CTEC313: Environmental Analysis

Water analysis: Guide to answers

1.
a)

The hardness is caused by the polyvalent cations (mainly Ca2+ &

Mg2+, you might also include Zn2+ but it wont make much
difference). We must find the amount of CaCO3 which would give
the same degree of hardness. Start by finding the molar
concentration of each of the polyvalent ions and then find the total
molar concentration (0.380 mmol dm-3). This (in terms of
hardness) is equivalent to 0.380 mmol dm-3 of CaCO3. The
hardness is then 38.0 mg(CaCO3)/L.

b)

Overall, any solution should be electrically neutral the total

concentration of the +ve charges should balance out the total ve
charges. So, find the total cation charge:
Concn
Cations (mg/L)
Ca2+
9.79
Mg2+
3.25
+
Na
23.6
2+
Zn
0.14

at wt
(g/mol)
40.08
24.31
22.99
65.39

Concn
(mM)
0.2443
0.1337
1.0265
0.0021

ionic
charge
2
2
1
2

charge
concn
(mM)
0.488523
0.26738
1.026533
0.004282

total
cations 1.787
Also find the total anion charge:

Anions
ClNO3SO42F-

Concn
(mg/L)
20.3
5.04
11.49
0.13

at wt
(g/mol)
35.45
62.01
96.07
19

Concn
(mM)
0.572638
0.081277
0.1196
0.006842

ionic
charge
1
1
2
1

charge
concn
(mM)
0.572638
0.081277
0.239201
0.006842

total
anions 0.900
It is clear that some anions are not accounted for.

c)

The Cl-, NO3- and SO42- are anions of strong acids and will not make
the water alkaline. F- is the conjugate base of HF, but is quite weak
and also quite dilute this will not fully account for the alkalinity.
CO32- and HCO3- are commonly found anions that could account for
the alkalinity. The missing anion is probably one (or both) of
these.
But, what will be the concentration? The charge shortfall is
0.887 mM; which would be equivalent to either 0.887 mM HCO3(= 54.1 mg/L) or to 0.443 mM CO32- (= 26.6 mg/L).
If the water has a very high pH, perhaps the missing anion is OH- in which case, the OH- concentration would be 0.887 mM (= 15.1
mg/L).

d)

TDS stands for Total Dissolved Solids and is the sum of all the
charge concentrations (mg/L) of the dissolved species, the
majority of which are ionized. TDS passes through a micro size
filter paper. It is estimated from the conductivity value of fresh
water sample since most of the dissolved solid are ionized.
The total concentration for the ions in the table comes to 73.7
mg/L. If the missing anion was OH- there is not enough of it to
account for the shortfall the OH- concentration would be only
15.1 mg/L. If we include the CO32- (26.6 mg/L) we still do not
come up to 120 mg/L. If we include HCO3- (54.1 mg/L) then the
calculated TDS comes to more than 120 mg/L. Therefore, the
missing anion is probably a mixture of CO32- and HCO3-.

e)

The capacity of the water to neutralize any acidic species as well as

resistance (buffering capacity) to lowering of pH.
1 mmol CaCO3 = 2 meq of alkalinity.
so, 1 meq of alkalinity = 0.5 mmol CaCO3 = 50 mg CaCO3
or, 1 meq/L = 50 mg(CaCO3)/L
so the total alkalinity = 0.63 x 50 = 32 mg (CaCO3)/L

2.
a)
i)

264 mgCaCO3/L

ii)

4.8 mgCaCO3/L

iii)

259 mgCaCO3/L

b)

2HCO3- (carbonate hardness) + Ca2+/Mg2+(aq) + heat

Ca2+/Mg CO3(S)(scales) + H2O(l) +CO2(g)

3.
a)

B has a higher carbonate/bicarbonate concentration because this is

associated with the temporary hardness.

b)

Carbonate and bicarbonate contribute to alkalinity, and can react with

any added acid so lake B will be more resistant to pH changes if an
acid is added (eg from acid rain etc).

a)

CO32- is a stronger base than HCO3-

b)

The stronger base i.e. -CO32-

c)

Find the number of moles of H+ used (= 0.0508 mmol)

From the stoichiometry (if the end point is at a pH 0f 8.3, the product
is bicarbonate only one proton is added):

4.

CO32- + H+ HCO3- {end point pH of 8.3 (phenolphthalein)

d)

find the number of moles of carbonate (= 0.0508 mmol) and then find
the concentration (= 1.015 mmol/L)
At the phenolphthalein end point, 0.0508 mmol of H+ were used this
is 0.0508 meq.
the sample volume was 50.00 mL; so the
phenolphthalein alkalinity was 1.015 meq/L
Or For 0.0508 mmol of H+ required for complete neutralization of
carbonate alkalinity in the titration, it is equivalent to (0.0508
mmol/2) CO32- (or CaCO3). Thus, mass of CaCO3 in 50 mL = 0.0254
mmol x 100 g/mol = 2.54 mg. Carbonate alkalinity (mg/L) = 50.8 mg
CaCO3 /L
= (50.8 mg CaCO3 /L)/(50 mg CaCO3/meq) = 1.015 meq/L

e)

Both CO32- and HCO3-

f)

This time (to a lower pH of 4.5) the reaction is:

CO32- + 2H+ H2O +CO2
So the 0.0508 mmol of CO32- will use up 0.1015 mmol H+ (twice as
much according to the mole ratio)

g)

From the titration, a total of 0.2014 mmol H+ were used, but as much
as 0.1015 mmol were used for the CO32So 0.2014 0.1015 = 0.0999 mmol reacted with original (native)
HCO3-.
So HCO3- concentration = 0.0999 mmol/0.05L)
= 2.00 mmol/L

h)

You can calculate this from the methyl orange end point,

remembering that 1 eqv. alkalinity = 1 mol H+ ions.

TA = 0.2014 mmol H+ /50x 10-3L
= 4.0289 mmol/
= 4.03 meq/L
Or For 0.2014 mmol of H+ required for complete neutralization of
total alkalinity in the titration, it is equivalent to (0.2014 mmol/2)
CO32- (or CaCO3). Thus, mass of CaCO3 in 50 mL = 0.1007 mmol x 100
g/mol = 10.07 mg. Total alkalinity (mg/L) = 10.07/50x10-3L = 201.4
mg CaCO3/L = (201.4 mg CaCO3 /L)/(50 mg CaCO3/meq) = 4.03
meq/L

i)

1 meq = 0.5 mmol CaCO3 = 50 mg CaCO3

TA = 4.0289 meq/L x 50 mg CaCO3 = 201.4 mg CaCO3/L

5.

See answers to 4

6.
a)
b)
i)
ii)
c)

d)
i)
ii)

e)
i)

BOD = 8.06 - 3.26 = 4.80 mg/L

BOD = (8.52 2.16) x 250/5 = 318 mg/L (Dont forget the dilution
factor this time)
If it wasnt diluted, there would not have been enough oxygen the
oxygen would have been the limiting reagent and not the analyte.
There probably wasnt a viable microbial population in the sample
maybe because of the low pH, maybe because of the source of the
waste. After dilution with the buffer, the pH would probably be
corrected, so adding a seed of bacteria would probably overcome the
problem.

You cannot calculate the BOD unless there is some oxygen left at the
end of the test.
This value definitely cannot be trusted if there is no dissolved
oxygen left at the end of the test you cannot be certain that the
organic oxidisable matter (the analyte) is the limiting reagent and the
real BOD may be greater than the determined value. The test should
be repeated with a more dilute sample.
BOD = (8.68 5.24) x 250/5 = 172 mg/L. If the test is working well,
the measured BOD of the check standard is within two standard
deviations of the average i.e. between 180 mg/L and 220 mg/L.

ii)

Therefore, the test is not working well.

This is a stoichiometry problem: first we need the reaction
equations
If the glucose was completely oxidized, the equation would be:
C6H12O6 + 6O2 6CO2 + 6H2O
For the glutamic acid the equation would be:
2C5H9NO4 + 9O2 10CO2 + 6H2O + 2NH3
For stoichiometric calculations we need to work with molar
concentrations. Then we can use the stoichiometry to work out the
concentration of oxygen that would be required to oxidize the glucose
and glutamic acid this is then the expected BOD.
glucose
glutamic
acid
Concn (mg/L)
150
150
-1
Molar mass (g mol )
180.2
147.1
Concn (mmol dm-3)
Oxygen demand (mmol dm-3)

0.833

1.02

5.00

4.59

Oxygen demand (mg/L)

160

147

Total

307 mg/L

Use stoichiometric molar ratios

7.
a)

Adding concentrated sulfuric acid to water generates a lot of heat and

the mixture might boil and shoot up through the condenser!

b)

Cr2O72- + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O

c)

2.064x10-3 mol

d)

First, find the number of moles of dichromate added to the sample

(=1.063x10-3) and then find out how many moles of dichromate
remained to react with the iron(II) used in the titration (= 0.344x10 3). Then find the number of moles dichromate that reacted with the
organic matter during the reflux = 7.187x10-4 mol.

e)

1.98x10-5 mol (use a similar calculation to that described in part d)

but use the endpoint volume for the blank.)

f)

moles used = 7.187x10-4 - 1.98x10-5 = 6.989x10-4 mol

g)

Remember that the COD is calculated in terms of the concentration of

oxygen that would have been required to do the same amount of
oxidation as the dichromate. By considering the relevant halfreactions we find that 1 mol Cr2O72- is equivalent to 1.5 mol O2. So:
mol O2 = 1.5 x 6.989x10-4 = 1.048x10-3 mol
mass O2 = 32.00 x 1.048x10-3 = 33.55x10-3 g = 33.55 mg

COD = 33.55/(0.025 L) = 1342 mgO2/L

h)

BOD would be most likely lower than the COD demand. COD uses
much stronger oxidation conditions and is more likely to completely
oxidize all, including normally matter that is not biodegradable.