De Belen, Jessica Mae P.

CE51FC1

Problem 1

Given the following information, what would the overall order of the reaction be?

The overall order of a reaction is the sum of the individual reaction orders.
The following reaction is first order for C6H5N2Cl and zero order for H2O.
To find the overall order you would add the order of C6H5N2Cl and H2O
1+0 = 1

Problem 2

The decomposition of aqueous hydrogen peroxide to gaseous oxygen and water is a first-order
reaction. If it takes 6.5 hours for the concentration of H2O2 to decrease from 0.70 to 0.35, how many
hours are required for the concentration to decrease from 0.40 to 0.10 ?

ln A = -kt + ln Ao
ln 0.35 = - (k) (6.5 hr) + ln 0.70
-1.0498 = - (k) (6.5 hr) - 0.356675
-0.693125 = - k (6.5 hr)
k = 0.1066346 hr-1

ln A = -kt + ln Ao
ln 0.10 = - (0.1066346 hr-1) (t) + ln 0.40
-2.3026 = - (0.1066346 hr-1) (t) - 0.9163
-1.3863 = - (0.1066346 hr-1) (t)
t = 13 hr

Problem 3

The half-life for a first-order reaction is 32.0 s. What was the original concentration if, after 2.00
minutes, the reactant concentration is 0.062 M?

k = (ln 2) / 32.0 s = 0.021661 s-1

ln A = -kt + ln Ao
ln 0.062 = - (0.021661 s-1) (120. s) + ln Ao
-2.78062 = -2.59932 + ln Ao
ln Ao = -0.1813
Ao = 0.834 M

Problem 4

The decomposition of hydrogen peroxide is a first-order reaction. The half-life of the reaction is 17.0
minutes.

(a) What is the rate constant of the reaction?

(b) If you had a bottle of H2O2, how long would it take for 86% to decompose?
(c) If you started the reaction with [H2O2] = 0.1 M, what would be the hydrogen peroxide concentration
after 15.0 minutes?

(a) k = (ln 2) / t1/2

k = (ln 2) / 17.0 min = 0.04077 min-1

(b) 86% decomposed means 14% remains.

ln A = -kt + ln Ao
ln 0.14 = - (0.04077 min-1) (t) + ln 1
t = 48.2 min

(c) 0.1 M is Ao
ln A = - (0.04077 min-1) (15.0 min) + ln 0.1
ln A = -2.914135
A = 0.0542 M

Problem 5

A certain reaction is first order, and 540. seconds after initiation of the reaction, 32.5% of the reactant
remains. What is the rate constant for this reaction? At what time after initiation of the reaction of the
reaction will 10.0% of the reactant remain?

Integrated form of first-order rate law:

ln A = -kt + ln Ao

ln 0.325 = - (k) (540. s) + ln 1.00

k = 0.002081352 s-1

k = 0.00208 s-1

Integrated form of first-order rate law:

ln A = -kt + ln Ao

ln 0.100 = - (0.002081352 s-1) (t) + ln 1.00

t = 1106 s

Problem 6

A certain first order reaction is 45.0% complete in 65 s. Determine the rate constant and the half-life for
this process.

Integrated form of first-order rate law:

ln A = -kt + ln Ao

45% complete means 55% remains:

ln 0.55 = - k (65 s) + ln 1

k = 0.0091975 s-1 (I kept a few guard digits for the next calculation.)

for the half-life:

ln 0.5 = - (0.0091975 s-1) (t) + ln 1

t = 75.4 s

Problem 7

Calculate half-life for first-order reaction if 68% of a substance is reacted within 66 s.

68% reacted means 32% remains:

ln A = -kt + ln Ao

ln 0.32 = - k (66 s) + ln 1

k = 0.0172642 s-1

ln 0.5 = - (0.0172642 s-1) (t) + ln 1

t = 40. s

Problem 8

T= 2.18 yr

Problem 9

T =2.9x104s

Problem 10
The half-life of a first-order reaction was found to be 10 min at a certain temperature. What is the rate
constant? Solution: Use this equation that relates half-life to rate constant for first order reactions:
Problem 11
An A + 2B  C + 2D reaction is carried out in solution at 90 °C in an isothermal, perfectly stirred batch
reactor. The reaction rate can be described as second-order, i.e. A B r  kc c , where k = 0.1 m 3
/(kmol·min). The solvent is fed into the tank reactor first, then 20 kg of material A (MA = 90 g/mol) and
50 kg of material B (MB = 90 g/mol) are added. The (liquid) reaction mixture has a volume of 900 dm3
at this point. The reaction causes no volume change. How much time is required to reach 90%
conversion? (t = 166.8 min)

Problem 12
What is the half-life of a zero order reaction?
Starting with the integrated rate law for a zero order reaction, we rearrange the variables so we can
make the substitution that [A] / [A]o = 0.5 when t = t1/2, we derive the following equation:

Problem 13
An A + B → C + D second-order reaction is carried out in a 0.12 m 3 ideal adiabatic tubular reactor.
The reaction rate coefficient can be calculated by the formula 6.52·105 ·e-42300/RT m 3 /(kmol·s). The
initial concentration of both A and B is 1.1 kmol/m3 . The feed contains no product, has a temperature
of 12 °C and a volumetric flow rate of 4·10-4 m 3 /s. The reaction enthalpy is -42600 kJ/kmol, the
mixture has a specific heat capacity of 2800 J/(kg·K) and a density of 840 kg/m3 . Calculate the
conversion! (X = 88.9%)

Problem 14
The time required for 10% completion of first order reaction at 298 K is equal to that required for its 25%
completion at 308K. If the pre exponential factor for the reaction is 3.56 ´ 109 s–1, calculate the energy
of activation.
Problem 15
An A + B  C + D reaction is carried out in solution at 80 °C in an isothermal, perfectly stirred batch
reactor. The reaction rate coefficient is k = 0.058 m 3 /(kmol·min). The solvent is fed into the tank
reactor first, then 30.5 kg of material A (MA = 90 g/mol) and 29.5 kg of material B (MB = 90 g/mol) are
added. The (liquid) reaction mixture has a volume of 890 dm3 at this point. The reaction causes no
volume change. How much time is required to reach 90% conversion? (t = 337.4 min)

Problem 16
6 ml of wastewater is diluted to 300 ml distilled water in standard BOD bottle. Initial DO in the bottle is
determined to be 8.5 mg/l. DO after 5 days at 20 C is found to be 5 mg/l. Determine BOD 5 of
wastewater and compute the ultimate BOD.

Problem 17
200 mL of Genesee river water was collected from just below the brewery. 2 mL of river water diluted to
1 L, aerated and seeded. The dissolved oxygen content was 7.8 mg/L initially. After 5 days, the
dissolved oxygen content had dropped to 5.9 mg/L. After 20 days, the dissolved oxygen content had
dropped to 5.3 mg/L. What is the ultimate BOD?
BOD5 = 7.8 mg/L – 5.9 mg/L = 950 mg/L
2 mL/1000 mL
BOD20 = 7.8 mg/L – 5.3 mg/L = 1250 mg/L
 2 mL/1000 mL
BOD5 = (1-e-k(5 days))
BOD20 (1-e-k(20 days))
950 = (1-e-k(5 days))
1250 (1-e-k(20 days))
0.76 = (1-e-k(5 days))
(1-e-k(20 days))
0.76 = (1-e-k(5 days))
(1-e-k(20 days))
0.76 – 0.76 e-k(20) = 1 – e-k(5)
e-k(5) – 0.76 e-k(20) = 1-0.76 = 0.24
BOD5 = BOD (1-e-k(5 days))
950 mg/L = BOD (1 – e-(0.28)(5))
BOD = 1261 mg/L

Problem 18
A wastewater stream has a BOD of 4000 mg/L. Calculate the flowrate of BOD (in kg/hr) if the 3
wastewater has a flowrate of 5000 m /3 hr. Assume, if necessary, the density of wastewater as 1,05
gr/cm.
BOD Flowrate Flowrate in kg/hr = (5000 m3/hr) x (4000 mg/L) x (1 k /106 ) (103 L/1 3 ) x (1 kg/10 ) 200
k /h 6mg) x(103 L/1 m3) = 200 kg

Problem 19
A sample of wastewater has an ul it mate BOD of 280mg/L and a 5‐day BOD of 240mg/L. Calculate 20‐
day BOD of this sample.
y20 = L0 (1‐e‐k*20 )
First calculate k using given data
y5 = L0 (1‐e‐k*5)
240 = 280 (1‐e‐k*5)
k = 0.39 d‐1
Then 20‐day BOD:
y20 = L0 (1‐e‐k*20) = 280 (1‐e‐0.39*20) = 279.9 mg/L
Problem 20
A 12.0-L sample of waste air from a smelter process was collected at 25°C and 1.00 atm pressure, and
the sulfur dioxide was removed. After SO2 removal, the volume of the air sample was 11.50 L. What
was the percentage by mass of SO2 in the original sample?

Under the conditions given, a mole of air occupies:

22.4L×(298 K/273 K) = 24.5 L/mol

Mol of air in 12.0 L air = 12.0 L/(24.5 L/mol) = 0.490 mol

Of this air, 0.50 L/(24.5 L/mol) = 0.0204 mol SO2

Using 29.1 g/mol for the molar mass of uncontaminated air

Mass of 0.490 mol “pure” air = 0.490 mol × 29.1 g/mol = 13.6 g

Mol of SO2 = 0.5L/(24.5 L/mol) = 0.0204 mol

Mass of SO2 = 0.0204 mol × 64.0 g/mol = 1.31 g

% SO2 by mass = 100 × 1.31 g/(13.6 g + 1.31 g) = 8.8% SO2

Problem 21
200 mL of Genesee river water was collected from just below the brewery. 2 mL of river water diluted to
250 mL, aerated and seeded. The dissolved oxygen content was 7.6 mg/L initially. After 5 days, the
dissolved oxygen content had dropped to 5.7 mg/L. A second sample was obtained 60 days later and
retested in identical fashion. The intial dissolved oxygen was 7.5 mg/L and, after 5 days, dropped to
5.3 mg/L. What is the ultimate BOD for each of the samples? Which water sample was cleaner?
BOD5,1 = 7.6 mg/L – 5.7 mg/L = 238 mg/L
2 mL/250 mL
BOD5,2 = 7.5 mg/L – 5.3 mg/L = 275 mg/L
2 mL/1000 mL
BOD5 = BOD (1-e-k(5 days))
238 mg/L = BOD (1 – e-(0.23)(5))
238 mg/L = BOD (0.6833)
BOD = 348 mg/L
275 mg/L = BOD (0.6833)
BOD = 402 mg/L
Problem 22
A 50 mL waste water sample is collected. 10 mL of 0.25 N K2Cr2O7 is added to the water sample and
to 50 mL of distilled water. Both samples are heated to 50°C for 30 minutes. The samples are allowed
to cool for 10 minutes and then titrated with 0.1015 N iron (II) ammonium sulfate. The waste water
sample requires 15.36 mL of titrant, while the blank sample requires 23.65 mL to reach a 1,10
phenanthroline endpoint. What is the COD of the waste water sample?
6 Fe2+ + Cr2O72- + 14 H+ → 6 Fe3+ + 2 Cr3+ + 7 H2O
The titration reaction has 6:1 stoichiometry of the Fe2+ titrant to the Cr2O72-.
i2M1V1 = i1M2V2
iFeMCrVCr = iCrMFeVFe
6 * MCr* 50 mL = 1* 0.1015 M * 15.36 mL
MCr = 5.20x10-3 M Cr2O72-

Problem 23
Three BOD bottles were prepared with sample and dilution water, as shown in the following table.
Bottle Sample (mL) Dilution Water (mL)
1 3 297
2 1.5 298.5
3 0.75 299.25
Calculate the dilution (D) for each.

Recall that the volume of a standard BOD bottle is 300 mL. For bottle 1, the dilution, D, is (Equation
9.2b):
D = 300
300 − 297
= 100
Similarly, for the other two bottles, D is calculated as 200 and 400.

Problem 24
Determine the 5‐day BOD for a 15 ml sample that is diluted with dilution water to a total volume of 300
ml when the initial DO concentration is 8 mg/l and after 5 days, has been reduced to 2 mg/l.
D0 = 8
D5 = 2
P = 15 ml/300ml = 0.05
BOD (mg/l) = (8-2) / 0.05 = 120
Problem 25
Consider a 1.67 *10–3 M glucose solution (C6H12O6) that is completely oxidised to CO2 and H2O. Find
the amount of oxygen required to complete the reaction.

C6H12O6 + 6O2 6CO2 + 6H2O

C6H12O6 + 6O2 6CO2 + 6H2O

180g (6*32g) (6*44g) (6*18g)

192g 264g 108g

180g C6H12O6 requires 192g of O2 to be completely oxidised. Thus find the concentration of the
organic compound using the equation below.

Concentration (mg/l) = Molarity (mol/l) * Mr (g/mol) * 103 mg/g

Mg/l = 1.67 * 10–3 M * 180 g/mol * 10–3 mg/g = 300 mg/l

180g C6H12O6 = 300 mg/l, therefore 192 g of O2 = 192 * 300 mg/l

180

= 320 mg/l

or if 192 g of O2 are required to completely oxidise 1M of C6H12O6, therefore how much O2 will be
required to oxidise 1.67 M of C6H12O6? = (1.67 * 192g) / 1 = 320g

Problem 26
Water has a total hardness of 255 mg/L as CaCO3 and a Mg2+ concentration of 55 mg/L as CaCO3.
How much water needs to be treated in split treatment if the water will be treated to the practical
solubility limits? What will be the final blended hardness?
Problem 27
A series of BOD test were run at three different dilutions. The results were as follows:
Bottle Dilution Initial DO (mg/L) Final DO (mg/L)
1 100 10.0 2.5
2 200 10.0 6.0
3 400 10.0 7.5
What is the BOD?

Solution First the individual BODs must be calculated. Then the results need to be compared. Recall
Equation 9.1:
BOD = (I − F)D
Therefore, the results of the lab test are

Bottle BOD (mg/L)

1 750
2 800
3 1000

Problem 28
Problem 29
Design a low rate filter to treat 6.0 Mld of sewage of BOD of 210 mg/l. The final effluent should be 30
mg/l and organic loading rate is 320 g/m3/d.
Assume 30% of BOD load removed in primary sedimentation i.e., = 210 x 0.30 = 63 mg/l. Remaining
BOD = 210 - 63 = 147 mg/l.
Percent of BOD removal required = (147-30) x 100/147 = 80%

BOD load applied to the filter = flow x conc. of sewage (kg/d) = 6 x 106 x 147/106 = 882 kg/d

To find out filter volume, using NRC equation

100
𝐸2 = 1
𝐹1 𝑏𝑜𝑑 2
1 + 0.44 ( 1 1 )
𝑉 𝑅𝑓
80 = 100 Rf1= 1, because no circulation.
1+0.44(882/V1)1/2

V1= 2704 m3

Depth of filter = 1.5 m, Fiter area = 2704/1.5 = 1802.66 m2, and Diameter = 48 m < 60 m

Hydraulic loading rate = 6 x 106/103 x 1/1802.66 = 3.33m3/d/m2 < 4 hence o.k.

Organic loading rate = 882 x 1000 / 2704 = 326.18 g/d/m3 which is approx. equal to 320

Problem 30
Calculate the theoretical oxygen demand (ThOD) of 150 ppm glucose?

C6H12O6 + 6 O2 = 6CO2 + 6H2O

MW of glucose = 180 g/mole
1 ppm = 1mg/l
glucose= 150ppm = 150mg/l
Therefore THOD = (6*32 g/mole O2 * 150 mg/L glucose) / 180 g/mole glucose = 160 mg/L