Applications of pH Test in Environmental Engineering

Introduction:pH is a measure of the activity of the (solvated) hydrogen ion. p[H], which measures the hydrogen ion concentration is closely related to, and is often written as pH. Pure water has a pH very close to 7 at 25C. Solutions with a pH less than 7 are said to be acidic and solutions with a pH greater than 7 are basic or alkaline. The pH scale is traceable to a set of standard solutions pH whose pH is established are by international using agreement. Primary standard values determined

a concentration cell with transference, by measuring the potential difference between a hydrogen electrode and a standard electrode such as the silver chloride electrode. Measurement of pH for aqueous solutions can be done with a glass electrode and a pH meter, or using indicators. pH measurements are important in medicine, biology, chemistry,

agriculture, forestry, food science, environmental science, oceanography, civil engineering and many other applications. Definition:pH is defined as minus the decimal logarithm of the hydrogen ion activity, aH+, in a solution.

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Applications:Water has a pH 7 at 25C; this value varies with temperature. When an acid is dissolved in water, the pH will be less than that of pure water. When a base, or alkali, is dissolved in water, the pH will be greater than that of pure water. A solution of a strong acid, such as hydrochloric acid, at concentration 1 mol/dm-3 has a pH of 0. A solution of a strong alkali, such as sodium hydroxide, at concentration 1 mol/dm-3, has a pH of 14. Thus, measured pH values will lie mostly in the range 0 to 14. Since pH is a logarithmic scale, a difference of one pH unit is equivalent to a tenfold difference in hydrogen ion concentration. The pH of an aqueous solution of a salt such as sodium chloride is slightly different from that of pure water, even though the salt is neither acidic not basic. This is because the hydrogen and hydroxide ions activity is dependent on ionic strength. pH in nature:pH-dependent plant pigments that can be used as pH indicators occur in many plants, including hibiscus, red cabbage and red wine. The juice of citrus fruits is acidic because of the presence of citric acid. Other carboxylic acids occur in many living systems. For example, lactic acid is produced by muscle activity. The state of protonation of phosphate derivatives, such as ATP is pH-dependent. The functioning of the oxygen-transport enzyme hemoglobin is affected by pH in a process known as the Root effect. Seawater:The pH of seawater plays an important role in the ocean's carbon cycle, and there is evidence of ongoing ocean acidification caused by carbon dioxide emissions. However, pH measurement is complicated by the chemical properties of seawater, and several distinct pH scales exist in chemical oceanography.

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As part of its operational definition of the pH scale, the IUPAC defines a series of buffer solutions across a range of pH values. These solutions have a relatively low ionic strength (~0.1) compared to that of seawater (~0.7), and, as a consequence, are not recommended for use in characterizing the pH of seawater, since the ionic strength differences cause changes in electrode potential. To resolve this problem, an alternative series of buffers based on artificial seawater was developed. This new series resolves the problem of ionic strength differences between samples and the buffers, and the new pH scale is referred to as the total scale, often denoted as pHT. The total scale was defined using a medium containing sulfate ions. These ions experience protonation, H+ + SO42 HSO4, such that the total scale includes the effect of both protons (free hydrogen ions) and hydrogen sulfate ions: [H+]T = [H+]F + [HSO4] Living systems:pH in living systems

Compartment

pH

Gastric acid Lysosomes

1 4.5

Granules of chromaffin cells 5.5 Human skin 5.5

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Urine Pure H2O at 37 C Cytosol Cerebrospinal fluid (CSF) Blood Mitochondrial matrix Pancreas secretions

6.0 6.81 7.2 7.3 7.347.45 7.5 8.1

The pH of different cellular compartments, body fluids, and organs is usually tightly regulated in a process called acid-base homeostasis. The most common disorder in acid-base homeostasis isacidosis, which means an acid overload in the body, generally defined by pH falling below 7.35. Alkalosis is the opposite condition, with blood pH being excessively high. The pH of blood is usually slightly basic with a value of pH 7.365. This value is often referred to as physiological pH in biology and medicine. Plaque can create a local acidic environment that can result in tooth decay by demineralization. Enzymes and other proteins have an optimum pH range and can become inactivated or denatured outside this range.

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References:1) Bates, Roger G. Determination of pH: theory and practice. Wiley, 1973. 2) Covington, A. K.; Bates, R. G.; Durst, R. A. (1985). "Definitions of pH scales, standard reference values, measurement of pH, and related terminology". Pure Appl. Chem. 57 (3): 531 542.DOI:10.1351/pac198557030531. 3) Sorensen, S. P. L., Enzymstudien. II, ber die Messung und die

Bedeutung der Wasserstoffionenkonzentration bei enzymatischen Prozessen, Biochem. Zeitschr., 1909, vol. 21, pp. 131304. Two other
publications appeared in 1909 one in French and one in Danisc 4) http://en.wikipedia.org/wiki/PH

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Guideline Value of pH for Drinking Water

General Description:The pH of a solution is the negative common logarithm of the hydrogen ion activity: pH = -log (H+) In dilute solutions, the hydrogen ion activity is approximately equal to the hydrogen ion concentration. The pH of water is a measure of the acid base equilibrium and, in most natural waters, is controlled by the carbon dioxidebicarbonatecarbonate equilibrium system. An increased carbon dioxide concentration will therefore lower pH, whereas a decrease will cause it to rise. Temperature will also affect the equilibrium and the pH. In pure water, a decrease in pH of about 0.45 occurs as the temperature is raised by 25 C. In water with a buffering capacity imparted by bicarbonate, carbonate, and hydroxyl ions, this temperature effect is modified. *The pH of most raw water lies within the range 6.58.5. Analytical Methods:The pH of an aqueous sample is usually measured electrometrically with a glass electrode. Temperature has a significant effect on pH measurement.

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Relationship with Water Quality Parameters:The pH is of major importance in determining the corrosivity of water. In general, lower the pH, higher is the level of corrosion. However, pH is only one of a variety of factors affecting corrosion. Effects on Laboratory Animals:When solutions differing in pH were injected into the abdominal skin of mice, skin irritation was manifested at pH 10 after 6 h. In the rabbit, intracutaneous skin irritation was observed above pH 9.0. In addition, a pH above 10 has been reported to be an irritant to the eyes of rabbits. No significant eye effects were reported in rabbits exposed to water of pH 4.5. Effects on Humans:Exposure to extreme pH values results in irritation to the eyes, skin, and mucous membranes. Eye irritation and exacerbation of skin disorders have been associated with pH values greater than 11. In addition, solutions of pH 1012.5 have been reported to cause hair fibers to swell. In sensitive individuals, gastrointestinal irritation may also occur. Exposure to low pH values can also result in similar effects. Below pH 4, redness and irritation of the eyes have been reported, the severity of which increases with decreasing pH. Below pH 2.5, damage to the epithelium is irreversible and extensive. In addition, because pH can affect the degree of corrosion of metals as well as disinfection efficiency, it may have an indirect effect on health. Conclusions:Although pH usually has no direct impact on water consumers, it is one of the most important operational water-quality parameters. Careful attention to pH control is necessary at all stages of water treatment to ensure satisfactory water clarification and disinfection.

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For effective disinfection with chlorine, the pH should preferably be less than 8. The pH of the water entering the distribution system must be controlled to minimize the corrosion of water mains and pipes in household water systems. Failure to do so can result in the contamination of drinking-water and in adverse effects on its taste, odour, and appearance. The optimum pH will vary in different supplies according to the composition of the water and the nature of the construction materials used in the distribution system, but is often in the range 6.59.5. Extreme pH values can result from accidental spills, treatment breakdowns, and insufficiently cured cement mortar pipe linings. No health-based guideline value is proposed for pH. References:1) American Public Health Association. Standard methods for the examination of water and wastewater, 17th ed. Washington, DC, 1989. 2) http://www.who.int/water_sanitation_health/dwq/chemicals/en/ph.pdf

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Calibration
Definition:Calibration is a comparison between measurements one of known magnitude or correctness made or set with one device and another measurement made in as similar a way as possible with a second device. The device with the known or assigned correctness is called the standard. The second device is the unit under test, test instrument, or any of several other names for the device being calibrated. Calibration Process:The calibration process begins with the design of the measuring instrument that needs to be calibrated. The design has to be able to "hold a calibration" through its calibration interval. In other words, the design has to be capable of measurements that are "within engineering tolerance" when used within the stated environmental conditions over some reasonable period of the time. Having of a design with these characteristics increases likelihood the actual measuring

instruments performing as expected. The exact mechanism for assigning tolerance values varies by country and industry type. The measuring equipment manufacturer generally assigns the measurement tolerance, suggests a calibration interval and specifies the environmental range of use and storage. The using organization generally assigns the actual calibration interval, which is dependent on this specific measuring equipment's likely usage level. A very common interval in the United States for 812 hours of use 5 days per week is six months. That same instrument in 24/7 usage would generally get a shorter interval. The assignment of calibration intervals can be a formal process based on the results of previous calibrations.
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The next step is defining the calibration process. The selection of a standard or standards is the most visible part of the calibration process. Ideally, the standard has less than 1/4 of the measurement uncertainty of the device being calibrated. When this goal is met, the accumulated measurement uncertainty of all of the standards involved is considered to be insignificant when the final measurement is also made with the 4:1 ratio. This ratio was probably first formalized in Handbook 52 that accompanied MIL-STD-45662A, an early US Department of Defense metrology program specification. It was 10:1 from its inception in the 1950s until the 1970s, when advancing technology made 10:1 impossible for most electronic measurements. Maintaining a 4:1 accuracy ratio with modern equipment is difficult. The test equipment being calibrated can be just as accurate as the working standard. If the accuracy ratio is less than 4:1, then the calibration tolerance can be reduced to compensate. When 1:1 is reached, only an exact match between the standard and the device being calibrated is a completely correct calibration. Another common method for dealing with this capability mismatch is to reduce the accuracy of the device being calibrated. Quality:To improve the quality of the calibration and have the results accepted by outside organizations it is desirable for the calibration and subsequent measurements to be "traceable" to the internationally defined measurement units. Establishing traceability is accomplished by a formal comparison to a standard which is directly or indirectly related to national standards (NIST in the USA), international standards, or certified reference materials. Quality management systems call for an effective metrology system which includes formal, periodic, and documented calibration of all measuring instruments. ISO 9000 and ISO 17025 sets of standards
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require that these traceable actions are to a high level and set out how they can be quantified. Instrument calibration:Calibration can be called for: 1) With a new instrument 2) When a specified time period is elapsed 3) When a specified usage (operating hours) has elapsed 4) When an instrument has had a shock or vibration which potentially may have put it out of calibration 5) Sudden changes in weather 6) Whenever observations appear questionable In general use, calibration is often regarded as including the process of adjusting the output or indication on a measurement instrument to agree with value of the applied standard, within a specified accuracy. For example, a thermometer could be calibrated so the error of indication or the correction is determined, and adjusted (e.g. via calibration constants) so that it shows the true temperature in Celsius at specific points on the scale. This is the perception of the instrument's end-user. However, very few instruments can be adjusted to exactly match the standards they are compared to. For the vast majority of calibrations, the calibration process is actually the comparison of an unknown to a known and recording the results. References:1) Crouch, Stanley & Skoog, Douglas A. (2007). Principles of Instrumental Analysis. Pacific Grove: Brooks Cole. ISBN 0-495-01201-7. 2) http://en.wikipedia.org/wiki/Calibration

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Factors affecting the pH of Natural Water

Natural Factors:a) Desorption of Carbon Dioxide:Plant growth and organic material found within a body of water affect the amount of carbon dioxide released into the water. Decomposition of plants is a process responsible for releasing carbon dioxide and ultimately forming carbonic acid when combined with water. Despite being weak, carbonic acid in large quantities will result in a lower effluent pH. b) Eutrophication:Eutrophication focuses on the process of aging or increasing productivity of a body of water. A young, clean lake, for instance, is still in the early stages of eutrophication. It is oligotrophic, exhibiting insufficiency in nutrients; this means the lake will be basic, related to the pH balance. As the lake ages, it accumulates materials from runoff and pollution, sewage often being the main source. This aging renders the lake acidic. c) Bedrock:Basic bedrocks, such as dolomite, limestone and calcite, have water with a basic pH level. Calcite in bedrock triggers the release of carbonates, which in turn increases water alkalinity, ultimately raising the pH. In contrast, sulfide minerals, quartz and granite will bestow an acidic or significantly lower pH to water. Runoff water from marshes and forests is
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often slightly acidic, since decaying vegetation in those areas have organic acids present. Non-Natural Factors:a) Waste-Water Precipitation:Communities, individuals and industries that dump chemicals into the water create chemical aberrations affecting the pH in water. The wastewater to be discharged either directly into a body of water or a local wastewater treatment plant, the former having the ability to alter external bodies of water based of the pH value of the waste. b) Acid Precipitation:Another factor that affects water pH is acid precipitation. Chemical compounds, such as sulfur dioxide and nitrogen oxide released by coalfired power plants and automobile exhausts, pollute the air. Traveling far from their place of origin, they eventually combine with water vapor to form nitric acid and sulfuric acid. The product can be acid rain and snow, which can potentially cause serious environmental issues, one of which can be affecting the pH of natural water supplies. References:1)http://www.ehow.com/info_8620998_natural-factors-affect-phwater.html 2) www.pure-aqua.com

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