TITN-SW

Potentiometric and Colorimetric Titration of Seawater

Dates of Experiment: October 14th and October 21st 2014
Date of Submission: October 28th 2014
Jade Frizzell- Lab ID: A22
Section: L12
TA: Jinliang (Leo) Li

Abstract
Seawater was collected from Wreck Beach, Vancouver and analyzed on site via direct
potentiometry using a LabQuest device calcium ion selective electrode which had been
calibrated using 10ppm and 1000ppm calcium ion stock solution. A week later, the same sample
was analyzed by a complexometric titration with EDTA, using the same LabQuest device.
Magnesium was precipitated out prior to analysis with diethylamine. Calcon was used as the
indicator. Calcium ion concentrations from direct potentiometry, colourimetric titration and
potentiometric titration, in order were: 19.673.33ppm, 241.982.68ppm and 200.083.28ppm.
F-tests showed all methods to have variances in statistical agreement. T-tests showed all methods
to be statistically different from one another.

Introduction
96% of Earths water is seawater. This water consists of many elements, including
sodium, magnesium, and calcium. The concentrations of these elements affect the species that
live in the water, and can change from ocean to ocean. Calcium largely contributes to a quality
known as water hardness, which can affect marine life. One way to measure the concentration of
calcium ions in seawater is via direct potentiometry using a calcium ion selective electrode. This
method is very quick and commonly used when on site analysis is necessary. When a more
accurate result is required, titrations can be performed in the laboratory. One method is called a
complexometric titration and involves a colorimetric and potentiometric titration using
ethylenediaminetetraacetic acid (EDTA). EDTA forms strong 1:1 bonds with metals and is
therefore very useful in determining the concentration of Ca2+. This paper will discuss the results
of the three methods, and compare them statistically using an F-test and T-test. The accuracy and
precision of all three methods will also be discussed.

Methods
Direct Potentiometry
Seawater was collected from Wreck Beach on October 14th using a plastic container, which was
then poured into a funnel containing glass wool, into a beaker. The sample was then analyzed for
180 seconds with a LabQuest device calcium ion selective electrode that had been calibrated in
the lab with 10ppm and 1000ppm calcium ion stock solution. The reading was repeated six times
on the same sample. Back in the lab, we determined a point where the readings stabilized and
recorded six values for calcium ion concentration, which we then calculated the mean, standard
deviation and relative standard deviation of. The seawater sample was stored in a plastic bottle in
a refrigerator for one week.
Complexometric Titration
One week later, on October 21st, one practice titration and 3 more titrations were performed.
Prior to the titrations, the LabQuest device was calibrated the same was as discussed above. For
each titration, a 15mL sample of seawater was collected using a pipette. This was put into a clean

100mL beaker. 5mL of diethylamine were then added dropwise, in the fume hood. The solution
was then stirred for 5 minutes to ensure that all of the magnesium was precipitated out. A burette
was then filled with 0.01M EDTA, and 13 drops of calcon added to the seawater sample. The
titration was then performed. Volumes and calcium ion concentrations were recorded every
couple mLs, with the frequency increasing closer to the colorimetric endpoint. Once the solution
reached the endpoint blue color, that value was recorded, and then several more concentration
readings were obtained. The concentrations were then calculated from the data, as shown in the
calculation section.

Discussion
1)
Total Ionic Strength Buffer (TISB) would not be effecting for our analysis of seawater for
two reasons. First, in our samples, the concentrations of Ca2+ were not high enough to
significantly differ from activity, which is what the calcium ion selective electrode measures.
Secondly, TISB usually buffers a solution to a pH of approximately 5 (Crompton 2006). At this
pH, the magnesium would not precipitate out, and because of its high formation constant with
EDTA, would likely affect the analysis. At this pH, the EDTA would also not be in the fully
deprotonated form, therefore having less binding sites which is not ideal for this titration.
2)

The Nernst Equation ( = ) shows the relationship between potential and

concentration (Q is the ratio of ion concentration inside and outside). Our LabQuest device gave
us readings of concentration, which we wrote, with the corresponding volume EDTA. Our
method of determining the end point volume was to plot the first derivative to see the abrupt
change in potential. Looking at the Nernst equation, we need to take the natural logarithm of the
concentration reading in order to properly apply the equation. That is why we took the natural
logarithm of each reading before calculating the first derivative.
3)
In analytical chemistry, the matrix refers to all components of an analyte other than the
one of interest (Harvey, 2000). The matrix effect is the combined effect of all these components
on the chemical of interest (Harvey, 2008). According to the online Encyclopedia Britannica
(2014), seawater consists of 96.5% water, 2.5% dissolved salts, and smaller amounts of other
substances such as dissolved gasses. The dissolved salts, which is the matrix of interest for this
study, consists of many elements, including: Na+, Cl-, SO42-, Mg2+, K+, and inorganic carbon,
bromide, boron, strontium and fluoride. The dissolved gasses consist of mainly nitrogen, oxygen,
argon and carbon dioxide. The matrix effect can affect the results of direct potentiometry
because the ionic strength of the calibrations may differ from the actual ionic strength. Seawater
was not used for the calibrations, therefore it is not a perfect scenario. The electrode is calcium
ion selective, but the presence of the other ions will affect the reading to some degree. In our
titrations, we first precipitated out Mg2+, but other ions are still present. They are in much
smaller concentrations compared to Ca2+ that the effect is likely quite small, but still present.
4)
The density of seawater ranges from 1.020-1.029 gm/cm3 (Encyclopedia Britannica
2014). The unit parts per million (ppm) translates to mg/L in aqueous solutions. When

converting units to ppm, it is usually assumed that the solution is in fresh water, which has a
density of approximately 1gm/cm3, making the conversion simple. However, that does not
necessarily work in our case because we are dealing with seawater which has a higher density.
Therefore this must be taken into consideration when doing any conversions.
5)
The potentiometric titration estimates a lower concentration than the colourimetric
titration, a significant difference in our case. This is due to the presence of the indicator calcon.
The calcium ion selective electrode only measures the activity of free Ca2+ ions, not ones that are
bound to EDTA or calcon. Initially, a small amount of Ca2+ is bound to calcon. As the end point
draws closer, EDTA displaces it, but still masks it from the electrode. Therefore the electrode
will show an endpoint that is earlier than the colorimetric endpoint. Assuming my reasoning is
correct, the colorimetric titration would therefore give more accurate results, as long as the
endpoint is accurately detected and not under or overshot.
Comparing the direct potentiometry and potentiometric titration, as well as direct
potentiometry with colorimetric titration, significant differences were also seen. This is likely
due to the low accuracy of the direct potentiometric method. Our results for the direct
potentiometry were off (in the tens instead of the hundreds), due to a possible calibration error,
so that is why the difference was so significant. If the readings has been what we expected, a
significant difference would likely still be present, but not to such a large extent.
6)
According to Encyclopedia Britannica (2014), the concentration of calcium in seawater is
approximately 400ppm. My experimental concentrations were 19.67ppm, 240.74ppm, and
200.08ppm, all of which are lower than the literature value. Waters receive their calcium
concentrations from dissolved rocks and from coral (Encyclopedia Britannica 2014). Vancouver
is known for having relatively soft (low calcium concentration) waters, so perhaps it is due to
less dissolved rocks such as limestone in the waters. Seasons can also affect the concentration,
but not to that large of an extent.
7)
Of the three methods, I believe the colorimetric titration is the most reliable. Direct
potentiometry is not very accurate or precise, and potentiometric titrations, while precise, result
in an earlier endpoint as discussed above. One important consideration is that the endpoint of the
colourimetric titration is not a very obvious one, so it is important to be careful when deciding on
the endpoint. The accuracy and precision depend largely on the ability to accurately determine
the endpoint. A reference color is needed to compare the sample to, and the person judging the
endpoint needs to be confident in their ability. Once the skill level in judging the endpoint is
adequate, then this method is the most accurate. We had never worked with calcon before, so we
were not very confident in our abilities to judge the endpoints. Another factor that can affect the
accuracy and precision of this method is consistency in preparing the analyte. The same volume
of seawater, diethylamine and calcon must be added to each. We were careful to do this, but
human error can occur.

Conclusions
Analysis of seawater is important in environmental chemistry to ensure the wellbeing of
marine life as well as humans. One component of seawater is calcium, which largely contributes

to water hardness, which is an important value to know in many disciplines. The concentration of
calcium ion in seawater can be measured by a variety of ways, including direct potentiometry
and complexometric titration with EDTA. Colorimetric and potentiometric titrations prove to be
more accurate and precise than direct potentiometry. Colorimetric titration has also proved to
give a better estimate of the endpoint than potentiometric titration due to calcon and EDTA
masking a portion of calcium from the electrode. Calcium ion concentration in Wreck Beachs
water is less than that of the average, which is consistent with the fact that Vancouver has softer
waters than many other areas. When determining which methods to use for an analysis, it is
always important to consider what is happening on a molecular level, as this can affect the final
result.

Appendix

A1. Direct Potentiometry Readings

Trial #
1
2
3
4
5
6

Concentration (mg/L)
24.0
20.0
21.2
20.8
15.3
16.7

A2. Complexometric Titration

[EDTA] = 0.01000M
A2.1 Colorimetric Titration
Trial #
1
2
3

Initial Volume EDTA

(mL)
18.11
17.51
18.89

A2.2 Potentiometric Titration

Trial 1
Burette Volume
Reading EDTA
[Ca2+]
(mL)
(mL)
Reading
18.11
0.00
23.6

Final Volume EDTA

(mL)
27.19
26.52
27.97

Total Volume EDTA

(mL)
9.08
9.01
9.08

19
20.02
21.09
22.2
23.11
24.12
25.08
26.1
27.19
28.02
28.12
28.2
28.3
28.49
28.53
28.7
28.9
29.08
30.21
31.1
32.12

0.89
1.91
2.98
4.09
5.0
6.01
6.97
7.99
9.08
9.91
10.01
10.09
10.19
10.38
10.42
10.59
10.79
10.97
12.10
12.99
14.01

21.6
15.8
13.2
9.26
6.77
4.08
1.82
0.158
0.0647
0.0599
0.0597
0.0578
0.0576
0.0568
0.0565
0.0563
0.0522
0.0549
0.0536
0.0534
0.0525

Trial 2
Burette
Reading Volume [Ca2+]
(mL)
(mL)
Reading
17.51
0.00
31.3
18.6
1.09
23.2
19.51
2.00
17.9
20.52
3.01
13.2
21.5
3.99
9.08
22.6
5.09
5.43
23.58
6.07
2.69
24.55
7.04
0.789
25.7
8.19
0.0915
25.8
8.29
0.0793
25.91
8.40
0.0726
26.05
8.54
0.0677
26.21
8.70
0.0643
26.31
8.80
0.0585
26.52
9.01
0.0571
26.63
9.12
0.0559
26.79
9.28
0.0555

26.91
27.1
27.21
27.35
27.44
28.43
29.5
30.6

9.40
9.59
9.70
9.84
9.93
10.92
11.99
13.09

0.0551
0.0548
0.0544
0.0541
0.0539
0.0512
0.0487
0.0465

Trial 3
Burette Volume
Reading EDTA
[Ca2+]
(mL)
(mL)
Reading
18.89
0.00
24.1
19.97
1.08
22.1
21.03
2.14
17.3
22.21
3.32
13.1
23.35
4.46
9.03
24.19
5.30
6.44
25.1
6.21
3.51
26.21
7.32
0.871
26.31
7.42
0.605
26.5
7.61
0.485
26.61
7.72
0.413
26.72
7.83
0.291
26.89
8.00
0.188
27.02
8.13
0.128
27.21
8.32
0.0852
27.3
8.41
0.0769
27.5
8.61
0.0729
27.6
8.71
0.0675
27.71
8.82
0.0641
27.86
8.97
0.0628
27.97
9.08
0.0621
28.07
9.18
0.0586
28.2
9.31
0.0579
28.3
9.41
0.0573
28.41
9.52
0.0571
28.49
9.60
0.0567
29.3
10.41
0.0548
30.3
11.41
0.0521

31.27

12.38

0.0511

A3. Potentiometric End Point First Derivative Plots

Trial 1

First derivative equivalence point determination

of the concentration of Calcium Ions in Seawater
3

ln[Ca2+]/V

2.5
2
1.5
1
0.5
0
0

10

Average Volume EDTA (mL)

Trial 2

12

14

16

First derivative equivalence point determination of

the concentration of Calcium Ions in Seawater
2
1.8
1.6

ln[Ca2+]/V

1.4
1.2
1

0.8
0.6
0.4
0.2
0
0

10

Average Volume EDTA (mL)

12

14

Trial 3

First derivative equivalence point determination

of the concentration of Calcium Ions in Seawater
4

ln[Ca2+]/V

3.5
3
2.5
2
1.5
1
0.5
0
0

Average Volume EDTA (mL)

10

12

14

References
Crompton, T.R. Analysis of Seawater. A Guide for the Analytical and Environmental Chemist, 1st
ed.; Springer: Berlin, Germany, 2006.
Harvey, D. Analytical Chemistry, 2nd ed.; Open Access Creative Commons International
License.; San Francisco, 2008.
Seawater. Encyclopedia Britannica [Online]; Encyclopedia Britannica Inc., 2014.
http://www.britannica.com/EBchecked/topic/531121/seawater (accessed 26 October 2014).