Titles 043806
Titles 043806
WATER
ABSTRACT
The determination of dissolved oxygen (DO) in water samples is essential for assessing water
quality and biological processes. This experiment employed the Azide Modification of the
Winkler Method, an iodometric titration technique, to measure DO levels accurately. Alkalinity,
pH and temperature of the water sample were also determined. The method involved the
addition of manganese sulfate and alkali-iodide-azide reagent to a water sample, forming a
precipitate of manganous hydroxide, which was then oxidized by DO. Upon acidification, the
oxidized manganese released iodine equivalent to the DO content, which was titrated with
mg
sodium thiosulfate using starch as an indicator. The results showed that DO was 2.416
L
(calculated using equation 1), temperature was 24.4°C, pH was 7.83 and alkali used was 1.5mL,
see results/appendix. This water sample was unsuitable for direct use in a boiler without proper
treatment. The high DO level and low alkalinity increases the risk of corrosion, while high pH is
slightly too low for optimal boiler performance. Proper treatment, including pH, adjustment,
oxygen removal, and alkalinity control is required. The final DO concentration was calculated
based on the titration results. The only downside of the experiment was over titration and poor
sampling leading to higher DO values than actual concentration in the water body.
INTRODUCTION
Dissolved oxygen (DO) is a critical parameter in assessing water quality, as it influences aquatic
life and chemical processes in water bodies. Oxygen enters water through diffusion from the
atmosphere and as a byproduct of photosynthesis by aquatic plants. The concentration of DO
varies depending on temperature, salinity, and biological activity (Chapman & Kimstach, 1996).
Insufficient DO levels can lead to hypoxia, negatively impacting aquatic organisms and
disrupting ecosystems (Wetzel, 2001). Therefore, accurate measurement of DO is essential for
monitoring environmental health and assessing water pollution levels.
The Winkler method, developed by Ludwig Winkler in 1888, is one of the most reliable
titrimetric procedures for DO determination. It involves the oxidation of manganous hydroxide
in an alkaline medium, which subsequently reacts with iodide in an acidic solution, liberating
iodine equivalent to the DO content (APHA, 2017). The released iodine is then titrated with a
standard sodium thiosulfate solution, providing a precise measurement of oxygen concentration.
This method is widely used due to its accuracy and suitability for various water samples,
including freshwater, seawater, and wastewater (Grasshoff, Kremling & Ehrhardt, 2009).
However, the presence of nitrites (NO₂⁻) in wastewater samples can interfere with the standard
Winkler method, leading to errors in DO determination. To overcome this issue, the azide
modification is employed, where sodium azide (NaN₃) is added to eliminate nitrite interference
(Sawyer, McCarty & Parkin, 2003). This modification is particularly useful for analyzing
wastewater, industrial effluents, and polluted natural waters, ensuring more accurate results.
Additionally, the method requires careful reagent preparation and sample handling to prevent
oxygen contamination, which could affect the final readings.
The objective of this experiment is to determine the DO concentration in water samples using the
Azide Modification of the Winkler Method. The study aims to demonstrate the importance of
DO in water quality assessment and evaluate the effectiveness of the azide modification in
minimizing interferences as well as. By applying this method, researchers and environmental
scientists can obtain reliable data for monitoring aquatic ecosystems, wastewater treatment
efficiency, and overall water quality management.
OBJECTIVES
MAIN OBJECTIVE
To measure the dissolved oxygen (DO) in the boiler system ( corrosion and scaling
properties of water).
SPECIFIC OBJECTIVES
THOERY
The determination of dissolved oxygen (DO) in water samples is crucial for assessing water
quality and understanding aquatic ecosystem health. The iodometric method, specifically the
Winkler method, is a widely accepted titrimetric technique for accurate DO measurement. This
method relies on the oxidation of manganous hydroxide [Mn(OH)₂] by dissolved oxygen in an
alkaline medium, forming higher oxidation states of manganese. Upon acidification, the oxidized
manganese reacts with iodide (I⁻), releasing iodine (I₂) in proportion to the DO content of the
sample. The released iodine is then titrated with a sodium thiosulfate (Na₂S₂O₃) solution, using
starch as an indicator, to determine the exact DO concentration.
The azide modification of the Winkler method is essential for samples that contain significant
levels of nitrites (NO₂⁻), which can interfere with the reaction and cause errors in DO
measurement. Sodium azide (NaN₃) is added to the reagent mixture to eliminate nitrite
interference by preventing the formation of nitrogenous oxidizing compounds. This modification
ensures accurate DO determination in wastewater, effluents, and natural water sources with high
nitrite concentrations.
Proper reagent preparation is essential for reliable results. The manganese sulfate (MnSO₄)
solution provides the divalent manganese ions required for the reaction. The alkali-iodide-azide
reagent, containing sodium hydroxide (NaOH), potassium iodide (KI), and sodium azide
(NaN₃), maintains the alkaline conditions and prevents nitrite interference. Sulfuric acid
(H₂SO₄) is used to acidify the sample, allowing the oxidation-reduction reactions to proceed. A
sodium thiosulfate (Na₂S₂O₃) solution of known molarity is used for titration, and starch
solution serves as the indicator for endpoint detection.
This method is effective for water quality analysis, particularly in monitoring pollution levels,
wastewater treatment efficiency, and oxygen availability in aquatic environments. By eliminating
interferences from nitrites, the azide modification enhances the accuracy of DO measurements,
making it a reliable technique for environmental and industrial applications. The chemical
equations for the reactions described above are:
REAGENT PREPARATION
Apparatus:
Reagents:
Sample Collection:
A clean bottle was submerged in a fish pond to collect the water sample.
The stopper was opened underwater to prevent air contamination and the bottle was
carefully sealed with the sample.
The pH and temperature were measured using the pH and temperature meter.
The sample was then transferred to a 300mL biochemical oxygen demand (BOD) bottle.
Reagent Addition:
1.0mL of manganese sulfate (MnSO₄) solution was added to the sample in a 300mL
biochemical oxygen demand (BOD) bottle, followed by 1.0mL of alkali-iodide-azide
reagent.
the bottle was carefully closed with a stopper and put to settle, ensuring no air bubbles
enter.
The bottle was inverted a few times to mix thoroughly.
The precipitate was then allowed to settle until it occupied about half of the bottle
volume.
Acidification:
1.0mL of concentrated sulfuric acid (H₂SO₄) was added to dissolve the precipitate.
The bottle was swirled gently to ensure complete dissolution of the flocs.
Where;
RESULTS
From group 1 to 6, the volume of Sodium thiosulphate (Na₂S₂O₃) used was calculated using a
factor of 6 and group 7 used a factor of 2 to obtain the amount that would have reacted with
sample volume (bottle volume) of 300mL (VS = 298mL) and 100mL (VS = 98mL) since only
50mL of acidified sample was titrated. The DO was calculated using equation 1. See appendix
for detailed calculations. The results were tabulated in table 1 below,
Table 1.0. summary table of experimental calculated for dissolved oxygen and alkalinity tests
Temperature ranged from 23.6°C to 25.2°C, indicating relatively stable water conditions.
pH values varied between 6.925 and 8.620, showing a slightly neutral to alkaline range.
Dissolved oxygen (DO) concentrations fluctuated significantly, with the lowest recorded
at 1.477mg/L and the highest at 13.289mg/L, suggesting differences in oxygen
availability across samples.
Alkalinity levels showed considerable variation, ranging from 30 mg/L to 138mg/L,
indicating differing buffering capacities of the water samples.
Overall, the data suggested a correlation between pH, DO, and alkalinity, with higher alkalinity
levels generally supporting higher DO concentrations. The variability in DO and alkalinity levels
might be due to factors such as water temperature, biological activity, or sampling
inconsistencies as well as over-titration.
DISCUSION
The experimental data indicates that there were variations in pH, temperature, alkalinity, and
dissolved oxygen across the water samples. the pH values ranged from 6.925 to 8.620,
suggesting that some samples were slightly acidic while others were alkaline. Group 3 had the
lowest pH (6.925), making it more prone to corrosion, whereas Group 2 had the highest pH
(8.620), which could lead to scaling issues.
Regarding temperature, the values varied between 23.6°C and 25.2°C, with Group 2 having the
highest temperature (25.2°C), which might have reduced dissolved oxygen levels and increase
the likelihood of biological activity in the water. On the other hand, Group 5 had the lowest
temperature (23.6°C), which might have contributed to slightly higher oxygen retention.
the alkalinity values based on the used volume ranged from 1.5 mL to 6.5 mL, indicating
differences in buffering capacity. The lowest alkalinity (1.5mL) was found in Group 4, which
suggested that this sample had less resistance to pH fluctuations, making it more susceptible to
acidic conditions. In contrast, the highest alkalinity (6.9 mL) was recorded in Group 3, indicating
a stronger buffering capacity, which could reduce corrosion but increase the risk of scaling.
In terms of dissolved oxygen (DO), the values varied significantly, ranging from 1.477mg/L to
13.289mg/L. It was noted that Group 3 had the highest DO level (13.289mg/L), which suggested
that the water was highly oxygenated, possibly due to aeration or cooler conditions. Meanwhile,
Group 7 recorded the lowest DO level (1.477mg/L), which could indicate stagnant water,
pollution, or a high rate of oxygen consumption by biological processes.
Furthermore, poor sampling techniques and over-titration might have affected the results.
Improper sample collection could have led to contamination, exposure to air, or changes in pH
and DO levels before analysis. It was also noted that overuse of thiosulphate in titration might
have resulted in inaccurate DO measurements, while excess acid or base titration could have
affected the recorded pH and alkalinity values.
Finally, some water samples had a higher risk of corrosion, particularly Group 3, which had a
low pH (6.925) and high DO (13.289mg/L). Group 2 and Group 6 had mild scaling tendencies
due to their higher pH and alkalinity levels.
In a boiler system, pH, temperature, alkalinity, and dissolved oxygen are critical factors that
determine efficiency, scaling, and corrosion risks. The experimental data provides valuable
insights into how these parameters interact and their potential effects in a boiler system.
1. pH Analysis
The pH values in the experiment ranged from 6.925 (Group 3) to 8.620 (Group 2).
Ideal Boiler pH: Boiler water should typically be between 8.5 and 12 to minimize both acidic
corrosion and alkaline scaling.
Impact of Low pH: A low pH, like in Group 3 (6.925), indicates acidic conditions, which can
lead to corrosion of boiler components, including pipes and tubes.
Impact of High pH: A high pH, like in Group 2 (8.620), may lead to scale formation, especially
when combined with high alkalinity.
Recommendation: A pH range of 8.5 to 10.5 should be maintained in boiler water using
chemical treatment such as sodium hydroxide (NaOH) or phosphate conditioning.
2. Temperature Effects
The temperature of the water samples ranged between 23.6°C (Group 5) and 25.2°C (Group 2).
Boiler Systems Operate at Higher Temperatures: In a real boiler system, temperatures can exceed
150 - 600°C, which greatly increases scaling and corrosion risks.
Effect of Temperature on Dissolved Oxygen: Higher temperatures reduce the solubility of
oxygen, which is beneficial since oxygen causes corrosion. However, if oxygen remains in the
system, corrosion can be accelerated at high temperatures.
Recommendation: The water should be preheated and treated with oxygen scavengers (e.g.,
sodium sulfite or hydrazine) before entering the boiler to reduce dissolved oxygen and prevent
corrosion.
CONCLUSION
The findings obtained showed that the water samples exhibited variations in pH, temperature,
alkalinity, and dissolved oxygen, which influenced their potential for corrosion and scaling. The
low pH and high dissolved oxygen levels increased corrosion risk, particularly in Group 3, while
high pH and alkalinity contributed to scaling, as seen in Group 2 and Group 6. Additionally, poor
sampling techniques and over-titration may have affected the accuracy of the results, leading to
possible discrepancies. The values obtained (group 4) had moderate characteristics. While the
alkalinity was the lowest among all groups, suggesting lower buffering capacity, pH and DO
levels were relatively balanced, indicating a lower risk of extreme scaling or corrosion. The
water samples were not suitable for use in a boiler system directly due to high, dissolved oxygen,
low alkalinity and low PH values which can accelerate corrosion due to low buffering capacity.
Overall, the experiment was successful. And the analysis procedure gave insights as to the
methodology of determining dissolved oxygen, alkalinity, temples and pH of water sample.
RECOMMENDATIONS
pH Adjustment: The water with low pH (such as Group 3 at 6.925) should be treated with
alkalinity boosters (e.g., lime or soda ash) to reduce corrosion, while high pH samples
(such as Group 2 at 8.620) should be monitored to prevent scaling.
Alkalinity Control: Since Group 4 had the lowest alkalinity (1.5mL), it was
recommended that buffering agents be added to prevent rapid pH fluctuations, which
could lead to instability in water quality.
Dissolved Oxygen Regulation: High DO levels (such as Group 3 at 13.289mg/L) need to
be reduced by using de-aeration methods or chemical oxygen scavengers to minimize
corrosion risks in pipelines. Meanwhile, low DO samples (such as Group 7 at 1.477mg/L)
should be aerated to improve water quality and prevent stagnation.
Improved Sampling Techniques: Proper sampling procedures be followed to prevent
exposure to air, contamination, or temperature fluctuations, which could affect pH and
DO readings.
Accurate Titration Practices: Since over-titration might have affected alkalinity and DO
results, standardized titration techniques be used with proper endpoint detection to
improve accuracy.
REFERENCE
Mugala, A.N., Chipili, P. and Musonda, J., 2023. Chemical Engineering Lab and Project
Manual for DCE 240 and CE 430. 4th ed. Kitwe: Copperbelt University, School of Mines
and Mineral Sciences, Chemical Engineering Department.
American Public Health Association (APHA) (2017) Standard Methods for the
Examination of Water and Wastewater. 23rd edn. Washington, D.C.: APHA.
Chapman, D. & Kimstach, V. (1996) Selection of water quality variables. In: Chapman,
D. (ed.) Water Quality Assessments: A Guide to the Use of Biota, Sediments and Water
in Environmental Monitoring. 2nd edn. London: UNESCO/WHO/UNEP, pp. 59–126.
Grasshoff, K., Kremling, K. & Ehrhardt, M. (2009) Methods of Seawater Analysis. 3rd
edn. Weinheim: Wiley-VCH.
Sawyer, C. N., McCarty, P. L. & Parkin, G. F. (2003) Chemistry for Environmental
Engineering and Science. 5th edn. New York: McGraw-Hill.
APPEDIX
Section 1: Calculation of the concentration of DO in the sample for each group using the
following formula:
DO ( mgL )= V × MVs−2
× 8 ×1000
Where;
V = Volume of sodium Thiosulphate used
GROUP 1
DO ( mgL )= V × MVs−2
× 8 ×1000
V is determined as follows:
0.6 × 300
V= = 3.6ml
50
M=0.025M
Vs.=300ml
GROUP 2
DO ( mgL )= V × MVs−2
× 8 ×1000
V is determined as follows:
0.45 ×300
V= = 2.7ml
50
M=0.025M
Vs.=300ml
DO ( mgL )= V × MVs−2
× 8 ×1000
V is determined as follows:
3.3 ×300
V= = 19.8ml
50
M=0.025M
Vs.=300ml
DO ( )
mg 19.8× 0.025 ×8 ×1000
L
=
300−2
= 13.289
mg
L
GROUP 4
DO ( mgL )= V × MVs−2
× 8 ×1000
V is determined as follows:
0.6 × 300
V= = 3.6ml
50
M=0.025M
Vs.=300ml
GROUP 5
DO ( mgL )= V × MVs−2
× 8 ×1000
V is determined as follows:
2 ×300
V= = 12.0ml
50
M=0.025M
Vs.=300ml
GROUP 6
DO ( mgL )= V × MVs−2
× 8 ×1000
V is determined as follows:
2.5 ×300
V= = 15ml
50
M=0.025M
Vs.=300ml
GROUP 7
DO ( mgL )= V × MVs−2
× 8 ×1000
V is determined as follows:
1.1 ×100
V= = 2.2ml
50
M=0.025M
Vs.=100ml
SIN: 21170496
INDUSTRIAL SAFEFY
DICSUSSION QUESTIONS
Dissolved oxygen (DO) refers to the amount of free, non-compound oxygen present in
water, which is essential for the survival of aquatic organisms. It is one of the most
important indicators of water quality, as it directly influences the biological and chemical
processes within an aquatic ecosystem (Chapman & Kimstach, 1996). High DO levels
promote biodiversity and support aerobic life, while low DO levels can lead to hypoxia,
negatively affecting fish, invertebrates, and microbial communities (Wetzel, 2001).
Additionally, DO plays a crucial role in wastewater treatment processes and industrial
applications, where it is necessary for aerobic decomposition of organic matter and
corrosion control.
DO levels typically vary with water depth due to differences in light penetration,
temperature, and biological activity. In shallow waters, DO is usually higher because of
greater surface interaction with the atmosphere and photosynthetic activity by aquatic
plants. However, as depth increases, DO concentrations tend to decrease due to limited
light penetration, reduced photosynthesis, and increased oxygen consumption by
decomposers at the bottom (Wetzel, 2001). In stratified water bodies, an oxygen-deficient
layer known as the hypolimnion can form at deeper levels, particularly in eutrophic lakes.
Pollution, especially from organic waste and nutrients, can significantly reduce DO levels
in water. When organic matter enters a water body, microorganisms decompose it,
consuming large amounts of oxygen in the process. This can lead to oxygen depletion,
causing hypoxic or anoxic conditions that are harmful to aquatic life (Sawyer et al.,
2003). High levels of nitrogen and phosphorus from agricultural runoff can lead to
eutrophication, where excessive algal blooms consume oxygen upon decomposition,
further reducing DO levels and leading to fish kills.
DO plays a crucial role in industrial water systems, particularly in scaling and corrosion.
In high-DO environments, oxygen can react with dissolved iron and other metals, leading
to corrosion of pipes and infrastructure. This is a significant problem in water distribution
systems and industrial cooling towers, where excessive corrosion can lead to equipment
failure and costly maintenance (Grasshoff, Kremling & Ehrhardt, 2009). On the other
hand, very low DO levels can cause reducing conditions, promoting the dissolution of
metals and leading to scaling, which affects water flow and heat exchange efficiency in
industrial settings.