MASS AND ENERGY

BALANCE
METRIC SYSTEM..
Weight in grams (g), milligrams (mg), or
micrograms (mg).
Volume in liters (L), milliliters (mL) or microliters (mL).
Concentration units in parts per million, mg/L,
mg/L, or mg/kg, gmt (grams per metric ton) for
solids

MEASUREMENTS
 Addition and Subtraction: Answer shall contain
no significant digits farther than the least
precise number:
163 000 000 +
217 885 000 +
96 432 768 = 477 300 000

SIGNIFICANT FIGURES
 MULTIPLICATION AND DIVISION
The product or quotient should contain no more
significant digits than the number with the
fewest significant digit:
113.2 x 1.43 = 161.876 reported as 162
113.2/1.43 = 79.16 rounded to 79.2
113.2 + 1.43 = 114.63 rounded to 114.6
113.2 1.43 = 111.77 rounded to 111.8

SIGNIFICANT FIGURES
 When the first digit discarded is more than 5 or is
a 5 followed by at least one digit other than 0,
the last digit retained should be increased by 1.
When the first digit discarded is 5 followed only
by 0 or less than 5 then retain the number.
8 367.505 rounded to four digits is 8 368.
8 367.500 rounded to four digits is 8 367.

ROUNDING OFF
1mg/L = 1 ppm (by weight) if fluids are
watery (sg= 1)
If
not, 1 mg/L = ppm (by wt) x sg of
mixture
Pollutant
concentration in air can be
expressed in parts per million
1ppmv (by volume) = 1 volume of
gaseous pollutant / 106 volumes of air
Concentrations are expressed as mg/m3

FOR GASES
 Relationship
between ppmv and mg/m3 is
dependent on pressure, temperature and
molecular weight of pollutant
PV = nRT
Pressurein atm, Volume in m3, molecular mass in
moles, R gas constant (0.082056 L-atm/mol- deg K,
and Temp in deg Kelvin
 Find
the volume that 1 mole of an ideal gas would occupy at
standard temperature and pressure conditions (STP) of 1 atm
and 0 oC. Repeat for 1 atm and 25 oC
Solution:

V (at 0o) = 1 x 0.0820 x 273.15 / 1 = 22.414 L

V (at 25o) = 1 x 0.0820 x 298.15 / 1 = 24.465 L

VOLUME OF AN IDEAL GAS

To convert ppm to mg/m3
mg/m3 = ppm x MW / 22.414 (at 0o and 1 atm)
At other temperatures:
mg/m3 = ppm x MW x 273.15 / 22.414 x Temp
Temp units are always in oK .

CONVERSION FOR GASES

Forgases, the Air Quality Standards use
the units mg/m3 or mg/m3 as shown in the
next problem.

CONVERTING PARTS PER MILLION

The minimum level of CO based on an 8-
hour measurement is 9.0 ppm. Express
this standard as a percent by volume
and as mg/m3
 Withina million volumes of air there are 9.0
volumes of CO no matter what the temp or
pressure is.
% CO = 9.0 x 100 / 1.0 x 106 = 0.0009 %
MW of CO = 28 and at 1 atm and 25 oC
CO = 9.0 x 28 / 24.465 =10.3 mg/m3

SOLUTION
MATERIALS BALANCE
When chemical reactions take place,
matter is neither created nor destroyed
Input = Output + Accumulation

LAW OF CONSERVATION OF MASS

State of equilibrium exists, nothing changes
with time.
Forsuch as system, there is no decay or
accumulation and the equation is simplified
Input rate = Output rate

STEADY STATE SYSTEMS

Inthe environment, a system contained
within boundaries such as rivers, lakes or
a section of a stream, the flow rate (Q)
and concentration of stream and
pollutants (C) going into a system should
be equivalent to the Q and C of the
pollutant coming out of the system.

QSCS + QWCW = QMCM

Astream flowing at 10.0 cu.m. per sec
has a tributary feeding into it with a flow
of 5.0 cu.m. per sec. The concentration
of chlorides upstream of the junction is
20.0 mg/L and the tributary chloride
concentration is 40.0 mg/L. Assuming
complete mixing, find the downstream
chloride concentration.

EXAMPLE
 Theflowrate downstream (mixture flow, QM)
can be estimated as the sum of the two
stream flows, QS and QW
The
chloride concentration downstream
can be calculated as

Convert to the same units:

1000 L = 1 cu.m.
Substitute values
C M = 26.67 mg/L
 For these type of cases, the contaminants undergo
chemical, biological or nuclear reactions at a rate
sufficient to treat them as non-conservative.
Input rate = Output rate + Decay rate
First order decay can be expressed as

where K is the reaction rate coeff (time-1)

The equation indicates the rate of change of
concentration or pollutant with respect to time.

STEADY STATE WITH NON-

CONSERVATIVE POLLUTANTS
Solving
the differential equation gives the
concentration at any time t as:

Fornon-conservative substance, the total rate of

decay can be written as:
Decay Rate = KCV
The mass balance can thus be expressed as
Input rate = output rate + KCV
 Consider a 10.0 x 106 cu.m. lake fed by a polluted
stream having a flow rate of 5.0 cu.m/sec and pollution
concentration equal to 10.0 mg/L. There is a sewage
outfall that discharged 0.5 cu.m/sec of wastewater
having a pollutant concentration of 100.0 mg/L. The
stream and sewage wastes have a reaction rate
coefficient of 0.20/day. Assuming the pollution is
completely mixed in the lake, and assuming no
evaporation or other water losses or gains, find the
steady state concentration.

SAMPLE PROBLEM
 Inputrate = QsCs + QwCw
= [(5.0 x 10.0) + (0.5 x 100.0)] x 103
= 100,000 mg/s or 100 kg/s
Output rate = QMCM
= (5.0 + 0.5) x C x 103
= 5,500C
Decay rate = [0.2 x C x 10 x 106 x 103]/[24 x 3600 sec/day]
= 23,100C
100,000 = 5,500C + 23,100 C C = 2.49 mg/L

SOLUTION
 Non-steady state condition
How will the system when there is a sudden change in the pollution entering
the stream?
System can be depicted as a box model with a volume V and a
concentration C and a flow rate Q out of the box.
Assuming a completely mixed system so that C in the box is the same as that
going out.
The total mass of pollutant in the box is VC and the rate of increase of
pollutant in the box is V dC/dt.
If total rate of pollution which enters the box is S (source strength), and
pollutants are non-conservative, then:
Accumulation rate = Input rate Output rate Decay rate

STEP FUNCTION RESPONSE

A steady state solution to this equation is equating the
rate of change in concentration to 0.

To get the concentration at any time t before it reaches

steady state,

Mathematical solution will give the simplified equation

STOICHIOMETRY
Chemical reactions when written down provides
qualitative and quantitative information.
Qualitatively, we can see what reactions are
taking place.
Quantitatively,
the law of conservation of matter
can be applied to give information on how much
of each compound is present during a reaction.

CHEMICAL REACTIONS
 CH4 + O2 CO2 + H2O
1 atom C = 1 atom C
4 atoms H 2 atoms H
2 atoms O 3 atoms H
CH4 + 2 O2 CO2 + 2 H2O
16g of methane reacts with 64 g of oxygen to
give us 44 g of carbon dioxide and 18 g of water

EXAMPLE
If
100 g of butane (C4H10) reacts with oxygen, how
much carbon dioxide is produced?
Solution: 2 C4H10 + 13 O2 8 CO2 + 10 H2O

PROBLEM #1
A 1.67 x 10-3 M glucose solution (C6H12O6) is completely
oxidized to CO2 and H2O. What is the theoretical oxygen
demand to complete the reaction?
Solution: C6H12O6 + 6 O2 6 CO2 + 6 H2O
Change M to mg/l: 1 mg/L = M (mol/L) x MW (g/mol) x
103 (mg/g)
Answer: Theoretical Oxygen Demand is 320 mg/l

PROBLEM #2
ENERGY BALANCE
 Energy can neither be created nor destroyed
Energy
may change forms (chemical energy
converted to heat or potential energy to
mechanical energy).
Total
Energy = Internal Energy + Kinetic Energy
+ Potential Energy
E = U + KE + PE

FIRST LAW OF THERMODYNAMICS

 BTU: British Thermal Units the energy required to raise 1
lb of water by 1 oF.
kcal: Kilocalories energy required to rais 1 kg of water
by 1 oC.
kJ/kg- oC: Kilojoules per kilogram-degree SI units for
energy
1 kcal/kg- oC = 4.184 kJ/kg- oC
1 BTU = 0.252 kcal =1.055 kJ = 0.293 Wh (watt-hour)
1kWh = 3412 BTU

UNITS OF ENERGY
 Theamount of energy required to raise the temperature of
a unit mass of substance by 1 degree.
Specific heat at constant volume (Cv) is used when a gas
does not change volume when it is heated or cooled or if
the volume is allowed to vary but is brought back to the
original.
Specific
heat at constant pressure (Cp) is used when the
system does not change pressure.

SPECIFIC HEAT
 When a process occurs without any change in volume,
change in internal energy is equivalent to the mass
multiplied by the specific heat by volume and the change
in temperature: U = mCvT
Underconstant pressure, for solids and liquids: enthalpy is
equivalent to the mass multiplied by the specific heat and
the change in temperature: H = mCpT
For
many environmental systems the substances being
heated are solids and liquids for which Cv = Cp and U = H
The change in stored energy is expressed as: mcT
 How long would it take to heat 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 energy required to
raise the temperature and the heat losses in
the water tank, if any.

EXAMPLE
 Electric
input is expressed in power units (kW) and can be
converted to energy (kWh)
Energy input = 5 k x t = 5t kWh
Assuming no losses from the tank and no water drawn out from
the tank, energy output = 0.
Density of water is 8.34 lbs/gal
Change in stored energy = mcT = 40 (8.34)x1x90 = 30,000 BTU
energy input = energy stored: 5t kWhx3412 BTU/kWh = 30,000
t = 1,76 hr or 1 hr 46 min.

SOLUTION
A coal-fired power plant converts 1/3 of the coals energy
into electrical energy. The electrical power output of the
plant is 1000 MW (megawatts). The other 2/3 of the energy
content of the fuel is rejected to the environment as waste
heat. About 15% of the waste heat goes to the smokestack
and the other 85% 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 oC.
A.If the cooling water is only allowed to rise in temperature
by 10.0 oC, what flow rate from the stream would be
required?
B.
What would be the river temperature just after it receives
the heated cooling water?
EXAMPLE
 Since 1000 MW represents 1/3 of the power delivered to the
plant by the fuel, the total input energy is:
Input energy = Output energy / efficiency
1000 MWo/(1/3) = 3000 MW
Total losses of the cooling water = 3000 1000 = 2000 MW
Stack losses = 0.15(2000) = 300 MW and Coolant loss = 1700 MW

SOLUTION
 To find the cooling water needed to remove 1700 MW, with
a temperature increase of 10.0 oC, using the specific heat of
water 4184 J/kg-oC:
Rate of change of stored energy = mcT

.
In terms of flow: 40.6 cu.m per sec
 To find the new temperature of the river, use the previous
equation, with 1700 MW being released into the river with a
flow rate of 100.0 cu.m/sec
Rate of change of stored energy = mcT
/

The temperature of the river will be elevated to 24.1

GROWTH EQUILIBRIA
 Mathematicaltools can shed light on the future of a
number of environmental problems.
Theexponential function is one of the most useful
and most powerful mathematical function for growth
in environmental systems.
Otherfunctions include the logistic and Gaussian
functions.

MATHEMATICS OF GROWTH
 This occurs in any situation where the increase in some
quantity is proportional to the amount currently present.
If we start with an initial amount, and end up with a
final amount after time t, and assume a growth rate
factor of r in fraction per year, then:

Example:

In general:

EXPONENTIAL GROWTH
 In 1995, the US produced 3.0 x 1012 kwh of electricity. The
average annual growth rate of the demand from the
previous 15 yeas was at 7 % per year. Estimate the
electricity consumption in 2050 if there were no change in
the consumption rate for the next years.
Solution:

EXAMPLE
 If
the events of interest in the environment assumes
continuous growth in a smooth continuous function
without the annual jumps, the calculation can be
called continuous compounding.
The growth curve becomes the true exponential
function which we will want to use the most.
The quantity grows in proportion to itself, or the rate of
change of the quantity N is proportional to N, with the
proportionality constant, r (rate of growth) and units of
time (-1)

CONTINUOUS COMPOUNDING


And the mathematical solution becomes

Using the previous example, consider the growth of

1.8% to be continuously compounded annually.
Starting with the 1995 electricity consumption of 3.0 x
1012 kwh/yr, what would be the consumption in 2050 if
the growth rate remains constant?
Solution:

EXAMPLE
A quantity that is growing exponentially requires a fixed
amount of time to double in size, regardless of starting time.
The doubling time (Td) at a fixed exponential rate r can be
calculated at N = 2No and t = Td

Simplifying, we can solve the equation as ln 2 = rTd

.

The length of time require to double a quantity growing at

a rate of r % is about equal to 70 divided by r%.

DOUBLING TIME
It took about 300 years for the worlds
population to increase from 0.5B to 4.0 B.
If we assume exponential growth at a
constant rate over a period of time,
what would that growth rate be? Do this
example first with a calculator then with
the rule of thumb suggested.

EXAMPLE


SOLUTION
 When the rate of decrease of a quantity is
proportional to the amount present,
exponential growth becomes exponential
decay.
Exponential decay can be expressed as:

K is the reaction coefficient, is the initial

amount and N is the amount at time t.

HALF-LIFE
 Number of Growth Factor
Doublings (n) ( )
1 2
2 4
3 8
4 16
5 32
10 1024
20 1.05 x
30 1.07 x

EXPONENTIAL GROWTH FACTORS FOR

NUMBER OF DOUBLING TIME
 Half-life,
relative to exponential decay, is
the point at which half of the material has
been consumed.
N = /2
/

When simplified,

RELATION TO HALF-LIFE
 If we start with a 1.0-Ci radon-222 source, what
would its activity be after 5 days? The half-life for
radon-222 decay is 3.8 days.

Solution:
/

EXAMPLE
 The curve below shows the typical growth rate
of bacteria and its complexities.

lag exp growth stationary death

Time

POPULATION GROWTH
 Populationgrowth projections can also be
mathematically modeled with a logistic or S-
shaped (sigmoidal) growth curve with an
exponential growth phase while conditions for
growth are optimal, followed by slower and
slower growth as the population nears the
carrying capacity of the environment.

LOGISTIC GROWTH
 If N is the population size, K is the carrying capacity of the
environment and r is the exponential growth rate, the
following equation applies.

When N is less than K, rate of change of population is

proportional to the population size or population grows
exponentially with a growth rate r.
As N increases, the rate of growth slows down, and as N
approaches K, stops altogether.

The factor is called the environmental resistance.

 As growth increases, the resistance to further
growth increases and solving for our equation
yields:
where t* is the population at
half the carrying capacity, where N = K/2.

At t = 0, we find t* as

No is the population at t=0.

 To find growth rate r, we introduce Ro, the
instantaneous rate of growth at t = 0.

 Assume that the human population follows a logistic

growth curve until it stabilizes at 15 billion. In 1995, the
population was at 5.7 billion with a growth rate of 1.5%.
When would the population reach 7.5 billion? 14 billion?
What would be our projected population now (2016)?
If
our targeted population for 2020 is 9 billion, will we be
able to achieve it at this growth rate?

EXAMPLE
 Given K = 15.0 B, Ro = 1.5% or 0.015, No = 5.7 B
.
, , ,
, , ,

Time required to reach 7.5 B (half of K)

, , ,

years
. , , ,
To reach 14 B:

SOLUTION
 At this time (2016), t = 21 years
, , ,
. )

In 2020, t = 25 years
, , ,
. )

No, unless growth rate increases.

 The logistic curve can also be useful in getting the maximum
sustainable yield (MSY) of an ecosystem.
This is the maximum rate at which individuals can be
harvested or removed without reducing the population size;
e.g. harvesting fish from a pond.
If the pond is at its carrying capacity, there will be no
population growth and any fish removed will reduce the
population.
The MSY corresponds to a population size less than the
carrying capacity and is calculated as the point on the
curve where the slope is at a maximum.

MAXIMUM SUSTAINABLE YIELD

 Yield = slope =
Setting the derivative of the slope to 0:

If we let N* be the population at the maximum yield point, then

or MSY can be obtained when the population is
half of the carrying capacity.

Maximum yield can be found Yield = which in
terms of current growth rate can be expressed as

SLOPE OF THE CURVE

 Observations of a pond newly stocked with 100 fish
shows their population doubling every year for the first
year or two, but after many years, their population
stabilizes at 4000 fish. Assuming a logistic growth curve
what is MSY of this pond?

Given data: Td = 1 year; K = 4000 fish; No = 100 fish

EXAMPLE
 Initialgrowth rate Ro can be calculated from doubling time
Td equation:

Maximum yield is:

.

Or, assuming that r ~ Ro, and that population size is highest

at half of the carrying capacity
Max yield =

SOLUTION
 1. Around 10,000 years ago, the worlds population
was estimated at 5 million. What exponential rate of
growth would have resulted in the population in 1850,
which was estimated at 1 billion? Assuming growth at
the same rate, what would have the population been
in the year 2000? Compare it with the actual figures for
world population at 6.1 billion in 2000.

PROBLEM SET (PLEASE ANSWER PER

GROUP)
 2.
Tuition fees in most universities in the
Philippines grew from PhP100 per unit in 1970
to PhP2,000/unit at the present. What
exponential rate of growth characterized that
period of time? If the same rate continues,
what is the average tuition fee you would be
paying for your children 20 years from now?
 3. World reserves for chromium are about 800
million tons and the current usage is at 2 million tone
per year. If the growth in demand for chromium
increases exponentially at a constant rate of 2.6%
per year, how long would it take to use up the
current reserves?
Ifthe total resource is 5 times the current reserves,
and the use rate continues at the same rate, how
long would it take to use up the total resource?
 4.
Human population is assumed to grow from 6.3 B in
2000 to an ultimate population of 10.3 B following a
logistics curve growth. Assuming a growth rate of 1.5% in
2000, when would the population reach 9.0 B? What
would the population be in 2050? How long would it take
to reach the ultimate population stated?
 5.In 1970, there were 3.65 B people and the
growth rate was 2.0% per year. If a steady-
state population of 10.3 B is used, what would
the projected population have been for1995
and 2025?
 6.A lake has a carrying capacity of 10000 fish.
At the current level of fishing, 2000 fish per year
are taken and the fish population seems to
hold firmly at a steady rate of 4000. If you
wanted to maximize the sustainable yield,
what would you suggest in terms of population
size and yield?
 7.
Bismuth 210 has a half-life of 4.85 days. If we start of
with 10 gm of it now, what would be left in 7 days?
 8.If sewage drifting down a stream decomposes with
a reaction rate coefficient of 0.2/day, what would be
the half-life of this sewage? How much would be left
after 5 days?
 9.
World population in 1850 has been estimated to have
been about 1 B people. It reached 4 B in 1975.
A.
Using the doubling time approximation, estimate the
exponential rate of growth that would produce those
numbers.
B.Use the exponential growth equation to find the
growth rate.
C.
Compare the values from B and C and write a short
comment.
 10. in India, the population in 1985 was estimated at
around 762 M. In 1995 it was found to be at 931 M.
Estimate the growth rate if a logistic curve was
followed? If the worlds population is estimated to be
at 7.5 B in 2015, what percentage would Indias
population be assuming no change in its population
growth rate exists?
 Pleasesubmit your problem set on August 22 on or
before 4 pm by email.
Usethe word format in preparing the answers but
submit in pdf format, with the file name in the following
format: PS082217(Group Name).pdf
Example: PS082217TeamBukto.pdf
Write
your group members names in the front sheet
please.
Individual submissions will NOT be accepted and only
one (1) file per group will be accepted and the first file
submitted based on the time stamp in the email will be
graded.