Chemistry for Environmental Engineering and Science, 5th Edition

CHAPTER 24 - PROBLEM SOLUTIONS

24-1 See page 629, Section 24.5

24-2 Aromatic hydrocarbons and pyridine

24-3 (a) Organic compounds are oxidized to carbon dioxide, water, and ammonia (Equation
24.1).
(b) No

24-4 Chloride is the most prevalent interfering inorganic species. To deal with this problem,
mercuric sulfate is added and the mercury forms a complex with chloride that is not
oxidized in the COD test.

24-5 Fatty acids can be oxidized in the COD test if a silver catalyst (Ag2SO4) is added.

24-6 (a) Higher (chloride will be oxidized if not complexed with mercury).
(b) Lower (fatty acids are not oxidized if a silver catalyst is not present).
(c) Higher (titrant strength decreases with time due to Fe(II) oxidation, thus normality
would here be assumed to be higher than is actually the case, giving high results).

24-7 The COD test generally measures both refractory and biodegradable organic materials,
while the BOD test measures only biodegradable organic matter. Additionally, the
COD test can result in near complete oxidation of organics, while the BOD does not
completely oxidize even biodegradable materials. For these reasons, the COD test
generally gives higher values than the BOD test. There are exceptions, for example
pyrimidine may be biologically degraded in the BOD test, while it is not oxidized in the
COD test.

24-8 The closed-reflux procedures make use of smaller quantities of toxic chemicals per test
(less amount for hazardous waste disposal) and samples for analysis are often
considered easier to prepare than for the open-reflux procedure. However, the chemical
cost per test is higher for the closed-reflux procedure. The problem with chemical
disposal can be reduced in the open-reflux procedure by using smaller sample size and
reduced chemical volumes than called for in the normal Standard Methods procedure.

24-1
24-9 Either 600 nm or 420 nm. When using 600 nm, the analyst measures the decrease in the
orange color of Cr(VI), which is removed in proportion to the amount of organic
material oxidized. When using 420 nm, the analyst measures the increase in blue color
of Cr(III), which is formed in proportion to the amount of organic matter oxidized. The
choice depends upon which provides the best precision for the test. Generally, if a small
percentage of the dichromate is consumed, it is best to use 420 nm, while if most is
consumed, then 600 nm would probably be preferred.

24-10 A weaker solution of dichromate is used for oxidation and more care in analysis is
required to allow for good precision for samples with low (< 50 mg/L) COD.

24-11 (a) The silver, chromium, and sulfuric acid used in the COD analysis are all chemicals
of environmental concern and waste samples containing them must be disposed of
properly.

24-12 Use Equation 23-1:

(a) CH3CH2OH + 3 O2 = 2 CO2 + 3 H2O

FW ethanol = 46
COD = 300[3(32)/46] = 626 mg/L
====
(b) C6H5OH + 7 O2 = 6 CO2 + 3 H2O
FW phenol = 94
COD = 300[7(32)/94] = 715 mg/L
====
(a) C4H9CHNH2COOH + 7.5 O2 = 6 CO2 + 5 H2O + NH3
FW leucine = 131
COD = 300[7.5(32)/131] = 550 mg/L
====
24-13 Use Eq. 23-1:
(a) CH3CH2CH2CH2OH + 6 O2 = 4 CO2 + 5 H2O
FW butanol = 74
COD = 500[6(32)/74] = 650 mg/L
====
(b) Assume k' = 0.3/d (0.23/d to 0.4/d is reasonable range):
BOD5 = 650[1- e-0.3(5)] = 500 mg/L
====
(varies from 440 mg/L if 0.23/d used to 560 mg/L if 0.4/d used)

24-2
24-14 A. Easily biodegradable
B. Poorly biodegradable or requires special adaptation
C. Normal biodegradability

24-3