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    Topic 2B Alkalinity

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    WATER QUALITY: DEHNITIONS, CHARACTERISTICS, AND PERSPECTIVES 23 react The slater 8 solution of solids ae accelerated by increased temperatures. Because biologie nS, 0% the other hand, devteass at elevated temperatures Pendent on anne oxation of organics in streams and impoundments is de- iS undesicable, Tens SUPPL of dissolved oxygen, decrease in oxygen solubility levels 1s shown in Tee between temperature and dissolved oxygen Tease “3 of the appendix. water inercanes yas fet other physical properties of water. The viscosity of OCCURS at 4°C- and en ee eINR temperature. The maximum density of water Phenomenon among her eieases OM either side ofthat temperature, a unique in platikescie sited igus Both temperature and density have a subtle effect temperatureand deo rSanisms in natural water systems. The relationship of and density to stratification of impoundments is discussed in Chap. 3. Chemical Water-Quality Parameters Ww: ; ie ie shee the universal solvent, and chemical parameters are related Ruorides aya babiltes of water. Tota dissolved solids alkalinity, hardness Tecan IS. organics, and nutrients are chemical parameters of concern in quality management. The following review of some basic chemistry related to solutions should be helpful in und lerstai 7 parameters nding subsequent discussions of chemical 2-7 CHEMISTRY OF SOLUTIONS An atom is the smallest unit of each of the elements. Atoms are building blocks from which molecules of elements and compounds are constructed. For instance, two hydrogen atoms combine to form a molecule of hydrogen gas: H+H — H, Adding one atom of oxygen to the hydrogen molecule results in one molecule of the compound water: H,+0 —— H,0 A relative mass has been assigned to a single atom of each element based on a mass of 12 for carbon. The sum of the atomic mass of all the atoms in a molecule is the molecular mass of that molecule. The atomic mass of hydrogen is | and the atomic mass of oxygen is 16. Thus, the molecular mass of the hydrogen molecule is 2and the molecular mass of water is 18. A mole of an element or compound is its molecular mass expressed in common mass units, usvally grams. A mole of hydrogen is 2.g, while a mole of water is 18 g. One mole of a substance dissolved in sufficient water to make one liter of solution is called a one molar solution Bonding of elements into compounds is sometimes accomplished by electrical forces resulting from transferred electrons. When these compounds dissociate 24 waren in water, they produce species wi chloride: opposite charges. An example 15 oq, m NaCl === Nat + Cl” 1s, Positively charged ions are called the charged species are called ion oa fn barat Sarged ions are called anions. The number of positive Siow, ait equal the number of negative charges (0 presen electrical neutratiy (2° hemical compound. The number of Charges on an On referred to as the vain ® Of that ion. Thus the valence of sodium (Na*) is 1, while the valence of cajgr"* (Ca®*)is 2. Some’ ‘compounds, called radicals, also possess charges. An exam le op ANionig cationic radical is ammonium (NH,"), while carbonate (CO,?>) is an radical ions or radicals react with each other to form new compound reactions may not always proceed on a one-to-one basis as was the case for ea the react, They do. however proceed on an equivalence basis that can be a cectroneutrality. Technically. the equivalence ofan element or radicals elt toe ero hydrogen atoms that element or radical can hold in comb fi as he Meplace na faction, In most case. the equivalence of anion isthe aa spre vale ofits valence. An eguialent ofan element or radical is aoe estar mas divided by i equivalence. A miliequivulent is the mole mole exed in miligrams divided by the equivalence and is often — a eaaterchemisity because concentrations of dissolved substances a Tore dften in the milligrams per liter range. Compounds are formed by the: eae are arnts or radials on a one-to-one equivalent bass. The calculation mPination fents is illustrated in Example 2-2 eauiva, Example 22: Calclating equivalents How many grams of cali eae with 90g of carbonate to form calcium carbonate? "um will be required ty Nation, same as MS gram SouuTion ‘Carbonate (CO,?") is aradicel composed of carbon and oxygen. In ocr reson haan seis maaof (Zand avalcace of -4. whee eae saromic mass of 16 and a valence of ~ 2. Therefore, the radical has a total eons ‘=? and an equivalence of 2. One equivalent of carbonate is, ‘valence of 12+ X16) y= prequiv 12. Thecalcium ion has an atomic mass of 40 and a valence of + 2;therefe of calcium is é eee teat 7 = Deeauiv 3, The number of equivalents of calcium must equal the number of pase of equivalents ofcarbo- 98 _ equiv of iggy BEA fcaronae “Therefore. 3 equiv x 20 glequiv » 60 g of calcium, and that amount wi react with 90g of carbonate. oe WATER QUALITY: DEFINITIONS, CHARACTERISTICS, AND PERSPECTIVES. 25 Equivalents are very important in water chemistry. In addition to being useful in calculating chemical quantities for desired reactions in water and wastewater {reaiment. equivalents also provide a means of expressing various constituents of dissolved solids in a common term, An equivalent of one substance is chemically equal to an equivalent of any other substance. Therefore, the concentration of substance A can be expresscd as an equivalent concentration of substrate B by the following method wba 2 Gequisya * WEAUIVIB = (B/L)A expressed as B (22) Historically. constituents of dissolved solids have been reported in terms of equivalent calcium carbonate concentrations. The following example illustrates this technique. Example 2-3: Determining equivalent concentrations What is the equivalent calcium carbonate concentration of (a) 117 mgyL of NaCl and (4) 2 x 10" mol of NaCI? SoutTion (a) 1. One equivalent of calcium carbonate is 4+ 124 ¥16) 5 '= 50 giequiv = 50,000 mg/equiv = 50 mg/mequiv 2. One equivalent of sodium chloride is 234355 : 5S 585 plequiv = $8.5 me/mequiv 3. By Eq. (2-2) 17 mel, 50 mgimequiv = 100 mg/L of NaCl 385 mg/mequiv * 5° ™B/mequiv = 100 mgiL of NaCl as CaCO, (0) 1. One mole of a substance divided by its valence is one equivalent. 2x 10°? mol/L Fovegun = 2 * 10" equivt 2. Thus, 2 x 10°? equiv/L x 50,000 mg/equiv = 100 mg/L Many solid substances, particularly those with crystalline structure, ionize readily in water. Water may or may not be a chemical reactant in the process. In Eq. (2-3), water is a reactant, while in Eq. (2-4) itis not. CaO + H,0 —— Ca?* + 20H" 23) NaCl + HO Nat +Cl- +H,0 (24) When water is not a reactant, it is customary to omit it from the equation 26 waTeR The double arrows in Eq, (2-4) indicate a reversible condition. That is, solid form (NaCl) may be dissociating into its ionic components (dissolution) ie the ionic components may be recombining into the sold form (precpitange When the solid materials first contacted with water the net reaction will betongr, the ionic form. Ifa sulficent mass of sold is preset, a condition of djman equilibrium will be reached in which the rate of dissolution and the rate ot pn ipitation will be exactly equal. At this point. the water is saturated with ih, dissolved species. Conditions of equilibrium can be expressed by the mass action equation, Fo, the generalized reaction A,B, <== xA+5B Solid compound onic components the mass action equation is (APBD _ A.B) @s) The brackets around the ionic and solid species indicate molar concentrations, The K value is an equilibrium constant for a given substance in pure water at a given temperature. ‘At equilibrium, the solid phase does not change concentrations because dissolution and precipitation are equal. Thus [A.B] =K,=const and [A}'[B) = KK, = k,, (2-6) The quantity K,,is known as the solubility product for the ion pair. Ifthe concentra- tion of either or both of the ions is increased, the product of the ionic concentration will exceed the K,, and precipitation will occur to maintain equilibrium conditions The solubility products for several substances common to natural water system are given in Table 2-3. Use of the solubility product to calculate ionic concentra, tions is illustrated in the following example. Example 2-4: Determining equilibrium concentrations The solubility product for the dissociation of Mg(OH); is shown in Table 2-3 as 9 x 10°". Determine the concent tion of Mg** and OH” at equilibrium, expressed as milligrams per liter of CaCO, Souumion 1. Write the equation for the reaction Mg(OH), === Mg?* + 20H~ 2. The solubility product equation becomes (Mg?*}[OH "P= 9 x 1077 WATER QUALITY: DETINITIONS, CHARACTERISTICS, AND PERSPECTIVES 27 Ura the number of moles of Mg?* resuking from the dissociation, then OH” ‘equal to 2x. Therefore, = ee GIP <9 «198 40 =9 x 19-8 X= 13 « 10°4 mol/l. = Me 2x = 26 x 10 molL = OH 13 x 10°4 mol/L, 3-5 moljequiv — * 50.000 mgvequiv = 130 mgil. of Mg as CaCO 26 x 10 * mol Tmoljequiv % 50.000 mgiequiv = 130 mg/L of OH as CaCO In addition to solid substances, many gases also dissolve in water. Elements from some of these gases may combine with water or with substances in the water to produce compounds or radicals that can be recovered in a solid form, thus becoming a part of the dissolved-solids load. An example is carbon dioxide. CO; +H,0 === H,CO, == H' + HCO, an and HCO, === H' +C0,? (28) Both the bicarbonate (HCO, ~) and carbonate (CO,*> ) are recoverable in solid form ‘Table 2-3 Solubility products of selected ion Kat Significance in Equilibrium equation 28 ‘environmental engineering MgCO, = Mg! + CO, 4x 10° Hardness removal, sealing MgiOH), = Mg? + 20H" 9x 10°! Hardness removal, sealing CaCO, C2" + CO 5% 10° Hardness removal. scaling CaOH); = Ca" + 20H™ 8x 10" Hardness removal 250, 2 Ca?" + 50,7 2 10°? Flue gas desulfurization CulOH), = Cu?” + 20H 2% 10° Heavy metal removal zu OH), = 70?" + 20H~ 3x 10°! Heavy metal removal NuOH), = Ni" + 20H 2x 10° Heavy metal removal CaOH), = CP? + 30H 6 x 10° Heavy metal removal AWOH), = AI! + 30H" 1x 10° Coagulation Fe(OH), = Fe’? + 308° 6 x 107% Coagulation, iron removal, corrosion Fe(OH), = Fe?" + 20H 5x 10°" Coagulation, iron removal, corrosion Mn(OH), == Mn" + 30H" 1x 1073 Manganese removal ‘Ma(OH); = Mn?" + 20H 8 x 10° Manganese removal CPO), = 3C2?* + 2PO.!* 1 10°27 Phosphate removal GaHPO, 2 Ca?" + HPO,' 3x 10°? Phosphate removal CaF, 2 Ca" + 2F 3x10" Fluoridation AgCl== Ag’ + CI” 3x10 Chloride analysis BaSO, == Ba?” + SO,?~ Tx 10! Sulfate analysis Source: Adapted from Sawyer and McCarty. [2-12] 28 water 2-8 TOTAL DISSOLVED SOLIDS The material remaining in the water after filtration for the suspended-solids is left us a solid residue upon analysis is considered to he dissolved. This matersil m evaporation of the water and constitutes # pact of total sols discusse nS 3 Sources action of water on solids, hquids, and "J substances may be organic OF moTBANIC be dissolved in water include minerals, Dissolved material results from the solvent gases. Like suspended material dissolve in nature. Inorgamie substances which may netats and gases. Water may come in contact with these substances the atmo sphere, on surfaces, and within the soil, Materials from the decay products of Negetation, from organic chemicals, and from the organi Masts fe ‘common organic dissolved constituents of water. The solvent capability of water makey tt an ideal means by which waste pr pe carried away from industrial roducts can sites and homes. Impacts Many dissolved substances are undesirable in water. Dissolved minerals, gases. and organic constituents may produce aesthetically displeasing valor, tastes, and adore, Some chemicals may be toxic, and some of the dissolved organic con Shuents have been shown to be carcinogenic. Quite often, two or more dissolved Substances. especially organic Substances and members of the halogen group will combine to form a compound whose characteristics are more ubjectionable than those of either of the original materials Not all dissolved substances are undesirable in water. For example. essentially pure, distilled water has a lat taste. Additionally, water has an equilibrium state Mrith respect to dissolved constituents, An undersaturated water will be “aggres- Give” and will more readily dissolve materials with which it comes in contact. Readily dissolvable material is sometimes added to a relatively pure water 10 reduce its tendency to dissolve pipes and plumbing Measurement |A direct measurement of total dissolved solids can be made by evaporating to dryness a sample of water which has been filtered to remove the suspended solids ‘The remaining residue is weighed and represents the total dissolved solids (1 DS) in the water. The TDS is expressed as milligrams per liter on a dry-mass basis. “The organic and inorganic fractions can be determined by firing the residue at 600°C as discussed in Sec. 2-2. ‘An approximate analysis for TDS is often made by determining the electrical conductivity of the water. The ability of a water to conduct electricity, known as the ves 29 WATER QUALITY: DEFINITIONS, CHARACTERISTICS, AND PERSPECT? specific conductance. is a function of its ionic strength, Specific conductance 1S measured by a conductivity meter employing the Wheatstone bridge principle The standard procedure is to measure the conductivity in a cubic-centimeter field at 25°C and express the results in millisiemens per meter (mSim). Unfortunately. specific conductance and concentration of TDS are not related on a one-to-one basis. Only ionized substances contribute to specific conductance. Organic molecules and compounds that dissolve without ionizing are not measured. Additionally, the magnitude of the specific conductance is influenced by the valence of the ions in solution, their mobility, and relative numbers. The temperature also has an important effect, with specific conductance increasing as the water temperature increases. Conversion of units to milligrams per liter or milliequivalents per liter must be made by use of an appropriate constant. A multiplier ranging from 0.055 to 0.09 is used to convert millisiemens to milligrams per liter. [2-15] To use specific conductance as a quantitative test. sufficient analysis for fiterable residue must be run to determine the conversion factor. For this reason, specific conductance is most often used in a qualitative sense to monitor changes in TDS occurring in natural streams or treatment processes, Use Because no distinction among the constituents is made, the TDS parameter is included in the analysis of water and wastewater only as a gross measurement of the dissolved material. While this is often sufficient for wastewaters. itis frequently desirable to know more about the composition of the solids in water that is in- tended for use in potable supplies. agriculture, and some industrial processes. ‘When this is the case, tests for several of the ionic constituents of TDS are made. Ton Balance ‘The ions usually accounting for the vast majority of TDS in natural waters are listed in Table 2-4. Those listed under major constituents are often sufficient to Table 2-4 Common ions in natural waters Secondary constituents, ‘Major constituents, 10-1000 mgit 0.01-10.0 mgt, Sodium Iron Calcium Strontium Magnesium Potassium Bicarbonate Carbonate Sulfate Nurate Chloride Fluoride Boron Silica Source: Adapted from Todd. 2-17] 30 waren characterize the dissolved-olids content of water. These are called common tons and are often measured individually and summed on an equivalent basis to represent the approximate TDS. As a check, the sum of the anlout should equal the sum of the cations because electroneutrality must be preserved. A signiicant imbalance suggests that addtional constituents are present OF U8) 20 e107 has been made in the analysis of one or more of the ions. The following example illustrates the ion balance procedure. Example 2-5: Testing for ion balance Tests for 60 water andthe results are shown below. Ifa 10 pereen should the analysis be considered ‘complete? Constituents cat = SSmpL HCO, Mp? = [sme SO? ‘Nat mel smmon ions are fun on a sample of error in the balance is acceptable, Sowvnoy rams per liter to milli 1. Convert the concentrations of cations and anions from mili ‘equivalents per liter and sum them. a eee Cations ‘Anions ta | Come Bay mrvcone)| ton | Conc, Bqiv, Equi cone soe mgimeguiv mea mg/L mglmequis mequivt. ae fs 22% co, | 20 sit 410 mer [18 M3218 so,: | @ 92 125 mf BN 436 a | asst 25 Total ons i 7 2. Calculate percent of error. 49 — 186 £09 — 188 199 = 8% 7386 8% < 10% ‘Therefore, accept analysis. ‘A common ion balance can be displayed conveniently in the form of a bar diagram. A bar diagram for the water in Example 2-5 can be drawn as shown below. mequivjL 0 295s! 42 849 mequiviL 0 410 $35 7.86 ‘WATER QUALITY: DEFINITIONS, CHARACTERISTICS, AND PERSPECTIVES 31 ness and the quantities of chemicals needed for softening, a subject more fully Several ofthe constituents of dissolved solids have properties that necessitate special attention. These constit ! ‘vents include alkalinity, hardness, fuoride, metals, organics, and nutrients 2-9 ALKALINITY Alkalinity is defined as the quantity of ions in water that will react to neutalize hydrogen ions. Alkalinity is thus a measure of the ability of water to neutraline acids. Sources Constituents of alkalinity in natural water systems include CO,?~, HCO,” OH HSO4" HpBOs", HPO”, H.PO,”, HS", and NH,?” [2-3] Thise compounds result from the dissolution of mineral substances in the soil wed atmosphere. Phosphates ‘may also originate from detergents. in. wastewater discharges and from fertilizers and insecticides ftom agricultural land, Hydrogen sulfide and ammonia may be products of microbial decomposition of organic material By far the most common constituents of: carbonate (COs), and hydroxide (OH). n addition to ther mineral origin {hese substances can originate from carbon dioxide, a constituent ofthe atmosphere and a product of microbial decomposition of organic material. These reactions are as follows. alkalinity are bicarbonate (HCO), CO, +H,0 === H,CO,* (dissolved CO, and carbonic acid) (2-9) H,CO;* === H' + HCO,” (bicarbonate) 2-10) HCO,” == Ht +C0,?- (carbonate) Qn COs*" + H,0 == HCO," + OH- (hydroxide) 12) ‘The reaction represented by Eq, (2-12) is a weak reaction: chemically. However, utilization ofthe bicarbonate ion as a carbon source by algae can drive the reaction to the right and result in substantial accumulation of OH~. Water with heavy algal growths often has pH values as high as 9 to 10, Because the reactions represented by the above equations involve hydrogen or hydroxide fons. te relative quantities ofthe alkalinity species are pH dependent, These relationships are shown graphically in Fig. 2-3. 32 waree 80 HOS ey { 20 to 1 H,co;"~] ‘OH 8 pre S57 75 8 oH alinity species vs. pH. Values ae calcu CaCO. (From Saxyer and McCarty (212}) Figure 23 Alki te for water at 25°C containinga ital alkalinity ‘of 100 mail as Impacts In large quantities, alkalinity imparts a bitter taste to water. The principal ob- jection toalaline water however is the reactions that can occur between alkalinity ‘and certain cations in the water. The resultant precipitate can foul pipes and other water-systems appurtenances. Measurement [Alkalinity measurements are made by titrating the water with an acid and de- termining the hydrogen equivalent. Alkalinity is then expressed as milligrams per liter of CaCO. 1f002 N H,SO, is used in the titration, then I mL. of the acid will neutralize | mg of alkalinity as CaCO). Hydrogen ions from the acid react with the alkalinity according to the following equations: H’+0H” === H,0 (2-13) COs" +H* === HCO,” (2-14) HCO," +H* === H,CO, 2-15) WATER QUALITY: DEFINITIONS, CHARACTERISTICS, AND PERSPECTIVES. 33 4 n 10 pi | Teo sncoy Milliiters of titrant Figure 24 Alkalinity tration curve If acid is added slowly to water and the pH is recorded for each addition. @ titration curve similar to that shown in Fig. 2-4is obtained, Ofparticular significance are the inflection points in the curve that occur at approximately pH 8.3 and pH 4.5. The conversion of carbonate to bicarbonate [Eq. (2-14)] is essentially complete at pH 83. However, because bicarbonate is also an alkalinity species, an equal amount of acid must be added to complete the neutralization. Thus. the neutraliza- tion of carbonate is only one-half complete at pH 8.3. Because the conversion of hydroxide to water is virtually complete at pH 8.3 (see Fig. 2-3). all of the hydroxide and one-half of the carbonate have been measured at pH 8.3. At pH 4.5 all of the bicarbonate has been converted to carbonic acid [Eq. (2-15)], including the bicarbonate resulting from the reaction of the acid and carbonate [Eq. (2-14)]. Thus, the amount of acid required to titrate a sample to pH 4.5 is equivalent to the total alkalinity of the water. This point is illustrated in the following example. Example 2-6: Determining total alkalinity A 200-mL sample of water has an initial pH of 10. Thirty milititers of 0.02 N H,SO, is required to titrate the sample to pH 4.5. What is the total alkalinity of the water in milligrams per liter as CaCO? SOLUTION Because each milligram of 0202 N H;SO, will neutralize 1 mg of alkalinity, there is 30 mg of alkalinity in the 200-mL sample. Therefore, the concentration of alkalinity expressed as milligrams per liter will be 30mg 1000 mL 200 mL * 150 mg/L. If the volume of acid needed to reach the 8.3 endpoint is known, the species of alkalinity can also be determined. Because all of the hydroxide and one-half Hwan of the carbonate have been neutralized at pH 83, the acid required 10 lower the PH from ,3 10.4.5 must measure the other one-half of the carbonate, plus all ofthe original bicarbonate. If Pis the amount of acid required to reach pH 8:3 and iy is the total quantity of acid required to reach 45, the following generalization, Concerning the forms of alkalinity can be made: iP = M. all alkalinity is OH P = M/2. all alkalinity is COs?” 4 Z P = 0(1e. initial pH is below 8.3), all alkalinity is HCOs P < M22, predominant species are CO,7~ and HCOs P > M,2, predominant species are OH” and COs 2-3, it is noted that th In observing the pH dependency of the species in Fig, i. quantity of OH= becomes significant at pH less than about 9.0. Without intro. ducing significant error, it can be assumed that the OH” of samples with pH less than 9.0 is insignificant. The CO?” would then be measured by 2P and the HCO, would be measured by the remainder (M — 2P). One method of calculat- ing the quantities of each species is illustrated in the following example. Example 2-7: Determining ahalnty species Determine the species, and the quantity of cach specie, of alkalinity i Example 2 ifthe 8.3 equivalence point is reached at 11 mL. of aid SoLution 1. Because the initial pH is 10, the initial pOH of the wateris4,A determination of the OH - ‘concentration can be made as follows. 1, 10°fmol OH" _t equiv $0,000 mg Caco, (OW ] =~ * ot OF Tequiv = Smg/L as CaCO, 2 Five milters of acid would be required to measure the OH ina I-L sample, How. ever this sample is only 200 mL so the necessary volume of acid is: 200 5 3, IE mL of acid measures the OH ~. then 10 mL of acid measures one-half of the carbon- ate and 10 more will be required to measure the remaining one-half of the CO,?~, avng 9 mL to measure he HCO (Sex Fig. 24) Ths the quantity ofeach species isas follows: OH” (calculated from pH) = 5 mg/L 2. _ Omg 1000 mL CO = sp «OE too mes 1000 mt «Oh 45 mal Total alkalinity = 150 mg. [WATER QUALITY: DPHNITIONS, CHARACTERISTICS, AND PERSPICTIVES 35 Use Alkalinity measurements are often included in the analysis of natural waters to determine their buffering capacity, It is also used [requently as a process control vartable in water and wastewater treatment. Maximum levels of alkalinity have not been set by EPA for drinking water or for wastewater discharges. 2-10 HARDNESS. Hardness i defined as the concentration of multivalent metallic cations in solution. At supersaturated conditions, the hardness cations will react with anions in the water to form a solid precipitate, Hardness is classified as carbonate hardness and noncarbonate hardness, depending upon the anion with which it associates. The hardness that is equavalent to the alkalinity is termed carbonate hardness. with any remaining hardness being called noncarhonate hardness Carbonate hardness is sensitive to heat and precipitates readiiy at high temperatures. Ca(HCO,), —4+ CaCO, + CO; + H,0 2-16) Mg(HCO,), —*—» Mg(OH); + 2CO, (2-17) Sources The multivalent metallic ions most abundant in natural waters are calcium and magnesium. Others may include iron and manganese in their reduced states, (Fe**,Mn?*), strontium (Sr?*), and aluminum (Al?*). The latter are usually found in much smaller quantities than calcium and magnesium, and for all practical purposes. hardness may be represented by the sum of the calcium and ‘magnesium ions. Impacts ‘Soap consumption by hard waters represents an economic loss to the water user. Sodium soaps react with multivalent metallic cations to forma precipitate, thereby losing their surfactant properties. A typical divalent cation reaction is: 2NaCO2C,7H53 + cation?*> ——+ cation?*(CO,C,Hy3)) + 2Na* Soap Precipate (2-18) Lathering does not occur until all of the hardness ions are precipitated. at which point the water has been “softened” by the soap. The precipitate formed by hard- ness and soap adheres to surfaces of tubs, sinks, and dishwashers and may stain clothing. dishes, and other items. Residues of the hardness-soap precipitate may remain in the pores, so that skin may feel rough and uncomfortable. In recent years these problems have been largely alleviated by the development of soaps and detergents that do not react with hardness. 36 waren ee ale, the result of the carbonate hardness precipitate may cause Ca le economic loss through fouling of water heaters and hot-water pipes a > in pH in the water distribution systems may also result in deposits vf cipitates. Bicarbonates begin to convert to the less soluble carbonates at phy Values above 9, re Magnesium hardness, particularly assoct laxative effect on persons unaccustomed to It than SO mg L are desirable in potable waters. although many public water supphes exceed this amount Calcium hardness presents no public bealth problem. tn fact, hard water is apparently benelicial to the human cardiovascular system. [2-4} jated with the sulfate 107, has Magnesium concentrations of lesy Measurement 1g spectrophotometric techniques oF chemical Hardness can be measured by usin Iewim and magnesium 10nS MM a given titration to determine the quantity of cal sample, Hardness can be measured directly by titration with ethylenediamine tetraacetic acid (EDTA) using eriachrome black T (EBT) as an indicator. The EBT. reacts with the divalent metallic cations, forming a complex that 1 red in color ‘The EDTA replaces the EBT in the complex. and when the replacement 'scomplete, the solution changes from red to blue. If 0.01 M EDTA 1s used. 1.0 mL of the titrant measures 1.0 mg of hardness as CaCO, Use hardness is commonly made on natural waters and on waters in- for certain industrial uses. Hardness may range | hundred, or even several thousand. parts per Is vary according to a consumer's acclimation Analysis for tended for potable supplies and from practically zero 10 severa million. Although acceptability level to hardness, a generally accepted classification 1s as follows: Soft <5 mg:L as CaCO, Moderately hard 50-150 mgiLas CaCO} Hard 150 300 mg Las CaCOs Very hard 300 mgrL as CaCO, The Public Health Service standards recommend a maximum of 300 med. of hardness in drinking water. [2-18] A maximum limit is not set by the EPA standards. 2-11 FLUORIDE Generally associated in nature with a few types of sedimentary or igneous rocks. fluoride is seldom found in appreciable quantities in surface waters and appears in groundwater in only a few geographical regions. Fluoride is toxie to humans and WATER QUALITY: DEFINITIONS, CHARACTERISTICS, AND PERSPECTIVIS. 37 other animals in large quantities, Concentrations of approximately dental cavities in children. During fo while small concentrations can be benefictl 1.0 mg/L in drinking water help to prevent mation of permanent teeth, fluoride combines sulting in harder, stronger teeth that are more quantities for good dental formati ion are not naturally present Excessive intakes of fluoride ii can result in discoloration of teeth. Noticeable elatively common when fluoride concentrations ‘ted by fluoride, although both the benefits and liabilities of fluoride during tooth-formation years carry over into adulthood. Excessive dosages of fluoride can also result in bone fluorosis and other skeletal abnormalities. Concentrations of less than S mgyL in drinking water are not likely to cause bone fluorosis or related problems, and some water supplies are known to have somewhat higher fluoride concentrations with no discernible problem other than severe mottling of teeth. On the assumption that people drink more water in warmer climates, EPA drinking-water standards base upper limits for er ambient temperatures. These standards are discussed more fully in Sec. 2-1 2-12 METALS All metals are soluble to some extent in water. While excessive amounts of any metal may present health hazards, only those metals that are harmful in relatively small amounts are commonly labeled toxic; other metals fall into the nontoxic group. Sources of metals in natural waters include dissolution from natural deposits and discharges of domestic, industrial, or agricultural wastewaters. Measurement of metals in water is usually made by atomic absorption spectro- photometry. Nontoxic Metals In addition to the hardness ions, calcium and magnesium, other nontoxic metals commonly found in water include sodium, iron, manganese, alurninum, copper, and zinc. Sodium. by far the most common nontoxic metal found in natural waters, is abundant in the earth’s crust and is highly reactive with other elements. The salts of sodium are very soluble in water. Excessive concentrations cause a bitter taste in water and are a health hazard to cardiac and kidney patients. Sodium is also corrosive to metal surfaces and. in large concentrations. is toxic to plants. Iron and manganese quite frequently occur together and present no health hazards at concentrations normally found in natural waters. As noted in Sec. 2-4, iron and manganese in very small quantities may cause color problems. Iron concentrations of 0.3 mg/L and manganese concentrations as low as 0.05 mg/L 3 wane on and mangan ea Nise color problems, Additionally, some bacteria use 10 wil MY rine £0 taseand Is for an energy source, and the resulting slime Br" odor problems N Significant quantities of iron are encountel it is usually assncrated with chloride (FeC1,). brcarbonate TFAHCO, | gy Sulfate [Fe(SOq)] amons and exists ita reduced state, In sere SeNCE OF OXypen the ferrous (He!) aan ts axnlized tthe ferric Fre") 10m and fOr A Noh Compound with hydroxide [Fe(OH),}, Thus, significant quan’ ee ron wath Usually be found only an systems devon of oxygen such as ROM! ers or Jhaps the bottom layers of stratified lakes, Sixmilarly. manganese en (Mn?" ang Mn") assoctated with chloride, nitrates, and sulfates are solul ee hile oxidized, compounds (Mn** and Ma’*)are vietually insoluble. [tis possibl however for organic acids derived from davomposing vegetation to chelate on and manguneye and prevent their oxidation and subsequent precipitation in ANNA wens, Fre ather nontoxic metals are generally found an very small quantities in natural water systems. and most woukl cause taste problems long Pelore tox Jevels were reached. However. copper and ine are synereeit a when both are present, even in small quantities, may be toxic (0 many biological species, sed in natural Waler syste Toxic Metals ‘As noted earlier, toxic metals are harmful to humans and other organisms in Srrall quantities. Toxic metals that may be dissolved in water include arsenic, burtum cadmium. chromium, lead, mercury, and silver. Cumulative toxins such ay arenic, cadmium, lead, and mercury are particularly hazardous. These metals are the food chain, thereby posing the greatest danger to organisms concentrated bj rear the top of the ebuin. Fortunately toxic metals are present in only minute quantities in most natural water systems, Althongh natural sources ofall the toxic metals exist significant Concentration in water can usually be traced to mining, industrial, or agricultural sources. 2-13 ORGANICS Many organic materials are soluble in water. Organics in natural water systems may come from natural sources or may result from human activities. Most natural organics consist of the decay products of organic solids, while synthetic organics are usually the result of wastewater discharges or agricultural practices, Dissolved ‘organics in water are usually divided into two broad categories: biodegradable and nonbiodegradable (refractory). Biodegradable Organics Biodegradable material consists of organics that can be utilized for food by naturally occurring microorganisms within a reasonable length of time, In WATER QUALITY: DEFINITIONS, CHARACTERISTICS, AND PERSPECTIVES 39) original ‘materials usually consist of starches, fats, proteins, alcohols. dccanpouilsal SE agate ‘They may be the end product of the initial microbial men ee n OF animal tissue, of they may result from domestic or Foe ate eg tet discharges. Although some of these materials can cause — é lor problems, the principal problem associated with bio- degradable organics is a secondary effect resulting from the action of micro- organisms on these substances, Microbial utilization of dissolved organics can be accompanied by oxidation (addition of oxygen to. or the deletion of hydrogen from, elements of the orgamic molecule) or by reduction (addition of hydrogen to, of deletion of oxygen from. ‘elements of the organic molecule). Although it is possible for the two processes to occur simultaneously, the oxidation process is by far more efficient and is pre- dominant when oxygen is available. In aerobic (oxygen-present) environments. the end products of microbial decomposition of organics are stable and acceptable compounds. Anaerobic (oxygen-absent) decomposition results in unstable and objectionable end products. Should oxygen later become available. anaerobic end products will be oxidized to aerobic end products. The oxygen-demanding nature of biodegradable organics is of utmost importance in natural water systems. When oxygen utilization occurs more rapidly than oxygen can be replenished by transfer from the atmosphere, anaerobic conditions that severely affect the ecology of the system will result. This situation is covered in more detail in the next chapter. The amount of oxygen consumed during microbial utilization of organics jis called the biochemical oxygen demand (BOD). The BOD is measured by de- termining the oxygen consumed from a sample placed in an air-tight container and kept in a controlled environment for a preselected period of time. In the standard test. a 300-mL BOD bottle is used and the sample is incubated at 20°C for 5 days. Light must be excluded from the incubator to prevent algal growth that may produce oxygen in the bottle. Because the saturation concentration for oxygen in water at 20°C is approximately 9 mg/L. dilution of the sample with BOD- free. oxygen-saturated water is necessary to measure BOD values greater than just a few milligrams per liter. ‘The BOD of a diluted sample is calculated by BO, = DO, P where DO, and DO, are the initial and final dissolved-oxygen concentrations (mg/L) and P is the decimal fraction of the sample in the 300-mL bottle. Ranges of BOD covered by various dilutions are shown in Table 2-5. These values assume an initial dissolved-oxygen concentration of 9 mg/L in the mixture, with a minimum of 2 and a maximum of 7 mg/L of O; being consumed. Calcula- tions of BOD, from this testing procedure are illustrated in the following example. BOD (2-19) Example 2-8: Determining BOD, The BOD of a wastewater is suspected to range from 50 t0 200 mgiL. Three dilutions are prepared to cover this range. The procedure isthe same in each case. Fitst the sample is placed in the standard BOD bottle and is then 4 WaTER Table 2-5 Ra Various dlutat’® % BOD values covered by By direct pipetting into Being percntmiunes 7 abt ote “emnture Range of BOD mL Range of BOD 901 29000-70000 002 39000-10500 9629000. pos 12000-42.00 Sos 4,000-14,000 0.10 6,000-21,000 al 2,000-7,000 020 02 1,000-3,500 0.50 as 400-1,400 10 10 200-700 20 20 100-350 so So wires woo ane 20 ose 50.0 aid 100.0 100.0 OF fea Sawyer and McCarty. (212) ‘Source: From oxygen-saturated Wi reanic-ree, tly stoppered and ) uted t0 300 mL with oF owes ti ee dacmined and the Pt a i nage 1 tem ph he ded onygen aga ermine Wateraet, DO, DOs, O26 soD.. m Bo Rat mak tn fee pels pa ee MO eh 3 jar Hose a woleT if $i eag aty 2 an 8 > gate aber nn If the third value is disregarded (the BOD of the wastewater is 140 mg/L, rater. The initial dissolved placed in the incubator at final DO being less than 2.0 mg/L), the average microorganisms that will cor must be added and the BOI determined and subtracted from tl er and municipal wastewaters will have a population of risume the organics. In sterile waters, microorganisms 1D of the material containing the organisms must be he total BOD of the mixture. The presence of Most natural wat toxic materials in the water will invalidate the BOD results. “The BODs only represents the oxygen consumed in S days. The total BOD, ‘or BOD for any other time period, can be determined provided additional informa- tion is known or obtained. The rate at which organics are utilized by micro- organisms is assumed to be a first-order reaction, that is, the rate at which organics ie WATER QUALITY: DEFINITIONS, CHARACTERISTICS, AND PERSPECTIVES. 4 utilized is proportional to the amount available. Mathematically, this can be expressed as follows dL, dem the (2-20) where L, is the oxygen equivalent of the organics at time 1, and k isa reaction con- stant, The units of L, are milligrams per liter, and the units of k are d=! Equation (2-20) can be rearranged and integrated as follows: bys Lye. (2-21) ‘The term Lo in this equation represents the total oxygen equivalent of the organics at time 0, while L, represents the amount remaining at time 1, and decays ex- ponentially with time, as shown in Fig, 2-5 The oxygen equivalent remaining is not the parameter of primary importance However, the amount of oxygen used in the consumption of the organics, the BOD, n be found from the L, value. If Lis the oxygen equivalent of the total mass of Oxygen equivalent and BOD, mg/L of O; Time, days Figure 2-5 BOD and oxygen-equivalent relationships 2 wartr = then the difference between the value Lo and L, is the oxygen equivalent ‘onsumed. or the BOD exerted. Mathematically Lobe y= Ly — Loe y, = Le(l - e“*) (2:22) where y, represents the BOD, of the water. The value of ; approaches L, asymptotically, indicating that the total, or ultimate, BOD (y,) is equal to the initial oxygen equivalent of the water Lo. These relationships are shown in Fig 25. Equation (2-22) represents the BOD exerted by the carbon component of the organic compounds, Other components of organics, such as nitrogen and sulfur, may also be oxidized by microorganisms, resulting in an oxygen) demand. Equations similar to Eq, (2-22) can be derived for these reactions. “The value of k determines the speed of the BOD reaction without influencing the magnitude ofthe ultimate BOD. Thisisshown graphically in Fig 2-6 Numerical values of k range from about 0.1 to 0.5"! depending on the nature of the organic molecules, Simple compounds such as sugars and starches are easily utilized by the microorganisms and have a high k rate, while complex molecules such as phenols ancdifficlt to assimilate and have low k values. Some typical values of k are shown in Table 2-6. ‘The value of k for any given organic compound is temperature-dependent Because microorganisms are more active at higher temperatures, the value of k increases with increasing temperatures. The change in k can be approximated by the van't Hoff-Arrhenius model: : kp = kz 97? (2-23) ‘A value of 1.047 for 0 is often used although 0 is known to vary somewhat with temperature ranges. [2-8] Time, days igure 2-6 BOD exertion asa function of reaction constant k WATER QUALITY. DEFINITIONS, CHARACTERISTICS, AND PERSPECTIVES 43 Table 2-6 Typical values of k and y, for v waters kat Pn Water ype base e imgl Tap water

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