FE Review for Environmental Engineering

Problems, problems, problems Presented by L.R. Chevalier, Ph.D., P.E. Department of Civil and Environmental Engineering Southern Illinois University Carbondale

FE Review for Environmental Engineering

CHEMICAL FOUNDATIONS

Problem

Strategy

Solution

Calculate the molecular weight, equivalent weight, molarity and normality of the following: a. 200 mg/L HCl b. 150 mg/L H2SO4 c. 100 mg/L Ca(HCO3)2

Problem

Strategy

Solution

Use periodic table to get molecular weight Convert mg/L to mol/L Determine n for each compound Apply equations
EW = MW/n N = Mn

Problem

Strategy

Solution
in an Acid/Base reaction, n is the # of hydrogen ions that a molecule transfers

a) 200 mg / L HCl MW ! (1)  35.45 ! 36.45 g mol EW ! 36.45 g equivalent

200 mg L molarity ! ! 0.00549M mg g (1000 g ) .45 mol 36 normality ! 0.00549  ! 0.00549 N 1

Problem

Strategy

Solution

b) 150 mg / L H 2 SO4 MW ! 2  32.06  4 ! 98.06 g mol 1 16 EW ! 98.06 / 2 ! 49.03 g eq 150 mg L molarity ! ! 0.00153M mg g (1000 g ) .06 mol 98 normality ! 0.00153 2 ! .00306 N

Problem

Strategy

Solution
in a precipitation reaction, n is the valence of the element

c) 100 mg / L Ca HCO3 2 MW ! 40  2(1)  2  6 ! 162 g mol 12 16 EW ! 81 g eq 100 mg L molarity ! ! 0.000617 M mg g (1000 g ) 162 mol normality ! 0.000617 2 ! .00123 N

Example

Solution

Convert 200 mg/L HCl to ppm

Example

Solution

200 mg/L = 200 ppm

Problem

Strategy

Solution

a)

Convert 300 ppm Mg 2+ to mg/L as CaCO3

b)

Convert 30 mg/L Mg2+ as CaCO3 to mg/L

Note: MW Mg2+ is 24.31 g/mol

Problem

Strategy

Solution

Determine the molecular weight of the species Determine n Equate EW=MW/n Apply equation

50 mg mg as CaCO3 ! as species EW L L species

Problem

Strategy

Solution

a)

Convert 300 ppm Mg 2+ to mg/L as CaCO3

300 ppm = 300 mg/L EW Mg2+ = 24.31/2 = 12.16 g/eq (300)(50/12.16) = 1233.55 mg/L as CaCO3

Problem

Strategy

Solution

b) Convert 30 mg/L Mg2+ as CaCO3 to mg/L

(30 mg/L as CaCO3)(12.16/50) = 7.3 mg/L

Example

Solution

Balance the following chemical equations: CaCl2 + Na2CO3 CaCO3 + NaCl C6H12O6 + O2 CO2 + H2O NO2+H2O HNO3 + NO

Example

Solution

CaCl2 + Na2CO3 CaCO3 + 2NaCl C6H12O6 + 6O2 6CO2 + 6H2O 3NO2+H2O 2HNO3 + NO

Example

Solution

What is the pH if [H+] = 10-3?

pH = 3

What is the pOH if [OH-] = 10-8?

pOH = 8

What is the pH if [OH-] = 10-8?

pH = 14 - 8 = 6

What is the [H+] if [OH-] = 10-5?

[H+]=105-14 = 10-9 mol/L

Problem

Strategy

Solution

Derive a proof that in a neutral solution, the pH and the pOH are both equal to 7.

Problem

Strategy

Solution

Evaluate the governing equation

?H A?OH A! K
 

! 10

14

@25 C

Problem

Strategy

Solution

?OH A! ?H A ?H A?OH A! ?H A?H A! ?H A

     

 2

! 10

14

H  A! 10 7 ? pH ! 7

Problem

Strategy

Solution

Find the hydrogen ion concentration and hydroxide ion concentration in tomato juice having a pH of 4.1

Problem

Strategy

Solution

Review how to convert

[H+]=10-pH 10-4.1 mol/L = 7.94 x 10-5 mol/L

Review governing equation

?H A?OH A! K
 

! 10

14

@25 C

Problem

Strategy

Solution

?H A! 10


 pH

! 10

 4.1

! 7.94 v 10 5 mol / L H  AOH  A! 10 14 ? ? 10 10 ?OH A! H  ! 7.94 v 10 5 ? A

 14 14

! 1.25 v 10 10 mol / L

...... end of example

Problem

Strategy

Solution

What percentage of total ammonia (i.e. NH3 + NH4+) is present as NH3 at a pH of 7? The pKa for NH4+ is 9.3.
NH m H  NH 3 K a ! 10
 9. 3  4 

H ?NH 3 A? !
 4

?NH A

Problem

Strategy

Solution

The problem is asking:

?NH 3 A v 100  ?NH 3 A ?NH 4 A

However, this expression has two unknowns. Therefore, we need a second equation.

?????

Problem

Strategy

Solution

The problem is asking:

?NH 3 A v 100  ?NH 3 A ?NH 4 A

Second Equation

K a ! 10

 9 .3

?NH 3 A?H !
 4

?NH A

Problem

Strategy

Solution

K a ! 10 K a ! 10

 9 .3

 9.3

?NH A ?NH A? A 10 ! ?NH A

 4 7 3  4

?NH 3 A?H !

A
Recall, pH=7 means [H] = 10-7

Problem

Strategy

Solution

K a ! 10
Therefore:

 9.3

?NH 3 A? 10
 4

7

A
3

?NH A

?NH A! 200?NH A
 4

Problem

Strategy

Solution

?NH 3 A v 100  ?NH 3 A ?NH 4 A ?NH 3 A ! v 100% ?NH 3 A 200?NH 3 A

! 0.5%

Problem

Strategy

Solution

Consider the problem of removing nitrogen from municipal wastewater Remove nitrogen to prevent the stimulation of algae growth Prevent excessive nitrate [NO3-] level in drinking water from causing a potentially lethal condition in babies known as methemoglobinemia

Problem

Strategy

Solution

One way to remove is a process known as ammonia stripping When organic matter decomposes, nitrogen is first released in the form of ammonia NH3 - low solubility in water (ammonia) NH4+ - highly soluble in water (ammonium ion)

NH m H  NH 3

 4

Problem

Strategy

Solution

By driving the equilibrium toward the right, less soluble gas is formed and encouraged to leave the solution and enter air stream in a gas stripping tower. This technique has been adapted for use in removing VOC s (volatile organic chemicals) from groundwater. How can the reaction be driven to the formation of ammonia (NH3)? Need to decrease [H+] or increase the pH.

 NH 4 m H   NH 3

Ka

?NH 3 A?  A H  9.3 ! 10 !

?NH A
 4

Problem

Strategy

Solution

Highly Soluble
 4 

Low Solubility

NH m H  NH 3
Ka

?NH 3 A?  A H  9 .3 ! 10 !

?NH A
 4

Want to consider [NH3]/[NH4+] Should we decrease this or increase this?

Problem

Strategy

Solution

Highly Soluble
 4 

Low Solubility

NH m H  NH 3
Ka

?NH 3 A?  A H  9 .3 ! 10 !

Increase it. How can we do this?

?NH A
 4

Problem

Strategy

Solution

Highly Soluble
 4 

Low Solubility

NH m H  NH 3
K a ! 10
 9 .3

?NH 3 A? H !
 4

Reduce [H+] Increase pH.

?NH A

Problem

Strategy

Solution

We want to derive an equation with pH as an independent variable.

Problem

Strategy

Solution

Let s start here:

Ka

?NH 3 A?  A H  9.3 ! 10 !

?NH 3  ?NH A!
4

?NH A A? A 10
 4  pH  9.3

10 9.3 pH ! ?NH 3 A10

Problem

Strategy

Solution

Ka

?NH 3 A?  A H 9.3 ! 10 !
4

?NH 3  ?NH A!

?NH A 10 A? A
 4  pH

10 9.3 ! ?NH 3 A10 9.3 pH

NH 3

?NH 3 A fraction !  ?NH 3 A ?NH 4 A

Problem

Strategy

Solution

NH 3

?NH 3 A fraction !  ?NH 3 A ?NH 4 A ?NH 3 A ! 9.3 pH A ?NH 3 A ?NH 3 A? 10

1 ! 9.3 pH 1  10

Problem

Strategy

Solution

1 .00 0.80 0.6 0 0.4 0 0.2 0 0.00 0 2 4 6 pH 8 10 12 14

----- end of example.

Fraction NH

Summary Of Example Problem

Nitrogen, in the form of ammonia (NH3) is removed chemically from the water by raising the pH This converts ammonium ion (NH4+) into ammonia NH3 is then stripped from the water by passing large quantities of air through the water

Problem

Strategy

Solution

A sample of water at pH 10 has 32.0 mg/L of carbonate and 56.0 mg/L of bicarbonate ion. Find the alkalinity as CaCO3.

Problem

Strategy

Solution

1. 2. 3. 4.

Determine the MW of HCO3- and CO3-2 Determine the EW of HCO3- and CO3-2 Convert the concentrations of HCO3- , CO3-2, H+ and OH- to mg/L as CaCO3 Add the concentrations in mg/L as CaCO3 of HCO3- , CO3-2, and OH-, and subtract H+

Problem

Strategy

Solution

CO : W ! 60, n ! 2, EW ! 30 HCO : W ! 61, n ! 1, EW ! 61

Now we need to convert to mg/L CaCO3
 3

2 3

Problem

Strategy

Solution

CO32  ! (32.0 mg L )50 30 ! 53.3 mg L as CaCO 3 HCO3 ! (56.0 mg L )50 61 ! 45.9 mg L as CaCO 3 H



! 5 v 10


 6 mg L

as CaCO 3
mg L

OH ! 5.0 mg L as CaCO 3 Alkalinity ! 53.3  45.9  5 ! 104.2

I will leave it up to you to check calculations for H+ and OH-

as CaCO3

...... end of problem

Problem

Strategy

Solution

The solubility product for the dissociation of Mg(OH)2 is 9 x 10-12. Determine the concentration of Mg2+ and OH- at equilibrium.

Problem

Strategy

Solution

1. 2. 3.

Write the equation for the reaction Write the solubility product equation Recognize from Eqn. 1 the relationship between the number of moles of Mg2+ and the number of moles of OH- resulting from the dissociation of Mg(OH)2, and how this relates to Eqn 2

Problem

Strategy

Solution

1. Write the equation for the reaction.

Mg OH 2 m Mg
 2

2

 2OH

2. The solubility product equation is:

?Mg A?OH A
2

! 9 v 10

12

Problem

Strategy

Solution

3. If x is the amount of Mg2+ resulting from the dissociation is given as x, then the amount of OH- is equal to 2x.

?x A?2 x A ! 9 v 10 12
4 x ! 9 v 10
3
12

x ! 1.3 v 10  4 moles / L ! Mg 2 x ! 2.6 v 10 moles / L ! OH

.....end of example
4

Problem

Strategy

Solution

Magnesium is removed from an industrial waste stream by hydroxide precipitation at a pH = 10. Determine the solubility of Mg2+ in pure water at 25 C and pKsp of 10.74.

Mg OH 2  s m Mg

2

 2OH

Problem

Strategy

Solution

1. Identify the two governing equations (Ksp and Kw) 2. Recognize that [OH-] = 10-14+pH 3. Substitute to derive an equation [Mg2+] = f(pH)

Problem

Strategy

Solution

1. What are your two governing equations?

?Mg A?OH A ! 10 ?OH A?H A! 10

2
  14

 2

10.74

2. Two unknowns, and two equations.

Problem

Strategy

Solution

3. Given the pH, we know [H+].

?H

A ! 10

 pH

! 10

 10

4. Solve for [OH-]2

10 14 10 14 !  pH ! 10 14 pH OH  A! ?  ?H A 10

?OH A

 2

! 10

 28 2 pH

Problem

Strategy

Solution

5. Substitute into 1st governing equation, and solve for [Mg2+].

?Mg

2

10 17 . 26  2 pH A ! 10  28  2 pH ! 10

10 . 74

Problem

Strategy

Solution

6. Substitute value of pH given in the problem statement, then convert to mg/L. NOTE: units in [ ] are moles per liter!

?Mg A ! 10 10 24 . 3
2  2 . 74 mol L

 2 . 74 mol g

10 mol 

3 mg

g !

44 . 2 mg

Problem

Strategy

Solution

7. For a pH of 11, the solubility is 0.442 mg/L. For a pH of 12 the solubility is 0.004 mg/L. Work these solutions on your own.
..... end of example.

Problem

Strategy

Solution

The chemical 1,4-dichlorobenzene (1,4-DCB) is used in an enclosed area. At 20rC (68rF) the saturated vapor pressure of 1,4-DCB is 5.3 x 10-4 atm. What would be the concentration in the air of the enclosed area (units of g/m3) at 20rC ? The molecular weight of 1,4-DCB is 147 g/mol.

Problem

Strategy

Solution

Rearrange the ideal gas law to solve for n/V [mol/L] and apply the appropriate conversions.

Problem

Strategy

Solution

Rearrange the Ideal Gas Law to solve for the concentration of 1,4-DCB in the air

n P 5.3 v10 atm ! ! L  atm V RT 0.0821 293o K mol  K g  5 mol 1000 L ! 2.2 v10 147 3 L m mol g ! 3 .2 3 m

4

Problem

Strategy

Solution

Anaerobic microorganisms metabolize organic matter to carbon dioxide and methane gases. Estimate the volume of gas produced (at atmospheric pressure and 25 C) from the anaerobic decomposition of 2 moles of glucose. The reaction is:

C6 H12O6 p 3CH 4  3CO2

Problem

Strategy

Solution

Recognize that each mole of glucose produces 3 moles of methane and 3 moles of carbon dioxide gases, for a total of 6 moles. Therefore, 2 moles of glucose produces a total of 12 moles.

C6 H12O6 p 3CH 4  3CO2

Use the ideal gas law to solve for V given n=12 moles

Problem

Strategy

Solution

Each mole of glucose produces 3 moles of methane and 3 moles of carbon dioxide gases, for a total of 6 moles. Therefore, 2 moles of glucose produces a total of 12 moles. The entire volume is then

L atm 12 mol 0.0821 298QK nRT K mol ! V! 1 atm P ! 294 L

Note: The volume of 1 mole of any gas is the same. Thus, 1 mole of carbon dioxide gas is the same volume of 1 mole of methane gas.

Example

Solution

Show that one mole of any ideal gas will occupy 22.414 L at standard temperature and pressure (STP). Note: STP is 273.13K and 101.325 kPa (0C and 1 atm).

Example

Solution

Use the ideal gas law to solve for volume. Note: J = N. m Pa = N/m2
N m mole K K  mole ! m3 V ! N m2 . 1 mole 8.3143 J K  mole 27316 K ! 1000 L m3 101.325kPa 1000 Pa kPa ! 22.414 L
......end of example

Example

Solution

Similarly, if we consider the volume at 25C

N m mole K K  mole V! ! m3 N m2 1mole 8.3143 J K  mole   25QK  L 273 ! 1000 m3 Pa 101.325kPa 1000 kPa ! 24.45 L
......end of example

Example

Solution

Convert 80 mg/m3 of SO2 in 1 m3 of air, 25 C, 103.193 kPa to ppm

Example

Solution

ppm !

Vp Va

M p L T2 101.325kPa MW 22.414 mole Q P2 273K ! L Va v 1000 m3 L 298 K Q 101.325kPa 22.414 273K Q 103.193kPa mole L Va v 1000 3 m

80 Qg g V p 64.06 mol ppm ! ! Va ! 0.03 ppm SO2

Problem

Strategy

Solution

A 1 m3 volume tank contains a gas mixture of 18.32 moles of oxygen, 16.40 moles of nitrogen and 6.15 moles of carbon dioxide. What is the partial pressure of each component in the gas mixture at 25C and 101.3 kPa?

Problem

Strategy

Solution

Convert temperature Use the ideal gas law to determine the pressure of each gas Apply Dalton s Law

Problem

Strategy

Solution

Convert temperature T ! 25.0  273 ! 298QK PO2 !

18.32 moles 8.314 J K mole 298QK

10m3 . ! 45389 Pa ! 45.39 kPa

PN2 ! 40.63 kPa PCO2 ! 15.24 kPa . P ! 45.39  40.63  15.24 ! 1013 kPa
.....end of example

Example

Solution

Calculate the concentration of dissolved oxygen (units of mol/L and mg/L) in a water equilibrated with the atmosphere at 25 C. The Henry s law constant for oxygen at 25 C is 1.29 x 10-3 mol/L-atm. Note: The partial pressure of oxygen in the atmosphere is 0.21 atm.

Example

Solution

mol 3 K H v PO2 ! 1.29 v10 0.21 atm L  atm  4 mol ! 2.7 v10 L
which you can convert to 8.7 mg/L

Problem

Strategy

Solution

A constant volume, batch chemical reactor achieves a reduction of compound A from 120 mg/L to 50 mg/L in 4 hours. Determine the reaction rate for both zero- and first-order kinetics. Clearly indicate the units of k.

Problem

Strategy

Solution

Using the two boundary conditions A = 120 mg/L at t=0 A = 50 mg/L at t=4 hrs Determine k using: C = Co - kt (zero order) C = Coe-kt (first order)

Problem

Strategy

Solution

Zero-Order

?C A! ?Co A kt
Co  C k! t 120  50 mg L ! 4hr ! 17.5 mg Lhr

Problem

Strategy

Solution

First-Order

?C A! ?Co Ae

 kt

C 50 ln ln C o !  120 k ! 4hr t ln 0.417 1 ! ! 0.219 hr 4hr

Note the difference in units. The units associated with rate constants are specific for the reaction order.

Problem

Strategy

Solution

Consider how the choice of a rate constant effects the design of a treatment facility. For Q = 0.5m3/s and an initial concentration of 150 mg/L, what size of reactor is required to achieve 95% conversion assuming a) b) Zero-order reaction First order reaction

Use the values of k from the previous problem Zero order k = 17.5 mg/Lhr First order k = 0.219 hr-1

Problem

Strategy

Solution

1. 2. 3. 4.

Note that 95% conversion means C = 0.05Co Solve for t in each case Recognize that Q = [L3/T] = Volume/time Solve for volume V= Qt for each case

Problem

Strategy

Solution

1. 95% conversion means C= 0.05Co 2. Zero-order

C ! Co  kt 0.05Co ! Co  kt 0.95150 mg L 0.95Co t! ! k 17.5 mg L hr ! 8.14 hr m3 V ! Qt ! 0.5 ! 14,657m 3

8.14 hr 3600 s hr  hr

Problem
3. First order

Strategy

Solution

C ! Co e  kt 0.05Co ! Co e  kt ln 0.05 !  0.219hr 1 t t ! 13.68 hr m3 V ! Qt ! 0.5 ! 24,622 m 3

13.68 hr  s hr  3600 s

Problem

Strategy

Solution

How long will it take the carbon monoxide (CO) concentration in a room to decrease by 99% after the source of carbon monoxide is removed, and the windows opened? Assume the first-order rate constant for CO removal (due to dilution by the in coming clean air) is 1.2 h-1.

Problem

Strategy

Solution

1. First order reaction is C=Coe-kt 2. If 99% is removed, C=0.01Co

Problem

Strategy

Solution

This is a first-order reaction, so use [CO]=[COo]e-kt When 99% of the CO is removed, [CO] = 0.01[COo] 0.01[COo] = [COo]e-kt where k = 1.2 h-1 Solve for t = 3.8 h

Problem

Strategy

Solution

An engineer is modeling the transport of a chemical contaminant in groundwater. The individual has a mathematical model that only accepts first-order degradation rate constants and a handbook of with a table for subsurface chemical transformation half-lifes . Subsurface half-lives for benzene, TCE and toluene are listed as 69, 231, and 12 days respectively. What are the first-order rate constants for all three chemicals?

Problem

Strategy

Solution

0.693 t1/ 2 ! k 0.693 k! t1/ 2

Apply this equation to each individual compound

Problem

Strategy

Solution

k benzene kTCE

0.693 0.693 ! ! ! 0.01 day 1 t1 / 2 69 days

0.693 0.693 1 ! ! ! 0.003 day t1 / 2 231 days 0.693 0.693 1 ! ! ! 0.058 day t1 / 2 12 days

k toluene

Problem

Strategy

Solution

After the Chernobyl nuclear accident, the concentration of 137Cs in milk was proportional to the concentration of 137Cs in the grass that cows consumed. The concentration in the grass was, in turn, proportional to the concentration in the soil. Assume that the only reaction by which 137Cs was lost from the soil was through radioactive decay, and the half-life for this isotope is 30 years. Calculate the concentration of 137Cs in cow s milk after 5 years if the concentration in milk shortly after the accident was 12,000 Bq/L. (Note: A Bequerel is a measure of radioactivity. One Bequerel equals one radioactive disintegration per second).

Problem

Strategy

Solution

1. Determine k 2. Apply the equation C=Coe-kt

Problem

Strategy

Solution

0.693 1 k! ! 0.023 yr t1 / 2

137

Cs

t !5

137

Cs

t !0

 kt

12,000 Bq 0.023 / yr 5 yr ! e L Bq ! 10,700 L

Problem

Strategy

Solution

A biological wastewater treatment process is known to exhibit first-order kinetics with a temperature correction factor equal to 1.023. For 20C, k=6.0 day-1. Determine the required reaction time required to meet 75% conversion in the summer and winter. Assume an average summer and winter temperature of 30C and 0C respectively.

Problem

Strategy

Solution

Correct k Solve for t given C=Coe-kt For 75% conversion, C=0.25Co

Problem

Strategy

Solution

kT ! k 20 5

(T  20 ) 1

6 k30 !  day 6 k0 !  day

1

1.023 1.023

( 30  20 )

! 7.53 day

1 1

( 0  20 )

! 3.807 day

Problem

Strategy

Solution

?C A! ?Co Ae

 kt

(1  0.75)Co C ln ln C Co o ! t! k k  1.386 ! k

Problem
Q

Strategy

Solution

For 30 C  1.386 ! 0.184 day ! 4.4 hr t! 1  7.53 day For 0 C  1.386 ! 0.364 day ! 8.74 hr t! 1  3.807 day
Q