Hazardous Waste Management, 2nd ed.

Instructors Manual Chapter 9 Physicochemical Processes

Chapter 9
(continued)

9 -10. 200 mL of a solution with a para-xylene concentration of 500 mg/L is placed

in each of six containers with activated carbon and shaken for 24 hours. The
samples are filtered and the concentration of p-xylene measured, yielding the
following analyses:

Container: 1 2 3 4 5 6
Carbon (grams): 24 20 16 12 8 4
p-Xylene (mg/L): 10.7 14.6 23 29 48 107

Determine the Freundlich constants, K and n, and plot the isotherm.

Sample Volume, V = Liters 0.2

Initial Concentration, Ci = mg/L 500

M Cf X=(Ci-Cf)V Cf X/M Log(X/M) Log Cf

(grams) (mgL) (mg) (mg/L) (m/g)
24 10.7 97.9 10.7 4.1 0.61 1.03
20 14.6 97.1 14.6 4.9 0.69 1.16
16 23 95.4 23 6.0 0.78 1.36
12 29 94.2 29 7.9 0.89 1.46
8 48 90.4 48 11.3 1.05 1.68
4 107 78.6 107 19.7 1.29 2.03

REGRESSION ANALYSIS ON Log X/M vs. Log Cf:

1/n = Slope 0.698058 -0.129959 Constant Log K
Std Error 0.031947 0.0476593 Std Error of Constant
R-Squared 0.991692 0.0258649 Std Error of y
F 477.4435 4 d.f.
SS reg 0.319406 0.002676 SS residual

K= 0.74 mg/gram
1/n = 0.698

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Hazardous Waste Management, 2nd ed. Instructors Manual Chapter 9 Physicochemical Processes

Adsorption Isotherm

X/M (mg/gram) 100

10

1
1 10 100 1000

Effluent Concentration (mg/L)

9 -11. Estimate the daily carbon utilization to remove chlorobenzene from 1.0 MGD of
ground water saturated with chlorobenzene. Assume a chlorobenzene concentration of
5 mg/L is acceptable for discharge to a POTW.
Given:
Contaminant = chlorobenzene [C6H5CI]
Final concentration of chlorobenzene (Cg) = 5 mg/L
Saturation = 500 mg/L (Appendix A)
Density = 1.107 at 20
Initial concentration = 500 mg/L

From Appendix A, for chlorobenzene, K = 91, l/n = 0.99

X 1
= kC f n = 91C f
0.99
where Cf is the final concentration.
M

Freundlich equation:
Since Cf = 5 mglL

X = 91 x 5 0.99 = 447. 73 mg Chlorobenzene/g Carbon = 0. 448 g Chlorobenzene/g Carbon

M

Carbon required = 0.448 g/g = 0.448 lb/lb

gal (500) mg 10 6 L
Chlorobenzene removed = 1 10 8.34 lb = 4128.3 lbChlorobenzene
6
day L mg gal day

Carbon required = 4128.3 lb Chlorobenzene/day = 9214.96 lb/day = 4. 6 tons/day

0.448 1b Chlorobenzene/lb Carbon

The density of chlorobenzene is greater than that of water. Hence Chlorobenzene can be considered as a
DNAPL and hence might be considered as a continuous source of contamination.

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9-12. Provide a preliminary design of a carbon adsorption system for removal of 2, 4, 6

trichlorophenol from 250,000 gal/day of water. The following data is provided:

Bohart-Adams Model: a = 2.3 days/ft; b = -10 days in laboratory. tests where trichlorophenol concentration was
reduced from 395 mg/L to 10 mg/L at a loading of 4.0 gal/ft2 min. The adsorption zone was 19.0 feet.

Given:

Contaminant = 2, 4, 6 trichlorophenol
water, Q = 250,000 gal/day
Bohart-Adams Model:
a = 2.3 days/ft
b = -10 days
Cin = 395 mg/L
Cout = 10 mg/L
Loading = 4.0 gal/ft2 min = V
AZ = 19.0 ft

Solution:

1. Height of Adsorption Zone = 19.0 ft = 5.79 m = 5.8 m

2. Number and Size of Units:

AZ 5.8
n = + 1 = + 1 = 3.52
d 2.3

No. of Units = 4 columns

Area of lab columns = 2.043 x 10-3 m2 (3.14in2)
Loading rate in laboratory columns = 4.09 gal/ft2 min
Applying the same loading rate for the full scale units

250,000 gal 1day

3

Q 3.7854 103 m hr
day gal 24hrs 60 min
A= = 2
= 4.03m 2 = 43.37 ft 2
V 4 gal 3 1 ft
3.7854 103 m
ft min
2
gal 9.2903 10 2
m2

3. BDST equation for 90% removal

Slope a = 2.3 days/ft = 7.52 days/m
Intercept b = -10 days
Equations of line: t = 7.52 x -10
1
Velocity of absorption zone = = 0.133m / day = (0.434 ft / day )
a
1
Carbon Utilization = Area UnitWeight
a
= 4.03 x 0.133 x 481 = 257.81 kg/day (5681bg/day)

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9-13. A ground water aquifer is contaminated with benzene. Contrast the relative effectiveness of
air stripping to activated carbon adsorption by providing a preliminary design of each
process.

[Note to instructors: This is a very open ended question that requires students to make and justify assumptions. We
have provided examples of the type of solutions that might be expected from advanced students. We also find it
helpful to discuss the problem with students before assigning it!]

Given Contaminant: Benzene

Water solubility - 1780 mg/L, M.W. - 78.11, Melting point - 5.5C, Boiling point - 80.1C,
vapor pressure - 95.2mm @25C, vapor density - 2.77, specific gravity - 0.8786 @20/4C,
Chemical formula C6H6, Diffusion coefficient - 0.09234 cm2/s

Constants for Henry's constant: A = 5.53, B = 3190, Koc = 83 ml/g.

Data from Appendix A, page 1040-41 of text book and from Verschueren, Karel: Handbook of Environmental Data
on Organic Chemicals - Second edition, 2nd edition Van Nostrand Reinhold Co., Inc., New York, NY

Solution:

Assumption: The groundwater is saturated with contaminant at the source.

As no information is given regarding the concentration of the contaminant, One approach would be to consider the
water at the source to be saturated with benzene. A second possible assumption that the level is below saturation,
say 150 mg/L.

From the above properties it is observed that the water solubility of benzene is 1780 mg/L.

In order to obtain a detailed information regarding the extent of the plume, first the site history and geology would
have to be reviewed. Both indirect and direct methods are employed to investigate subsurface conditions. (See
Chap. 15)

Indirect methods include different geophysical methods like electromagnetic induction, earth resistivity, ground
penetrating radar, magnetic techniques and seismic refraction and reflection. These geophysical techniques are
employed to decut the parameters of interest. Direct methods are employed to verify the interpretations of
geophysical methods. Boring, sampling and testing are direct field methods of subsurface exploration. These
techniques includes installation of ground water monitoring wells.

Soil gas surveys are performed to investigate the distribution and transportation of contaminants in the subsurface
zone. Soil gas surveys establish a vapor phase plume in the void space of the soil in the vadose zone. This
information can then be interpreted in the context of source detection and plume delineation. They have been used
as a low cost alternative to ground water sampling and testing to assess the nature of the ground water plume.

Sampling is done and the gas is analyzed by using different instruments like organic vapor analyzer, a
photoionization detected and gas chromatography. The plume migration would be as shown in figure 15-31 on page
941 and figure 4-18(b) in page 165.

Considering that the water is saturated with benzene at source with 1780 mg/L, the concentration is too high to use
air stripping. (Air stripping is not effective for concentrations greater than 200 mg/L.) Therefore carbon adsorption
would be the more suitable method for treatment where the concentrations is greater than 200 mg/L.
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Comparison of two treatment methods

Consider a point where the concentration of benzene is 150 mg/L and the concentration has to be reduced to 130
g/L for discharge to a POTW. (Note: another reasonable value for the effluent requirement would be 5 g/L, the
maximum contaminant level (MCL) under the safe drinking water act. This lower limit would be difficult to achieve
by either method.

AIR STRIPPING:
The following data is obtained for the above contaminant:
1. KLa = 0.015 sec-1 (from example 9-1, p. 453), flow rate = 50,000 gal/day = 2.19 L/sec, temperature = 15C, from
appendix A Henrys Constant can be obtained as follows
At 25C, A=5.53, B= 3.19x 103

5.58 3.1910
3
B
A
H = e =e = 0.00566atm m 3 / mol = 5.66 10 3 atm m 3 / mol
T 298

Assumptions : column diameter = 2.5 ft (0.765m)

Air to water ratio(QA/QW) = 50
Determine: Liquid loading rate, L
Stripping factor, R
HTU, NTU and height of packing column
Solution
From Eqn.3-7:
H 5.66 10 3
H = = 5
= 0.231
1. Liquid loading rate RT 8.205 10
298
Cross-sectional area of the column = 0.7652 = 0.459 = 0.46m 2
4
mass rate = 1.0 Kg/L x 2.19 L/sec = 2.19 kg/sec
mass loading = 2.19 / 0.46 = 4.76 Kg/secm2
L = (4.76 kg/secm2) x (103 g/kg) x (1/18 mol/g) = 264.5 mol/secm2)
2. Stripping factor: R =
Q
H A = 0.231 50 = 11.55(dim ensionless )
QW
3. Height of transfer units: HTU = L
MW K La
Mw = 55.6 mol/m = 55.6 x 10 mol/m3
3 3

4. Number of transfer units:

C in (R 1) + 1)

R C out
NTU = ln
R 1 R

11.55
=
(
150000
130
)
(11.55 1) + 1)
= 7.62transferunits
ln
11.55 1 11.55

5. Height of packing in column Z:

NTU x HTU=7.62 x 0.317 = 2.416 m = 2.42 m

Adding a factor of safety of 20%, the height of the packing

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=2.42 x 1.2= 2.902 m = 8.88 ft = 9ft

Use Z = 9 ft

CARBON ADSORPTION METHOD:

100 mg/L of a 150 mg/L solution of benzene are placed in each of five containers with different amounts of
activated carbon and shaken for 48 hrs. The samples are filtered and the concentrations of benzene
measured, yielding the following analysis:

Container 1 2 3 4 5
Carbon (mg): 600 400 200 100 50
Benzene (mg/L): 5 20 45 96 130

Initial Contaminant: CI = 150mg/L, Volume = 0.1 liter

The Freundlich constant, K and n can be obtained in the following manner:

M(grams) Cf(mg/L) X=(Ci-Cf)V(mg) X/M (mg/g) Log10(X/M) Log10(Cf)

0.6 5 21.75 36.25 1.56 0.698

0.4 20 19.5 48.75 1.687 1.30
0.2 45 15.75 78.75 1.896 1.653
0.1 96 8.1 81 1.908 1.982
0.05 130 3 60 1.778 2.11

Regression analysis on the last two columns yields:

slope 0.212950778 1.43598459 constant
STD Error 0.083441887 0.13615356 STD error of constant
R-squared 0.684646617 0.09520355 std error of y
F 6.513137194 3 degrees of freedom
ss Reg 0.059033227 0.02719115 sum of squares of residual

The following is a plot of Log(X/M) vx. Log (Cf):

K = 101.435 = 27.22 , 1/n = 0.21

Hence using the adsorption Isotherm for 50,000 gal/day of water contaminated, the daily carbon required is
The cost of air stripping and carbon adsorption can be compared through contact with venders and the most cost
effective method employed for treatment.

The software ReOptTM can be used to compare the two alternatives. (Reference: White, M. K. and Bryant, J. C.
ReOptTM V.2.1, Pacific Northwest Laboratory operated by U.S. Department of Energy by Battelle Memorial
Institute, June 1993.) The engineering and design parameters for Carbon adsorption are:

Adsorption Isotherm
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ram)

100
Hazardous Waste Management, 2nd ed. Instructors Manual Chapter 9 Physicochemical Processes

Parameter Value

Regeneration of activated carbon on-site regeneration practical for carbon usage > 1000 lb/day

Adsorbent lifetime Activated carbon losses per regeneration cycle are typically 3 to
8%. Activated carbon loses about 25% of its virgin adsorption
capacity to new steady state capacity in about 3 cycles.

Maximum activated carbon 800 C to 975 C.

regeneration temperature

Capacity 15 to 100 gal/min capacities reported for activated carbon.

Hydraulic loading 0.25 to 2.5 gal/min/ft3 for activated carbon

Linear Flow Rate 0.4 to 3 gal/min/ft2 for activated carbon column cross sectional
area

Column dimensions bed depths range from 8 to 40 ft and column height: diameter
ratio is typically 2:1 for activated carbon

Both carbon adsorption treatment and air stripping can be used for a wide range of contaminants like most
Halogenated compounds, nitrated aromatics and aliphatics, heterocycles, non-halogenated aromatics and other
non-halogenated compounds. But this method cannot be applied to non-volatile metals like alkali metals, to most
anions containing metals, volatile metals, other inorganics and radionuclides. The date required for carbon
adsorption are:

Data Requirement Purpose

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Flow rate Needed to size system

Contaminant identity and For determining feasibility of technology and selecting

concentrations candidate adsorbents.

Adsorption isotherms for Available from the literature; used for screening candidate
contaminants adsorbents and for determining optimum pH and
temperature of solution.

Column test Bench-scale test needed for designing a full system

including data on adsorbent usage rates and competitive
adsorption effects.

A detailed description of carbon adsorption system can be obtained from following references:

1. Weber Weber, W. J., Physicochemical Processes for Water Quality Control,

John Wiley and Sons Publishing, New York, 1972.

2. Faust and Aly Faust, S. D. and Aly, O. M., Adsorption Processes for Water Treatment,
Butterworth Publishers, Boston, 1987.

3. Corbitt Corbitt, R. A., Standard Handbook of Environmental Engineering,

McGraw-Hill Publishing, New York, 1990.

4. Breton et al. Breton, M., P. Frillici, S. Palmer, C. Spears, M. Arienti, M. Kravett, A.

Shayer, N. Suprenant 1988. Treatment Technologies for Solvent
Containing Wastes, Noyes Data Corp., Park Ridge, NJ.

5. De Renzo De Renzo, D. J., 1978. Unit Operations for Treatment of Hazardous

Industrial Waste, Noyes Data Corp., Park Ridge, NJ.

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The engineering and design parameters for air stripping are:

Parameter Value

Water flow rates for single tower Dependent on the solution matrix. Typically used for a
contaminant range between 10 and 10,000 ppb VOC.

Contaminant range 10 - 40 ft.

Water inlet temperature 50 - 75 degrees F

Nominal packing size 0.5 - 3 in diameter

Range of hydraulic loading rates 10 - 30 gpm/ft2 (higher rates tend to flood the tower)

Air flow/motor power relationship 4000 cfm with 10 HP

Stripping efficiency Strongly dependent on contaminants, stripping conditions,

and column design. The efficiency can be up to 99.999%
with less than 100 ppm contaminants.

Materials of construction Fiber-reinforced plastic, PVC, or aluminum.

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The data required for air stripping are:

Data Requirement Purpose

Water characterization Required to select air stripping as an applicable technology,

to design the stripping unit, and to determine the
effectiveness of the technology.

Required removal efficiency Needed to determine stripper size and operation time.
These values should be determined from the least volatile
component.

Henry's law coefficient and liquid Required to estimate mass transfer rates which are used to
and gas phase diffusion coefficients determine the unit size, and air flow rate.
for each compound

Required water flow rate In combination with other parameters this determines the
size of the stripping tower.

Water temperature Required to estimate the operating temperature of the

tower. The tower temperature affects the design of the
stripping unit.

Air temperature Required to estimate the operating temperature of the

tower. The tower temperature affects the design of the
stripping unit.

Inorganics in water Affects removal efficiency; especially need to know iron

and carbonate content since these can cause fouling of the
air stripping unit.

Water pH Determines need to adjust pH to enhance stripper efficiency

and/or reduce corrosion.

A detailed description of air stripping can be obtained from following references are:

1. Byers, W. D. Byers, W. D., 1990; "Air Stripping Technology", in Physical and

Chemical Processes, Innovative Hazardous Waste Treatment
Technologies Series, ed. H. M. Freeman, Technomic Publishing
Company.

2. CH2M Hill CH2M Hill, 1987, "Cost of Remedial Action Model. Users Manual",
EPA Contract 68-01-7090, Version 2.1, CH2M Hill, Portland, OR, June
1988, pp. 3-149 to 3-154.

3. Derammelaere Derammelaere, R., and Helgerson, R., 1990, "Integrated Zero-Emission

and Helgerson Groundwater and Soil Remediation Facility at Lockheed, Burbank, "Proc.
HAZMACOn 90, Vol. II, 256-266, April 17-19, 1990, Anaheim, CA;
Eds. T. Bursztynsky and M. L. Loss.

4. Holden et al. Holden, T., Newton, J., Sylvestri, P., Diaz, M., and Baker, C., 1988,
"Technology Screening Guide for Treatment of CERCLA Soils and
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Hazardous Waste Management, 2nd ed. Instructors Manual Chapter 9 Physicochemical Processes

Sludges", EPA/540/2-88/004, Sept. 1988, p. 85.

5. Weston Weston, Roy F., Inc., 1986, "Pilot Investigation of Low-Temperature

Stripping of Volatile Organic Compounds (VOC's) From Soil: Volume I -
Technical Report and Volume II - Appendices", USATHAMA Tech.
Report, June, 1986, p. 123.

The other technologies which can be used for benzene are:

Aerobic Biological Treatment Liquid-Liquid Extraction

Anaerobic Biological Treatment Media Filtration
Catalytic Destruction Neutralization
Coagulation and Flocculation Oil-Water Separation
Freeze Crystallization Oxidation
Gravity Separation Photolysis
Liquid Adsorption Pyrolysis

A detailed description of the above technologies can be obtained from ReOptTM Software.

9-14. Using the information in Example 9-6, determine the Bohart-Adams coefficients N and K.

Given:
From Example 9-9:
V = 0.245 m3/m2 min
a = 6.34 days/m; b = -7 days
Cin = 89 mg/L; Cout = 8.9 mg/L

Solution:
F1 N
N is obtained by the equation. a=
CinV

aCinV
= 6.34 days 24 hr 89 mg 0.245 m 2
3
N= 60 min
F1 m days L m min hr

= 199070.93 mg = 199070.93 mg 1Kg = 0.199 0.2 Kg

m3 m3 (1000 1000)mg m3

"K" is obtained by the equation Cin

F2
b = KC
ln 1

in
Cou t




C 89
F2 ln in 1 ln 1

ou t
C = 8.9
K= = 0.001469 L
Cin b mg hr
89 mg 7days 24 hrs
L day
3
0.0001469 L 10 3 m
= L = 0.147 m 3
6 Kg Kg hr
mg 10
mg hr

N = .02 Kg/m2, K = 0.147 m3/Kghr

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9-15. Revise Example 9-6 for a flow rate of 250,000 gallons per day.
Given:
Water flow rate = 250,000 gal/day
concentration Cin = 89 mg/L
Cout = 8.9 mg/L
Height of the column, d = 2.3 m (7.5 ft)
Diameter of the column = 0.051 m (2 in)
Flow rate = 0.5 L/min (190.2 gal/day)
Unit weight of column = 481 Kg/m3

Solution:
1. Height of adsorption zone, AZ = 2.5 m (8.25 ft) (from Fig. 9.20)
2. Number and size of units AZ 2.5
n = + 1 = + 1 = 2.09
d 2 . 3
Therefore number of units = 3 columns

Area of Lab columns = (0.051) 2 = 2.043 10 3 m 2 (3.14 in2)
4
Loading rate in laboratory columns:

(
V = 5.0 10 4 m
3

min
)/(2.043 10 3
m 2 ) = 0.245 m
3

m 3 min (6.14 gal/ft2min)

Using the same loading rate for the full scale unit yields
day hr
Area = Q = 250,000 gal
3
3.7854 10 3 m
V day 24hrs 60 min gal

3
= 0.245 m = 2.682m 2 (8.8 ft2)
m min
2

Diameter = 3.414 m (11.2 ft)

3. BDST equation for 90% removal (use curve for 10% of feed concentration in Fig. 9.20)

Slope: a = 5.8 days/0.91 m = 6.34 day/M (1.93 days/ft)

for flow rate = 250,000 gal/day

V 55000 days
a = a = 6.34 = 1.39 = 1.4
V 250000 m (1.93 days/ft)

Intercept: b = -7 day
Equation of line: t =1.4X - 7

1
Velocity of adsorption zone = = 0.716 m
a day

Carbon utilization =

Area
1
unitweight = 0.59m 2 0.716 m 481 kg 3 = 203.19 kg 447 lb
a day m day
day

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9-16. Revise Example 9-6 for a contaminant concentration in ground water of 239 mg/L.
Given:
Water flow rate = 55,000 gal/day
Concentration, Cin = 239 mg/L
Height of the column, d = 2.3 m (7.5ft)
Diameter of the column = 0.051 m (2 in)
flow rate = 0.5 L/min (190.2 gal/day)
Unit weight of column = 481 kg/m3
Assumptions:
Concentration, Cout = 23.9 mg/L (90% removal)

Solution:
1. Height of the adsorption zone, AZ = 2.5 m (8.25 ft) (from fig. 9.19)
AZ 2.5
2. Number and size of units, n = + 1 = + 1 = 2.09 m
d 2.3
Therefore number of units = 3 columns

Area of Lab columns = (0.051) 2 = 2.043 10 3 m 2 (3.14 in2)
4
Loading rate in laboratory columns

V = ( 5.0 x 10-4 m3/min) / (2.043 x 10-2 m2)=0.245 m3/m2min(6.14 gal/ft2min)

Using the same loading rate for the full scale yields
Q 0.145m 3 / min
Area = = = 0.59m 2
V 0.245m / m min
3 2

Diameter = 0.867 m (2.84 ft)

3. BDST equation for 90% removal (using curve for 10% of feed concentration in Fig.9.20)
Slope a= 6.34 days/m

Using Equation 9-41:

Cin 89
a = a = 6.34 = 2.36days / m
Cin 239

Intercept: b = -7 days

C

Cin
ln in 1
C out 89 ln
239
23.9
1 {( ) }
b = b
Cin

Cin
ln
Cout

1
= 7
239

ln 89
8.9
1 {(
= 2.6days
) }

Intercept: b' = -2.6 days

Equation of line: t = 2.36 X - 2. 6
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Velocity of adsorption zone = 1 / a = 1 / 2.36 = 0.423 m/day (1.3 ft/day)

1
Carbon utilization = Area unitweight
a

= 0.59 m2 x 0. 423 m/day x 481 kg/m3 = 120 kg/day (264 lb/day)

Probelm 9-16 TOC

X/M (mg/gram)

1000
100
10
1
1 10 100 1000
Effluent Concentration (mg/L)

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9-17. Derive the conversion factors F1 and F2 in the Bohart-Adams model.

F1 N
(i) a= (Equation 9-34)
CinV
(a) For metric units
a = hr/m, N = Kg/m3 Cin = mg/L V = m/hr
Substituting the units on the RHS of the equation

Kg 10 3 m
Kg L hr
3 Kg L hr
= m = 3 = = = L
6
= 10 3 hr
mg m m mg m 10 Kg m
m 4 mg
L hr mg
which is equal to LHS of the equation (hr/m) F1 = 10 for metric units.
3

(b) For US customary units

a = hr/m
N = lb/ft3
Cin = mg/L
V = gal/min. ft2
Substituting the units in the equation (1) on RHS

lb
ft 3 lb L min ft 2
= = 3
mg gal ft mg gal

L min ft 2

= 6552.3 hr/m = 1998 hr/ft F1 = 1998 for English units.

F2 Cin 1
(ii) b=
K C
ln
in C ou t
(a) For Metric units: K = m3/Kg hr , Cin = mg/L
Substituting the units in the equation (2) on RHS F2 =103

mg K = ft
3
m3
L 10 3
1
ln
L 1 = Kg
lb hr
hr

L
=
Kg hr
L
3 mg 3
m3 6 Kg
m

mg m mg
mg 10

L

Kg hr L mg
(b) For US Customary units: Cin = mg/L
Substituting the units

1 Cin lb hr L
3
ln
1
= 3

ft

mg Cout ft mg
lb hr L

Kg m3
lb 0.4536 hr L 10 3
lb L
3
6 Kg
ft (0.3048)
3 m
3
mg 10
ft 3 mg
F2 = 16,025 hr

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9-18. Derive a simplified Nernst equation (Eq. 9-54) from Eq. 9-51.

Nerst Equation : E = E RT ( nF
)ln Q
where
E = standard electrode potential (Volts)
R = gas constant = 1.98 x 10-3 Kcal/gmolK
T = temperature (K)
n = number of electrons exchanged during the reaction per gmol
F = Faraday constant = 23.062 Kcal/(Voltequiv)

Substituting the above values in Nernst Equation and taking temperature = 25C = 298K

1.98 10 3 298 0.0256 0.0256 2.303

E = E ln Q = E ln Q = E log10 Q
n 23.062 n n

(conversion factor from ln to log = 2.303)

E = E - (0.059/n) log10Q which is equation 9-56.

9-18. A plating waste with a flow of 50 L/min contains 274 mg/L of NaCN. Determine the amounts
of chlorine as Cl2 and NaOH required to:

(a) Oxidize the cyanide to cyanide; and

(b) Oxidize the cyanide to CO2 and H2O.

Amount of NaCN = 274 mg/L

Molecular Weights: CN- : 26; Cl2: 70.9; NaOH: 40;

Solution:
The conversions of CN- to CO2 and H2O occurs through eqns 9-64 and 9-67.
Mass of NaCN required daily = 50 L/min x 274 mg/L =13700 mg/hr =19.73 kg/day

1) Oxidation of Cyanide to Cyanate.

From eqn. 9-64, the required molar ratio OCl- / CN- = 1
Based on Eqn. 9-62, C12 / OC1- = 1

the molar ratio Cl2 / CN- = 1 and the mass ratio Cl2 / CN- = 1 x 70.9 kg/kg
2.73
The mass of Cl2 required per day is 19.73 kg/day x 2.73 kg/kg = 54 kg/day
The mass of chlorine required = 54 kg/day
Mass of NaOH required daily = none according to eq. 9=64.

2) Oxidation of cyanide to CO2 and H2O

Step 1 - As calculated above, 54 kg/day of Cl2 are required.

Step 2 - From eq. 9-67, the molar ratio Cl2 / CNO- = 3 = 1.5 and the mass ratio is
2

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Hazardous Waste Management, 2nd ed. Instructors Manual Chapter 9 Physicochemical Processes

The mass of Cl2 required daily is 19.73 x 4.09 = 80.69 = 81 kg/day

Total mass of Cl2 required = 54+81=135 kg/day
Total mass of NaOH required daily = ??

Step 1 - none 4
=2
Step 2 - From eq. 9-67, the molar ratio NaOH/CNO-, 2

and from eq. 9-64, the molar ratio CNO-/CN- = 1.

40
the molar ratio NaOH / CN- = 2 and the mass ratio NaOH / CN = 2 = 3.08kg / kg
26

The mass of NaOH required daily is 19.73 kg/day x 3.08 kg/kg = 60.77 = 61 kg/day
Total mass of NaOH required = 61 kg/day.

9-19. A plating waste with a flow of 40,000 gal/day contains 274 mg/L of NaCN. Determine the
amounts of chlorine as Cl2 and NaOH required to oxidize the cyanide to CO2 and N2.

Amount of Plating Waste = 40,000 gal/day

Amount of NaCN = 274 mg/L

Solution:
Amount of NaCN required daily = 40, 000 gal/day x 274 mg/L
40,000 gal 37854 L / gal 274mg 10 6 kg / mg
= = 41.48kg / day
day L
Step l: To oxidize to cyanate

From eqn. 9-64, the required molar ratio OCl- / CN- = 1

Based on eqn. 9-62, Cl2 / OCl- = 1

the molar ratio Cl2 / CN- = 1 and the mass ratio Cl2 / CN-

1 709
= = 2.73kg / kg
26

The mass of Cl2 required per day is 41.48 x 2.73 =113.26 =114 kg/day

Step 2: Oxidation of Cyanide to CO2 and N2

From eqn. 9-67, the molar ratio Cl2 /CNO- = 3 = 1.5 and the mass ratio is 1.5 x 70.9 = 4.09 kg/kg
2 26

The mass of Chlorine required daily is 41.48 x 4.09 =169.7 =170 kg/day
Total mass of chlorine required = 114 + 170 = 284 kg/day
Total mass of NaOH required daily is

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Step 1: None
Step 2: From eqn. 9-67, the molar ratio NaOH / CNO- 4 = 2, and from eqn. 9-64, the molar
2
ratio CNO- / CN- = 1
the molar ratio NaOH / CN- = 2, and the mass ratio NaOH / CN- = 2 x 40 = 3.08 kg/kg
26
The mass of NaOH required daily is 41.48 x 3.08 =127.78 =128 kg/day
Total mass of NaOH required = 128 kg/day.

9-20. Demonstrate that reactions 9-63 and 9-64 are equivalent to reaction 9-62.

Equation 9-63
NaCN + Cl2 CNCl +NaCl
Equation 9-64
CNCl + 2NaOH NaCNO + H2O + NaCI

Solution:
Equation 9-62 can be written as
CN- + Cl2 CNCl + Cl- Note: Cl- is the chloride ion - it is not an oxidant.
Equation 9-66 can be written as
CNCl + 2OH- CNO- + H2O + Cl-

Combining both equations:

CN- + Cl2 CNCl + Cl-
CNCI + 2OH- CNO- + H2O + Cl-

CN- + Cl2 + 2OH- CNO- + H2O + 2C1- (1)

But chlorine in aqueous medium gets converted to hypochlorous acid solution (eqn 9-62).
(1) can be written as
CN- + HOCl + OH- + Cl- CNO- + H2O + 2Cl-

or CN- + OCl- + H2O CNO- + Cl- + H2O

CN- + OCl- CNO- + Cl- which is equation 9-64.

9-22. An industrial waste stream contains 650 mg/L of hexavalent chromium at a

flow rate of 35 L/min. Determine the amount of sulfur dioxide required to
reduce the chromium to the less toxic trivalent form.

Atomic weights: S: 32; Cr: 52; 0:16

From Table 9-8, page 509:
3SO2 + 3H2O 3H2SO3
2CrO3 + 3H2SO3 Cr2 (SO4 )3 + 3H2O

3SO2 + 2CrO3 Cr2 (SO4 )3

This implies that 1.5 moles of sulfur dioxide is required for 1 mole of Chromium.
The total mass of Chromium discharged daily is:
mg 1g 1kg L 60 min 24hr
= 650 35 2001Environmental
Resources
= 32.Management
76kg / day
L 1000mg 1000 g min 1hr 1day
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Kg moles of Chromium discharged daily =

32.76kg / day
= 0.63kg mol / day
Sulfur dioxide required daily 52kg / kg mol
= 1.5 x 0.63 = 0.945 kg mol SO2 x 64 = 60.48 kg/day

Hence 60.5 kg/day of SO2 is required (Stoichiometric)

On a practical level, at least 10% mole SO2 would be required yielding a daily utilization of 67 kg of SO2.

9-23. A waste contains 150 mg/L of copper at a flow rate of 75 L/min. Determine
the amount of sodium borohydride required to treat this waste.

Atomic Weights: Cu: 64; Na: 23: B: 11; H:1

NaBH4 + 8Cu+ + 2H2O 8Cu + NaBO2 + 8H+

This implies that 1/8 mole of NaBH4 is required to treat 1 mole of Copper.
The total mass of Copper discharged daily:

mg 1g 1kg L 60 min 24hr

= 150 75 = 16.2kg / day
L 1000mg 1000 g min 1hr day

16.2 Kg / day
Kg moles of Copper discharge daily = = 0.253kg molCU
64kg / kg mol
Sodium Borohydride required to treat this waste
= (0. 253 kgmol CU) x (38 kg/kgmol) = 9.62 kg/day of NaBH4 required (Stoichiometric)

Adding 10% mole of NaBH4 for practical level, the amount of NaBH4 required is 10.6 kg/day.

9-24. A waste contains 250 mg/L of cadmium and 450 mg/L lead at a flow rate of 45,000 gal/day.
Determine the amount of sodium borohydride required to treat this waste.

Atomic Weights: Na: 23: B: 11; H:1, Cd = 112, O = 16, Pb: 207

The following table is from page 7.49 of Fochtman (Reference 65):

Table 7.45 Weight Ratios: Reduced Metal Obtainable from Ionic Species/Theoretical Amount of Sodium
Borohydride
Metal Valence Weight ratio*
Lead Pb2+ 22
Cadmium Cd2+ 12
Mercury Hg2+ 21
Hg+ 42
Copper Cu2+ 7
Silver Ag+ 22
Gold Au3+ 14
Nickel Ni2+ 6
2+
Palladium Pd 11
Platinum Pt4+ 10
Cobalt Co2+ 6
Rhodium Rh3+ 7
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Iridium Ir4+ 10
" Weight ratio = maximum kilograms of metal reduced per kilogram of sodium borohydride.

This implies that 12 Kg of Cd requires for 1 Kg of NaBH4 and 22 Kg of Pb requires for 1 Kg of NaBH4.
mg gal L g
The total mass of cadmium daily = 250 45,000 3.7854
L day gal 1000mg

=42585.75 g/day = 42.59 kg/day

NaBH4 required daily = 42.59 = 3.55 kg/day
12 mg gal L g
The total mass of lead per day = 450 L 45,000 day 3.7854 gal 1000mg

= 76654.35 g/day = 76.7 kg/day

NaBH4 required daily = 76.7 = 3.49 kg/day
22
Total mass of NaBH4 required daily = 7.04 kg/day stoichiometric

9-25. Provide a preliminary design of an electrodialysis unit to treat a plating waste

with the following characteristics: Ni concentrations = 2.1 % as NiSO4; flow
rate = 20 gpm. Determine the number of membranes, power required, and
annual electrical cost @ $0.07/kWh. The effluent Ni concentration must be
less than 500 mg/L.

Given:
Ni concentration = 2.1% as NiSO4
flow rate = 20 gal/min
annual electric cost = $0.07/Kwh
effluent concentration < 500 mg/L

Assumptions:
E1= E2 = 90% = 0. 9
Resistance through unit = 10.5
Current efficiency = 90%
Maximum CD/N ratio = 6000 (A/m2)/(g - equivalent/L)
Membrane area = 1.0 m2
The removal efficiency = 90%
Solution:
Concentration of NiSO4 = 2.1 % = 21,000 mg/L = 21 g/L
Mol. wt. NiSO4 = 154.7
At.wt. of Ni = 58.7
Concentration of Ni = 58.7 (2.1 %) = 0.797% = 7970 mg/L = 7.97 g/L
154.7
(i) Normality:
Equivalent weight of NiSO4 = Molecular weight = 154. 7 g/gmol
g - equivalent/gmol 2 g - equivalent/gmol
= 77. 4 g/g - equivalent
Normality = 21 = 0.27 = 0.27N 77.4

(ii) Maximum current density = 6000 x 0. 27 = 1620 Amp/m2

current = 1620 x 1.0 m2 =1620 Amps

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Hazardous Waste Management, 2nd ed. Instructors Manual Chapter 9 Physicochemical Processes

(iii) No. of cells:

FQN E1
I = but E1 = E2 = 0.9
n E2
Q = 20ga1/min x 0.06308 =1.26 L/sec

Amp sec
96487 1.26 0.27
FQN g equivalent
n = = = 20.26cells
I 1620 Amp

No. of membranes = 2 x 20.26 = 40.5 ~ 44 membranes in 22 cells.

(iv) Power = I2 R = (1620)2 x 10.5 = 27.5 x 106 watts = 27.5 x 103 KW

(v) Annual Electric Cost

= 27.5 x 103 KW x $0.07/KWh x (365 x 24)hr =
$16,897,500 = 16.9 million dollars/year

9-26. Determine if the following mixtures of organics 'in wastewater are good candidates for
steam stripping. State reason. ~ Apply the OCPSF discharge limitations as criteria
for the stream stripper bottoms concentrations.

Mixture A Mixture B Mixture C

93 mg/L benzene 133 mg/L phenol 56 mg/L ethanol

127 mg/L acetone 27 mg/L nitrotoluene 182 mg/L acetone
42 mg/L methanol 158 mg/L methyl ethyl ketone

In Mixture A: Benzene is sparingly soluble in water. Hence steam stripping can be used.
In Mixture B: Nitrotoluene is sparingly soluble in water. Hence steam stripping can be used.
In Mixture C: All are highly soluble in water. Hence steam stripping cannot be used.
Note: Solution to be revised.

9-27. Show, through material balances, that the ratio of liquid to gas (L/G) in the
stripping section of a steam stripper is higher than in the rectifying section.
State any necessary assumptions or given.

9-28. Using the equilibrium curve in Fig. 9-16, and given the following equations
for operating lines:

Stripping sections: y= 1.38x

Rectifying sections: y = 0.05x + 0.39

Use the McCabe-Thiele method to estimate the number of theoretical trays.

Assume: Xb = 0.05; XF = 0.35; X0 = 0.9.

[Note: There was a typographical error in the first printing of the book. The above equation represent the
correct problem]
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The feed tray is at XF = 0.35, i.e., at the operating line.

X Stripping Section Rectifying Section

0 0 0.39
0.1 0.138 0.4507
0.2 0.276 0.5114
0.3 0.414 0.5721
0.4 0.552 0.6328
0.5 0.69 0.6935
0.6 0.828 0.7542
0.7 0.966 0.8149
0.8 1.104 0.8756
0.9 1.242 0.9363
1 1.38 0.997

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