urn)

FIGURE 1.22 Wien's rule for finding the wavelength at which the spectral emissive power
of a blackbody reaches its maximum value.

The second is Wien's displacement rule, which tells us the wavelength at which
the spectrum reaches its maximum point:
2,898

Wlm -K

1.8

2,898
Amax = T(K)

Am" (jLm) ~
10-8

1.6

FIGURE 1.21 The extraterrestrial solar spectrum (solid line) compared with the spectrum
of a 5,800-K blackbody (dashed).

where
E ~ total blackbody emission rate (W)
0' ~ the Stefan.Bolt
_
zmann constant ~ 5 67 X
T:= absolute temperature (K)
.
A - surlace area of the object (m2)

39

,"

2000

.~
c

Energy Fundamentals

T(K)

(1.63 )

where wavelength is specified in micrometers and temperature is in kelvins. Figure 1.22 illustrates this concept, and Example 1.16 shows how it can be used.

40

Chapter 1

Problems

Mass and Energy Transfer

1.5

If we approximate the atmosphere to be 79 percent nitrogen (N2) by volume and 21 percent oxygen (02), estimate the density of air (kg/m ') at STP conditions (O'C, 1 atm).

1.6

Five million gallons per day (MGD) of wastewater, with a concentration of 10.0 mg/L of
a conservative pollutant, is released into a stream having an upstream flow of 10 MGD
and pollutant concentration of 3.0 mg/L.

EXAMPLE 1.16 The Earth's Spectrum

Consider the Earth to be a blackbody with average temperature 15'C and surface
area equal to 5.1 X 1014 m2 Find the rate at which energy is radiated by the
Earth and the wavelength at which maximum power is radiated. Compare this
peak wavelength with that for a 5,800-K blackbody (the sun).

Solution
E

=
=
=

(a) What is the concentration

5.67
2.0

X 10-8

W/m2_K4

5.1

X 1014

m2 X

(15.0

1.7
273.15 K)'

X 1017 Watts

The wavelength at which the maximum point is reached in the Earth's spectrum is
A

(m)
rnax

I-'

= 2,898 = 2,898 _
T(K)

in ppm just downstream?

(b) How many pounds of substance per day pass a given spot downstream?
want the conversions 3.785 Llgal and 2.2 kg/Ibm from Appendix A.)

Using (1.62), the Earth radiates

aAT4

41

288.15 - 10.11-'m (Earth)

(You may

A river with 400 ppm of salts (a conservative substance) and an upstream flow of 25.0 m3/s
receives an agricultural discharge of 5.0 m3/s carrying 2,000 mg/L of salts (see Figure P1.7).
The salts quickly become uniformly distributed in the river. A municipality just downstream withdraws water and mixes it with enough pure water (no salt) from another
source to deliver water having no more than 500 ppm salts to its customers.
What should be the mixture ratio F of pure water to river water?

For the 5,800-K sun,

500 ppm

A
max

(m
JL)

1+__

= 2,898 _

25.0 m3/s

5,800 - 0,481-'m (sun)

FQm3/s
Oppm

400 ppm

hi hT~is trem~ndous rate of energy emission by the Earth is balanced by the rate at
w IC It e Eart absorbs energy from the sun. As shown in Example 1.16 however,
t hedi so darb energy
striking the Ea th h
h
' energy
k
r
as much Sorter
wavelengrhs than
ra late ac to space by the Ear.th ThiISwaveIengrh shift
. plays a crucial role in the
green h ouse effect.I As described in Chapter 8,car b on dioxide and other greenhouse
gases are re Ianve y transparent t the i
.
h
they tend to absorb the out Din 0 e incommg s orr wavelengths from the sun, but
g g, longer wavelengths radiated by the Earth As those
green h ouse gases accumulate in 0
h
.
velops the planet, upsets the radiat:::n ~mosp ere, they act like a blanket that en
alance, and raises the Earth's temperature.
0

3
50m /s
2,000 ppm

FIGURE Pl.7

1.8

A home washing machine removes grease and dirt from clothes in a nearly first-order
process in which 12 percent of the grease on the clothes is removed per minute. The washing machine holds 50.0 L of water and has a wash cycle of 5.00 minutes before discharging the wash water. What will be the grease concentration (in mg/L) in the discharge
water if the clothes initially contain 0.500 g of grease?

1.9

Plateau Creek carries 5.0 m3/s of water with a selenium (Se) concentration of 0.0015 mg/L.
A farmer starts withdrawing 1.0 m3/s of the creek water to irrigate the land. During irrigation, the water picks up selenium from the salts in the soil. One-half of the irrigation
warer is lost to the ground and plants, and the other half is returned to Plateau Creek. The
irrigation run-off to the creek contains 1.00 mgIL of selenium. Selenium is a conservative,
nonreactive substance (it does not degrade in the stream), and the stream does not pick up

PROBLEMS
1.1

The proposed air quality standard for Own (0)' 0

e 3 IS .08 ppm
(a) Express that standard in l-'g/m3 t 1
f
'
a atrn 0 pressure and 25'C
b
( ) At the elevation of Denver the
d ar d at that pressure and at' a t pressure ISabo ut 0 ,82 atm. Express the ozone stanemperature of 15'C
Suppose the exhaust gas from an aut
bOI
.
id
omo I e co t
10
rnonoxi e. Express this concentratio
g/ 3 n ams . percent by vol ume of carbon
n III m m at 25'C
d
Suppose the average concentration of SO .
an 1 atm.
1 atm. Does this exceed the (24 h)
2 IS measured to be 400 JLg/m3 at 25'C and
for atomic weights.)
- r air quality standard of 0,14 ppm? (See AppendiX B
0

1.2

more selenium from any other source.

(a) If the farmer irrigates continuously, what will be the steady-state concentration of
selenium in the stream downstream from the farm (after the irrigation run-off returns
to the stream)?
(b) Fish are sensitive to selenium levels over 0.04 mg/L. The farmer agrees not to use
more warer than will keep the stream selenium level below this critical concentration.
How much water can the farmer withdraw from the stream to use for irrigation?

1.3

1.4

A typical motorcycle emits about 20

f CO
(a) What volume of CO would a 5- glo
per mile,
b)
rm
e
tnp
produce
f
h
l
( Per meter of distance traveled h
a ter j e gas cools to 25'C (at 1 atm)
,w
at
volum
f
stan d ar d 0f 9 ppm'
eo air could be polluted to the air quality
0

7//'

1.10

When methanol is used to generate hydrogen, it reacts with the following reaction:
2CH20H

--->

2CO

+ 3H2

The reaction is second order in methanol (CH20H), and it is observed that 100 g of
carbon monoxide (CO) can be produced in one day in a batch reactor, if you start with
200 g of methanol. What is the rate constant for this reaction?

Problems
Chapter

42
1.11

with an inversion layer above it). Consider a town having an inversion at 250 m, a 20-km
horizontal distance perpendicular 10 the wind, a winds peed of 2 mis, and a carbon
monoxide (CO) emission rate of 60 kgis (see Figure P1.16). Assume the CO is conservative and completely mixed in the box.

irh
I
10 X 106 mJ is fed by a pollution-free stream with flow rate
A lak e Wit constant vo ume
.'
31
A f tory dumps 5 m3/s of a nonconservative waste with concentranon
50 m s.
ac
ff
K fOnd
100 mgiL into the lake. The pollutant has a reaction rate coe rcienr
0
.i ay.
Assuming the pollutant is well mixed in the lake, find the steady-state concenuanon of

1.12

43

Mass and Energy Transfer

What would be the CO concentration

pollutant in the lake,

The two-pond system shown in Figure P1.12 is fed by a stream with flow rate 1.0 MGD
(millions gallons per day) and BOD (a nonconservative pollutant) concentratton 20.0 mgIL,
The rate of decay of BOD is 0.30/day. The volume of the firsr pond IS5,0 million gallons,
and the second is 3,0 million,
Assuming complete mixing within each pond, find the BOD concentrarion

Wind
2 m1s

in the box?

--

---f-.

..

c=?
2 m/s

------_.,-

leaving
250 m

each pond,
20km

60 kgls
I

or co

20 mglL
1 MOD

FIGURE Pl.16

1.17

Consider the air over a city 10 be a box 100 km on a side that reaches up to an altitude of
1.0 km. Clean air is blowing into the box along one of its sides with a speed of 4 mls. Suppose an air pollutant with reaction rate k = 0.20/hr is emitted inro the box at a total rate of
10.0 kgis. Find the steady-state concentration if the air is assumed to be completely mixed,

1.18

If the windspeed in Problem 1.17 suddenly drops to 1 mis, estimate the concentration

FIGURE Pl.12

1.13

1.14

1.15

1.16

A lagoon is to be designed 10 accomodate an input flow of 0.10 m3/s of nonconservative

pollutant with concentration 30.0 mgiL and reaction rate 0.20/day. The effluent from the
lagoon must have pollutant concentration of less than 10.0 mgiL. Assuming complete
mixing, how large must the lagoon be?
Ozone is sometimes used as a disinfectant for drinking water, Ozone is highly reactive,
It will react With many benign species found in water, as well as the pathogens it is in
tended to kill, It ISfound that ozone reaction in water nearly follows first-order kinetics
m ozone concentration, such that its concentration decreases by 50 percent in 12 minutes
(t1/2 = 12 min), A water supplier wants to inject Ozone into a pipe bringing water 10 the
water treatment
plant to predisinfecr the influent. The 3 .0 -ft. diiarneter pIpe
" IS 3 ,400 feet
'
Iong with a. steady
flow
rate
of
10000
galimin
Wh
t
ion
of
.
,.
a concentration 0 ozone (iIII mgILl
should be injected
at
the
head
of
the
pipe
so
that
the
he ni ,
"
re WI'II b e an ozone concentra rion
I of
1 .0 mgIL ar t e pipe s exit into the plant) The o:
b
"
s
an ideal PFR.
. e pipe may e realistically assumed 10 act a
You~ stomach is a chemic~lkreactor.When you devour a fast food 99 special hamburger
a
,t
lI1 h lout a mll1Ule'h acts , e an IOstantaneousinput of 325 g of food entering the srom
ac . n response, t e stomach starts p duci
"
'
ously excreted into the st
h
ro ucmg gastric liquids (acids), which are connnu'
The fluid also leaves the s~:~~cha:oat~ate of 12.0 mLimin as the hamburger is digested,
the volume of liquid in the st
h e small IOtestmeat a flow rate of 12.0 mLlll1ln, SO
omac stays co r
1
'
inn
rate constant is 1.33 hr-',
ns ant at .15 L. The hamburger dlgesno
(a) What kind of ideal reactor would yo
d I
'
u mo e your stomach as)
(b ) What fractton of the hamburger'
,
"
h
one hour after you eat the hamb s m)assWill remam undigested in your stomar
.
urger.
A simple way to model air pOllution ov
"
,
plete mixing and limited capabill't f hera CItyIS WIth a box model that assumes com"
y or t e pollur'
d'
' IlY
except 10 the dtrection of the pr 'I'
,
Ion to Isperse horizot1lally or vertICa
eValmg wmds (fOr example, a town located in a vaIIey

1.19

of

pollutants two hours later.

A lagoon with volume 1,200 m3 has been receiving a steady flow of a conservative waste
at a rate of 100 m3/day for a long enough time to assume that steady-state conditions
apply. The waste entering the lagoon has a concentration of 10 mgiL. Assuming completely mixed conditions,
(a) What would be the concentration of pollutant in the effluent leaving the lagoon?
(b) If the input waste concentration suddenly increased to 100 mgiL, what would the
concentration in the effluent be 7 days later?

1.20

Repeat Problem 1.19 for a nonconservative

pollutant with reaction rate k

1.21

A nuclear power station is situated in Coal Valley, which is a roughly rectangular valley
that is 5 km long, 2 km wide, and 200 m deep. You have been asked to evaluate the effects
of a worst-case scenario where the reactor housing fails, and radiation is released to the
atmosphere. In your evaluation, you determine that 120 kg of Iodine-131 (a radioisotope
that causes thyroid gland and liver damage) could be released into the atmosphere,

0.20/d.

(a) Assuming the release of Iodine-131 was very rapid and all of it was uniformly distributed through the valley's atmosphere with none escaping the valley, what would
the concentration of lodine-131 be in the valley'S air? Your answer should be expressed in units of ppmv, and you may assume an atmopheric pressure of 1.0 atm and
a temperature of 20"C.
(b) Assuming the Iodine-131 concentration you calculated in part (a) is the initial concentration in the valley, you now want to determine the time it will take for tbe concentration to decrease to the safe limit of 1.0 X 10-5 ppmv. The average windspeed
through the valley (entering at one end and exiting at the other) is only 1.5 mlmin.
However, Iodine-131 also is removed by two other processes: 1) radioactive decay

Chapter 1

44

Problems

Mass and Energy Transfer

Fifty percent of that sunlight is captured by the collector and heats the water flowing
through it. What would be the temperature rise of the water as it leaves the collector?

with a half life of 8.1 days, and 2) sedimentation to the ground with a rate constant
of 0.02 d-I. Draw a picture of the situation, and label the approprIate variables.

1.22

(c) Now derive an equation that expresses the concentration of lodine-131 in.the vall~y's
air as a function of the time since the accident. Use the equation ro determine the time
needed for the concentration to decrease to a safe level.
When a strong acid is added to water, it completely dissociates its proton (H+). For
example, the dissociation of sulfuric acid in water is
H2S04

+ H20

+ SO~- +

-->2H+

1.24

An uncovered swimming pool loses 1.0 in of water off of its 1,000 ft2 surface each week due
to evaporation. The heat of vaporization for water at the pool temperature is 1,050 Btu/lb.
The cost of energy to heat the pool is $10.00 per million Btu. A salesman claims that a $500
pool cover that reduces evaporizative losses by rwo-thirds will pay for itself in one 15-week
swimming season. Can it be true?

1.25

Two-thirds of the energy content of fuel entering a 1,000-MW, nuclear power plant is
removed by condenser cooling water that is withdrawn from a local river (there are no
stack losses, as is the case for a fossil fuel-fired plant). The river has an upstream flow of
100 m3/s and a temperature of 20C.
(a) If the cooling water is only allowed to rise in temperature by 10C, what flow rate
from the river would be required? Compare it to the coal plant in Example 1.12.

H20

Or more simply:

+ SO~-

H2S04-->2H+

(Pl.l)

A similar type of reaction occurs if a strong base is added to water, except hydroxide
ions (OH-) are dissociated. For example, the dissociation of the strong base, sodium
hydroxide (NaOH), in water is
NaOH

+ H20

-->OH-

+ H20 +

1.26

Na +

Or more simply:
NaOH-->OW

+ Na+

(Pl.2)

When both a strong acid and a strong base are added to water together, the protons from
the acid react WIth the hydroxides from the base to produce more water molecules until
the supply of either excess protons or hydroxides is used up. The reaction is
W

+ OW

The rate constant for reaction (P1.3) is 1.4

-->H20

(P1.3)

.0
til t

1.23

Compare the energy required to evaporate a kilogram of water at 15C to that required to
raise it 3 km into the air. (Recall that 1 kg on Earth weighs 9.8 N, and 1 J = 1 N-m.)

1.28

Compare the potential energy represented by 1 lb of water vapor at 59F (15C) and an
elevation of 5,000 ft to the energy that would be released when it condenses into rain
(1 Btu = 778 ft-Ib).
A 600-MW, power plant has an efficiency of 36 percent with 15 percent of the waste heat
being released to the atmosphere as stack heat and the other 85 percent taken away in the
cooling water (see Figure Pl.291. Instead of drawing water from a river, heating it, and returning it to the river, this plant uses an evaporative cooling tower wherein heat is released
to the atmosphere as cooling water is vaporized.
At what rate must 15C makeup water be provided from the river to offset the water
lost in the cooling tower?

1.29

he as s.water at the same insranr, what will be the half-life of the added protons
e waterr

A 4 X 8-ft solar collector has water cir I'

h
.
minute (gpm) while exposed to sunli h en a~lOgt rough It at the rate of 1.0 gallon per
g t wit mtensirv 300 Btu/ft2-hr (see Figure p1.23).

o~,"
4'

(b) How much would the river temperature rise as it receives the heated cooling water?
Again, compare it to Example 1.12.
Consider a 354-mL can of soda cold enough to cause moisture from the air to condense on
the outside of the can. If all of the heat released when 5 ml of vapor condenses on the can
is transferred into the soda, how much would the soda temperature increase? Assume the
density and specific heat of the soda are the same as water, neglect the thermal capacitance
of the can itself, and use 2,500 kj/kg as the latent heat of vaporization (condensation).

1.27

lOll L mol-I. s-b.

(a) 8.00 mg of H2S04 is added to 1.00 L of water in a flask. How much NaOH (in mg)
must be added to neutrahze the acid' Neutrall'zatl'on
.
f II of the
from the aci
.
means conversron 0 a
protons rom the acid to water as shown in reaction (P1.3).
(b) If
t the
th 8.00
fI k'mg of H 2SO4 and the amount a f base you calculated in part (a) are ad ded

45

~~~ Stack heat

"
(

""
((

Evaporative
cooling

f/?

1 gpm

r---~
...

River

To=Tj+6.T

L.-3~:~e~-~~~:nt
--.J---r..F~~M_akeUp~wat_e,

x 8'

I gpm

T,
FIGURE Pl.29
FIGUREPl.23

1.30
"From Moore and Pearson, Kinetics and M h .
ec antsm, 3rd ed 1981
,

W,ley-Interscience, New York, NY.

An electric water heater held at 140F is kept in a 70F room. When purchased, its insulation is equivalent to R-5. An owner puts a 25-ft2 blanket on the water heater, raising its

46

Chapter 1

Mass and Energy Transfer

total R value to 15. Assuming 100 percent conversion of elecrriciry inro heated water,
how much energy (kWhr) will be saved each year? If electriciry COStS8.0 cenrslkWhr
how
much money will be saved in energy each year?

1.31

A 15-W compact fluorescent lightbulb (CFL)

60-W incandescent while using only one-fourth
one CFL, compute carbon, S02, and particulate
replaces incandescents and the electricity comes
in Example 1.13.

1.32

Suppose a utility generates electricity with a 36 percent efficient coal-fired power plant
errurnng the legal limit of 0.61b of S02 per million Btus of heat into the plant. Suppose
the utility encourages Its customers to replace their 75-W incandescents with 18-W compact fluorescent lamps (CFLs) that produce the same amount of light. Over the 10 OOO-hr
lifetime of a smgle CFL,
(a) How many kilowatt-hours

produces the same amount of lighr as a

the power. Over the 9,000-hr liferime of
emissions that would be aved if one CFL
from the coal-fired power plant described

Environmental
Chemistry

CHAPTER

of electricity would be saved?

(b) How many 2,000-lb tons of S02 would not be emitted?

(c)

If the utility can sell its rights to emit SO

50

1.33

1.34

1.35

t $800
( h
11 d
Ch
7 h
2 a
per ton t ese are ca e
saved by'a ;~ngle a~;~? ), ow much money could the utiliry earn by selling the

"allowances"

No.6 fuel oil has a carbon COntent of 20 k carbon

9
""
.
cent efficient power plant f' d h
b
g
per 10 J. If It IS burned in a 40 per, In t e car on ernissi
kil
".
duced, assuming all of the carbon in the fu " Ions per 1 owatt-hour
of electricity prooil-fired power plant emissl"on
I"'
deliS released into the atmosphere.
By law, new
s are mute to 86
f SO
" .
f
thermal input and 130 mg NO 1M] E .
mg o.
2 per million joules (M]) 0
emissions per kilowatr-hour.
x
stlmate the maximum allowable
502 and NO,

2.1

Introduction

2.2
2.3
2.4
2.5

Stoichiometry
Enthalpy in Chemical Systems
Chemical Equilibria
Organic Chemistry

2.6

Nuclear Chemistry

Problems
References

Mars radiates energy with a peak wavelength of 13 2

(a) Treating it as a blackbody what w ld i
. /Lm.
b
'
au Its temperature be)
( ) What would be the frequency ad'
n energy COntent f
h
The rate at which sunlight
h
a a paton
at that wavelength?
1 370
2
reac es the Outer d
f
"
,
W/m (the solar constant for E hi Th e ge 0 the atmosphere
of Earth IS
6
150 X 10 km. Solar radiation de
art.
e Earth's orbit has an average radius of
E'
h
creases as the
snmare t e solar constants for
square of the distance from the sun.

It often matters much how given atoms combine, in what arrangement, with

what others, what impulse they receive, and what impart. The same ones make
up earth, sky, sea, and stream; the same the sun, the animals, grain and trees,
but mingling and moving in ever different ways.
-Lucretius (95-52 B.C.) in The Nature of Things

(a) Mars, whose orbit has a radius of 228 X 1 6

(b) Venus, wbose orbit has a radius of 108

1.36

Obi

O/m.

tects not only radiate energy b

h
.
b d
diati
f
' ut t ey absorb
di
o y ra ration or an object at temperat
T"
ra ianr energy as well. The net blackgiven by
ure I m an e "
"
nVlronment with temperature
T2 IS

En" = <TA[(TJi4 - (T )4]

1.37

2.1 I Introduction

X 10 krn

Suppose an unclothed human b d

2
perature of 32'C and' .
0 y has a surface area
f 13
2
.
b
,IS
in a room with surf
a
. 5 m , an average skin tern'
a d y (a very good
".
aces at 15'C T
.
approXlmatlOn), find the net h
. reatmg this person as a blackA hot-water radiator has a surface t
eat loss by radiation (watts).
Treating It as a black bod f
emperature of 80'C
2
(see Problem 1 36)
y, ind the net rate at which"
'11 and a surface area of 2 m .
.
.
It WI rad,ate energy to a 20'C room

Almost every pollution

qualitative descriptions

problem that we face has a chemical basis. Even the most

of such problems as the greenhouse effect, ozone depletion,

toxic wastes, groundwater contamination, air pollution, and acid rain, to mention a
few, require

at least a rudimentary

understanding

of some basic chemical

concepts.

And, of course, an environmental engineer who must design an emission control

system or a waste treatment plant must be well grounded in chemical principles and
the techniques of chemical engineering.
In this brief chapter, the topics have been
selected with the goal of providing only the essential chemical principles required to
understand
the nature of the pollution problems that we face and the engineering
approaches

to their solutions.

47