ION SELECTIVE ELECTRODES

Determination of Alkalinity in Swimming Pool Water

Introduction
In pure water, the addition of small amounts of a strong acid or a strong base causes a dramatic
change in the pH. Although it is expected for natural waters to exhibit this dramatic change in pH
due to acid rain, natural water continues to sustain life. In other words, the effect of the ‘’pH
change’’ is not observed. This is because natural waters contain ionic compounds that can react
quickly with acid to buffer the system and thus resist a change in pH. The acid neutralizing capacity
(alkalinity) of swimming pool water is potentiometrically determined in this experiment.

Materials and methods

 Results
Table 1: the pH readings at different HSO volume and the calculated data points for the first and second derivatives

first second
derivativ derivativ
e e
volume(m pH mean delta delta delta pH/ Delta2 Delta2 Delta2 pH/delta2
l) volume(ml pH(mV) volume(m delta pH(mV2) volume(ml2 volume
) l) volume ) ( mV2/ml2)
(mV/ml)
0.00 7.43 0.13 -0.03 0.25 -0.12 -0.04 0.00 -0.16
0.25 7.40 0.38 -0.07 0.25 -0.28 -0.02 0.00 -0.08
0.50 7.33 0.63 -0.09 0.25 -0.36 -0.08 0.00 -0.32
0.75 7.24 0.88 -0.17 0.25 -0.68 0.01 0.00 0.04
1.00 7.07 1.13 -0.16 0.25 -0.64 -0.10 0.00 -0.4
1.25 6.91 1.38 -0.26 0.25 -1.04 0.05 0.00 0.2
1.50 6.65 1.63 -0.21 0.25 -0.84 -0.15 0.00 -0.6
1.75 6.44 1.88 -0.36 0.25 -1.44 0.11 -0.15 -0.733333333
2.00 6.08 2.05 -0.25 0.10 -2.50 -0.02 0.00 -0.2
2.10 5.83 2.15 -0.27 0.10 -2.70 -0.09 0.00 2.02662E+14
2.20 5.56 2.25 -0.36 0.10 -3.60 -0.13 0.00 -2.92734E+14
2.30 5.20 2.35 -0.49 0.10 -4.90 0.15 0.00 1.5
2.40 4.71 2.45 -0.34 0.10 -3.40 0.06 0.00 0.6
2.50 4.37 2.55 -0.28 0.10 -2.80 0.03 0.00 0.3
2.60 4.09 2.65 -0.25 0.10 -2.50 0.07 0.00 0.7
2.70 3.84 2.75 -0.18 0.10 -1.80 -0.06 0.15 -0.4
2.80 3.66 2.93 -0.24 0.25 -0.96 0.06 0.00 0.24
3.05 3.42 3.18 -0.18 0.25 -0.72 0.04 0.00 0.16
3.30 3.24 3.43 -0.14 0.25 -0.56 -2.96 -3.80 0.778947368
3.55 3.10 3.55 -3.10 -3.55 0.87 3.10 3.55 0.873239437
 Figure 2: pH versus volume of HSO added

8
7
6
5
4
Ph
3
appro x. end point
2
1
0
0 0.5 1 1.5 2 2.5 3 3.5 4
volume HSO(ml)

Veq= 2.3 ml

Figure 3: 1st derivative graph

0
0 0.5 1 1.5 2 2.5 3 3.5 4
-1
d. ph/d. vol

-2

-3

-4

-5
equivalence point
-6
mean volume(ml)

Veq=2.35ml
 Figure 4: 2nd derivative graph

300000000000000

200000000000000

100000000000000
Delta2/delta2 vol

0
0 0.5 1 1.5 2 2.5 3 3.5 4
-100000000000000

-200000000000000

-300000000000000

-400000000000000
volume HSO (ml)

Veq=2.2ml

Veq,AVERAGE= (2.35+2.20) ml=2.28ml

Calculations
1) Approximated endpoint from fig. 1= 2.3ml
2) At equivalence point, moles acid added= moles calcium carbonate:

CaCO3 (aq) + H 2 SO 4 (aq) → H 2 CO 3 (aq )+CaSO 4 (aq)

2−¿
CO 3(aq) +2 H 3 O +¿→ H 2 CO 3( aq )+ H 2 O( l)¿
¿

C 1 V 1=C 2 V 2

C 1 V 1 0.01 M∗2.28∗10−3 L
∴ C2= = =4.361∗10− 4 M
V2 −3
52.28∗10 L
Since for every 1mole of CO32- there’s I mole of CaCO3, conc. CaCO3 = conc. CO32-
g 3
∗10 mg
−4 mol mol mg mg
∴ total alkalinity =4.361∗10 ∗100.0869 =43.649 =43.6
L 1g L L
CaCO3
 3) The pH at the equivalence point
Graphically, pH= 5.2

As per calculations
At the equivalence point, the only source of free H+ ions is the dissociation of the weak
carbonic acid. This is illustrated by the equations below:

H 2 CO 3 (aq ) ⇄ H(a+¿q )+ HCO 3(aq)

−¿
¿ ¿………. K1

−¿ +¿ −¿
HCO 3(aq) ⇄ H (aq) +CO 3(aq) ¿ ¿ ¿……….. K2

H2CO3 H+ HCO3-
Initial 0.0004398 0 0
change x x x
final 0.0004398 - x x x

Assuming x ≪ 1.398∗10−4

−7
K a =K 1=4.46∗10 =¿ ¿

∴ x=√ 4.46∗10 ∗4.361∗10 =1.395∗10 M

−7 −4 −5

HCO3- H+ CO32-
Initial 0.00001395 0.00001395 0
change -x +x +x
final 0.00001395-X 0.00001395 +x x

Assuming x ≪ 1.395∗10−4

−11
K a =K 2=4.69∗10 =¿¿
−5 −11 −5
+¿=1.395 ¿10 +4.69∗10 =1.395∗10 M ¿
∴ conc . H

This indicates that the second dissociation is significantly low, hence concentration doesn’t change.

∴ pH =−log [ 1.395∗10−5 ] =4.855=4.86

Answers to questions

1. Preparation of 0.01M sulphuric acid (see Appendix A for calculations)

2. The construction of a glass electrode [1]
The glass electrode is made up of the following components:
 A bulb(a sensing part), made from specific glass
 Internal electrode(usually silver-silver or calomel electrode)
 An internal pH7 buffered solution (usually 0.1M KCl for pH electrode or 0.1M MeCl
for pMe )
 A reference electrode
 A reference internal solution, usually 0.1M KCl
 Junction with studied solutions, usually made up of ceramics or capillary with
asbestos or quarts
 Body of electrode made from non-conductive glass or plastic
3. Possible errors and interferences
 Cross-contamination. This is caused by the negligence of rinsing the electrode with
deionised water in between calibrations, thus transferring one buffer into another.
This will make wrong calibration hence a pH adjustment is made on the pH meter.
However, suppose the mistake was not noticed and the experiment progressed as if
nothing was amiss, the results would be systematically erroneous. Therefore the
conclusion would be unreliable.
 Contact between the magnetic stirrer bar and the glass electrode. This will damage
the fragile silicone gel membrane of the electrode.
 Temperature. This affects the electrode slope, the liquid junction potential, and the
solubility of the salts in the reference system. [5]
 No stirring. The measurements need to be taken at equilibrium
 Conversely, stirring for long hours. This can produce heat thus affect the potential
measurements
 Cleaning procedures. Intense wiping and rubbing of the electrode may damage the
fragile gel.
 Electrode left out of solution. The membrane would be dehydrated if left out of
solution. Thereafter, the pH sensor would have a slower response and a higher than
normal impedance [1]. The electrode would no longer function properly because the
electrolyte would leach out of the electrolyte cavity and form crystals at the
junction.
4. The advantages of using an automated burette
 It delivers the exact volume of titrant, even very small volumes
 Avoids human errors (error of parallax)
 Low wastage of titrant [2]
 Convenience in exchange of titrant (i.e. less challenges) [2]
 Simple control of flow rate [2]
 5. The ions contributing to the total alkalinity originate from the dissolution of geological
minerals in rain and ground water [3]. Some come from the leaching of rocks and soil into
ground water

6. Similar experiment carried out as given in the procedure

Table 2: the pH readings at different HSO volume and the calculated data points for the first and second derivatives

first derivative seco

total volume pH mean Delta Delta delta pH/ delta Delta2 Delta2
added(ml) volume(ml volume(ml) pH(mV) volume (mV/ml) pH(mV2) volume(ml2
)
0.00 7.107 0.125 0.25 -0.139 -0.556 -0.003 0
0.25 6.968 0.375 0.25 -0.142 -0.568 -0.008 0
0.50 6.826 0.625 0.25 -0.15 -0.6 -0.011 0
0.75 6.676 0.875 0.25 -0.161 -0.644 -0.026 0
1.00 6.515 1.125 0.25 -0.187 -0.748 -0.043 0
1.25 6.328 1.375 0.25 -0.23 -0.92 0.123 -0.15
1.50 6.098 1.55 0.1 -0.107 -1.07 -0.032 -2.2E-16
1.60 5.991 1.65 0.1 -0.139 -1.39 -0.03967 2.22E-16
1.70 5.852 1.75 0.1 -0.17867 -1.78667 -0.09467 -2.2E-16
1.80 5.673333 1.85 0.1 -0.27333 -2.73333 -0.19267 2.22E-16
1.90 5.40 1.95 0.10 -0.47 -4.66 0.02 0.00
2.00 4.93 2.05 0.10 -0.45 -4.48 0.19 0.00
2.10 4.49 2.15 0.10 -0.26 -2.59 0.09 0.00
2.20 4.23 2.25 0.10 -0.17 -1.67 0.05 0.00
2.30 4.06 2.35 0.10 -0.12 -1.21 -0.09 0.15
2.40 3.94 2.53 0.25 -0.21 -0.83 0.07 0.00
2.65 3.73 2.78 0.25 -0.14 -0.56 0.04 0.00
2.90 3.59 3.03 0.25 -0.11 -0.42 0.02 0.00
3.15 3.49 3.28 0.25 -0.08 -0.33 0.01 0.00
3.40 3.41 3.53 0.25 -0.07 -0.28 0.01 0.00
3.65 3.34 3.78 0.25 -0.06 -0.23 0.01 0.00
3.90 3.28 4.03 0.25 -0.05 -0.20 -3.18 -4.40
4.15 3.23 4.15 -4.15 -3.23 0.78 3.23 4.15
 Figure 5: pH versus volume HSO added

8
7
6
equivalence
5 point

4
pH

3
2
1
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
volume HSO(ml)

Veq=2.0ml

Figure 6: 1st derivative graph

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
-1
pH

-2

-3

-4
equivalence
-5 point
volume HSO (ml)

Veq= 1.95 ml
 Figure 7: 2nd derivative graph

600000000000000

400000000000000

200000000000000

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
-200000000000000
pH

-400000000000000

-600000000000000

-800000000000000

-1000000000000000 volume HSO (ml)

Veq= 1.8 ml

Veq,AVERAGE= (1.8+1.95) ml=1.88ml

Total alkalinity
4) At equivalence point, moles acid added= moles calcium carbonate:

CaCO3 (aq) + H 2 SO 4 (aq) → H 2 CO 3 (aq )+CaSO 4 (aq)

2−¿
CO 3(aq) +2 H 3 O +¿→ H 2 CO 3( aq )+ H 2 O( l)¿
¿

C 1 V 1=C 2 V 2

C 1 V 1 0.01 M∗1.88∗10−3 L −4
∴ C2= = =3.624∗10 M
V2 −3
51.88∗10 L
Since for every 1mole of CO32- there’s I mole of CaCO3, conc. CaCO3 = conc. CO32-
g 3
∗10 mg
−4 mol mol CaCO3
∴ total alkalinity =3.624∗10 ∗100.0869 =36.3 mg/L
L 1g

Discussion
 Comparison of the two alkalinities

The total alkalinity in swimming pool water was determined and found to be 43.6 mg/L CaCO 3.
Another experiment was carried out as given in the procedure and the total alkalinity was found to
be 36.3 mg/L. As per this experiment, the alkalinity was found to be 43.6 mg/L CaCO 3. Both of these
findings lie within the reported alkalinity range of 20 - 500 mg/ CaCO 3(analytical laboratory manual,
pg. 21). This therefore indicates that the swimming pool water is less susceptible to acidification.
On the contrary, the alkalinity of the swimming water sample is not consistent with literature which
reports that the pool alkalinity should be a range of 80 – 120 mg/L [6] . this total low alkalinity might
have been caused by: 1) addition of low alkalinity water, which consequently reduced the total
alkalinity of the pool 2) the alkalinity may have been lowered too much during ‘alkalinity
adjustments’ by the addition of too much of the reducer [6].However, the alkalinities determined in
the two experiments are evidently different, though the procedure was the same. This shows that
the water samples are not from the same swimming pool.

The results in Table 1 show that the initial pH of the water sample was 7.43. However, it is reported
in Table 2 that the initial pH of the water sample in the second experiment was 7.107. This means
that the water sample that was analysed in this experiment was more basic than the other sample,
analysed in the second experiment. Presumably, there might have been cross-contamination of
buffers in either one of the experiments, resulting in wrong pH calibration which ultimately affected
the pH readings. This thus means that the corresponding equivalence point was also affected. Hence
the dissimilar alkalinities were also obtained. Furthermore, the membrane of the electrode may
have been damaged, rendering the glass electrode inefficient in measuring the pH. Another possible
error that might have occurred is stirring for a long time. It results in heat being produced thus
increase in the temperature of the mixture being increased. This affects the electrode slope, the
liquid junction potential, and the solubility of the salts in the reference system. [5]

Initial pH change of the sample

The pH of the water sample was 7.2 on the day of collection. According to the pH reported in table 1,
it is shown that the initial pH of the sample changed to 7.43. This increase is due to the oxidation
reaction occurring in the closed container (closed system), thus increasing the basicity of the water
sample

In this experiment, the pH at the endpoint was found to be 4.86 (about 4.9) – a value not far from
the theoretical pH value of 4.5, as stated by the analytical laboratory manual, pg. 19. This suggests
that the swimming pool water sample being analysed is in fact capable to resist any pH changes,
since there pH remained at virtually the same pH at the endpoint.

Recommended corrections and improvement

 Avoid cross-contamination at all costs. Ensure cleaning and rinsing with deionised water
 Prevent any contact between the magnetic stirrer bar and the electrode
 Avoid stirring for long periods
 Always keep electrode in electrolyte solution
 Never rub the electrode while cleaning.
 Use buffers only once. This minimises cross-contaminations
  Ensure that the level of electrolyte is right up to the filling hole

Reference
1. http://milanco.com/training/careofph.htm, 11 March 2014
2. http://www.tau.ac.il/~advanal/TitrimetricMethodsOfAnalysis.htm , 14 Mar 2014
3. http://edis.ifas.ufl.edu/ss540, 14 Mar 2014
4. http://ion.chem.usu.edu/~sbialkow/Classes/3650/Alkalinity/Alkalinity.html ,
5. http://www.nico2000.net/datasheets/faq.html#13 ,
6. http://www.poolforthought.com/raising-pool-alkalinity/ ,

Appendix A
Preparation of about 0.01 M sulphuric acid

Calculations
Stock solution is 95% sulphuric acid∴ MW H 2 SO 4 =0.95∗MW =0.95 m
m
ρ=
V

1.84∗1000 g
∴ m= ∗1 L=1840 g
L

mH SO4 1840 g
∴ nH SO4 = 2
= =19.7478=C H SO4
2
MW 0.95∗98.079 g /mol 2

n 19.7478
∴V= = =1974.78 g
C 0.01