2d 4. Wash bortte. O80 mb e Maynetie stirrer toptiowsal, 3. Reagents 4. Ozone-demant-free water: See Section 2350034 4, Sulfuric acid, H.SO,. 2N: Cautiously add $6 mt. cone H,SO, 10 800 mL ozone-demand-free water in a I-L volumettic flask, Mix thoroughly, cool. ad up co mnatk with ozone-detnand- hee water ©. Potassium iodide, Kl: Dissolve 20 g KI in about 800 mL. of ozone-deimand-free water in a I-L volumetric flask, Make up t0 ‘with ozone-demand-free water. 4. Standard sodium thiosulfate titans, Na,S,0y, O.AN: See Section 4500-C1.B.2e ¢, Suindard sodium thiosulfate titrant, NajS;0y, 0.00SN: Di- le the proper volume (approximately $0 inl.) of standardized (IN Na,$,0, to VL £. Starch indicator solution: See Section 4500-C.B.2¢. 4, Procedure Determine the ouput of the ozone generator by passing the vn gas tough wo serial Kl taps Laps A and) for abo TC ugh For best resus, keep gas flow below approximately NRE Each tap is gas wshingbotle conatning 2 known x least 200 in) of 2% Ki--Quunttavely wansfer Comets ofeach tap into a heuer al 10 nL of 201,80. ad {ite with sana ©:005HNe.50y wl te yellow tine cole Imost disappears. Add | 10.2 mL starch indicator sobution sand continue titrating tw the disappearance of blue color. Put a knows volume (at least 200 mL) of sample im a separate tts washing bottle abel gas washing bottles 10 avoid cout inating the reaction vessel with iodide). Direct ozone gas through this reaction vesse For ozone demand studies, direct leaving reaction vessel dhrough a KE wap (Trap C) prepared as above. Ozonate sample for a given contact time, For ozone slemiand studies, uum ozonator aff at end of contact time and pour wcontents of Trp C ino a beaker. Add 10 mL 21 HzSO, and litte with 0.005W NayS,0, as described above. For ozone ‘requirement studies. remove a portion from the reaction vessel st the end of contaet time and measure residual ozone concentra tion by the indigo method, = PHysi 8 AGGREGATE PROPERTIES (2000) 5, Calculation, a. Ozone dose + BRN XD Orme dose, _ 7 A= mL titrane for Trap A, B= mL titrant for Trap B. N= normality of Na;S,03, and T= ozonation time, min . Ozone demand: CxNxu ‘Orone dons mploin = ope dose, matin 7 on titrant for Trap C Report sample ozone demand and blank ozone demand, o70ne Jose. ozonation time, sample temperature, sample pH, sample volume, and analytical method. Because the ozone transfer rate is hiighiy dependent on experimental conditions, alse report ow rate, and sample volun, © Ozone requirement: The wrone requirement in the semi ‘batt test the ozone dose. angi, reyuieed to obtain he e. See Section vessel volume, vessel Iype, fovone residual after the desieed ozonation i 2350851 to calculate dose, When reporting ozone requirement, alsa include target oxidant residual as well as other experimental racteristies Fisted inf 6. Precision and Bias See Si sion 23501 6, 7. Bibliography See Section 4500.0,.B.7 and 8 2510 CONDUCTIVITY* 2510 A. Conductivity, k, is measure of the ability of sm aqueous solution (o carry an electric current. This ability depsnds ou the prevence of ions; on their (otal concentration, mobility, and * Apwved by Standard Methods Co Jit Tack Group: 200 ition Rott M. Beggin (chr, Suphen W. Jetson, Witisn F, Koch, Reecell W, Lane, Mise Pam, Introduction valence; and on the temperature of measurement, Solutions of tnvst inorganic compounds are relatively good conductors. Con versely, molecules of organic compounds that do not dissociate iqueous solution conduct a current very poorly, if at all. iCONDUCTIITY (2510)"ntroduction Tans 251031, Howat Coxoucrvy, A an Cospuctisty. k oF Porassium Caowe ar 2500-2? * Equi Conductivity. A Conductivity, &, ponhvem iho-en equivalent y see Cult 7 KCI Concentration Mor equivalent. ° 99 0.0001 1489 lao 6.0005 77 no 0001 469 1469 0.005, 136 7175 001 Mi Lanz 002 1382 2165 0.05 33 6 667 ou nso 12 890 02 i240 24 800 05 173 58 670 1 un 11 800 blue ob. the 1968 temperate sundard, and he volume andi? Values are accurate 19 20.1% oO yumbulem, whichever greten 1. Definitions and Units of Expression ance, G, is defined as the reciprocal of resistance, R: L ® where the unit of Ris ohm and G is ohn ho). Conductance of a solution is measured between two spatially fixed and chemically inert electeodes. To avoid po: larization at the electrode surfaces the conductance measure- ment is made with an alternating current signal.' The con to the clectrode surface area, A, cin’, and inversely proportional to the distance between the electrodes, 1. cts, The constant of proportionality, &, such that oft is called “conductivity” (preferred to “specie conductance”) 1k is a characteristic propery of the solution between the electrodes. The units of k are Hohm-em or mho per centime tex_Zonductivity is customarily reported in micromhos per centimeter (4umhofem). In the International System of Units (SI the reciprocal ofthe ohm is the siemens (S) and conductivity is reported as milli- siemens per meter (mS/n); 1 mS/m =" 10 pambosfem and 1 wSfem = 1 jmbolem. To report results in SI units of mS/m umhos/em by 10. To compare CONDUCTities, values of & are reported relative to electrodes with A = 1 cm? and L = 1 em. Absolute conduc- lances, Gy, of standard potassium chloride solutions between electrodes of precise geometry have been measured; the corre- sponding standard conductivities, &, are shown in Table 25101. The equivalent conductivity, A, of a solution is the conduc~ tivity per unit of concentration. As the concentration is decreased toward zero, A approaches a constant, designated as A. With k * (sometimes w ductance of a solution, G, is directly proportion in units of micromhos per ee concentration to units of equivalents per cubic centimeter; there: fore: imeter itis necessary to convert A= 0.001Kéconceatration where the units of A. £, and concentration are mko-ct equivalent, yamhovem, and equivalent, respectively. Equiv alent conductivity, A. values for several concentrations of KCI are iisted in Table 2510, In practice, solutions of KCI more dilute than 0.0014 will not maintain stable conduectiv. ities because of absorption of atmospheric CO,, Protect these dilute solutions from the atmosphere, 2, Measurement 4. Instrumental meastrenents: Inthe laboratory, conducts G,, (oF resistance) of a standard KCI solution is measured and from the corresponding conductivity, &,. (Table 2510:1) a eet! constant, C. em”, is calculated: hy G, ‘Most conductivity meters donot display the actual solution conductance, (, or resistance, A; rather they generally have a dial that permits the user to acljus the internal cell constant to mach the conductivity. &, of a standard, Once the cell constant has been determined, or Se the condactivity of an unknown solution, LCG, will be displayed by the meter Distilled water produced in 3 Luhoratory generally has a conduc Livity im the range 015 to 3 yurbosfem, The conductivity increases shortly after exposure to both air and the seater container The conductivity of potable waters in the United States anges generally from 50 0 1500 ymhoslem, The conductivity of domestic wastewaters may be near that of the local water supply, although some industrial wastes have conductivities above 10.000 jumhos/en, Conductivity instruments are used in pipe lines, channels, lowing streams, and lakes and can be incorpo- rated in multiple-parameter monitoring stations using recorders. Most problems in obtaining good data with conductivity mon itoring equipment are related (o electrode fouling and to inade- uate sample circulation, Conductivities greater than 10 000 to Taste 2510. Saves ANALYSIS IaustRATING CALCULATION oF CowmucTiVity yay. Hom Naat. Wartas? fons ae et Amar Patt c 33 138 1642 332 Me 2 09 520 | 196 Na 2% 122 ou 122 K 32 0s, 59 08 HCO, 170 279 142 279 $0, n 030 1280 320 a 0 036 056 15332.46 50.000 pmbofer or Tess than abut 1 pfu may be dif it to measure with usual measurement cleeteonies and el} Vactanee, Consult the instruiwent manulaerurer’s manual OF published references.’ “* Laboratory conductivity measurements are sed (9 + Establish degree of mit total concentration of fons on chemical equilibria. physiological feffect on plants or animals, corrosion rates ele Assess degree of mineralization of distilled and deionized water. rer galuate variations in dissolved minerat concentration of raw water or wastewater, Minor seasonal variations found in aservoir Waters contrast sharply with the daily fluctuations in Some polluted river waters, Wastewater contsiing sigiticant rade wastes also miay show a considerable daily variation. Ewtimate sample size to be used for common chemical erminations and 10 check results of a chemical analysis + Determine amount of ionic 1 cipitation and neuraization reactions. the end point being de- trated by a change in slope of the curve resulting from plowing conductivity against buret readings mae tonal dissonveat solids (emg/l) in a sample by ml= tiplying conductivity (in mierombos per centimeter) by an em Pal factor, This factor may vary from 0.35 10 09. depending ie soluble components oF the water ane an the temperate eagurement, Relatively high factors may be required for cane pr boiler waters, whereas Hower factors may apply where SOheiderabte hydroxide or free acid is present. Even though sample evaporation rcs ization to assess the effect of the fof carbonate to car= Ipowate the empirical f 1 by diving dissed sli by conductivity ire the anificquivatents per Titer of either cations o waters hy snuliptying condctivity 18 ants of rnicromhos. per centimeter by 001 1. Caleulatian of conduetvizs: For 0 or is derivado a coveparatively COM water suppl “4 rally oseurring waters Fr mostly Ca?? Met. HCO, SO, and CL anal_with ‘TDS less than about 2506 1 following proces ised to calcubate conductivity from measired Tanic concentrations.” The ablrev ted water analysis in Table Seton illostrates the caleutation procedure ‘At infinite clifton the contribution to conductivity by differ- cent Kinds of fons is itive, In general the restive contribution teach eation and anion is calculated by mwliplying equivalent Won A nbo-en equivalent, by concentetion Ee iNiatens per liter and correcting nis, Table 251010 Tone a short ist of equivalent conductances for fons cmt only found in natural waters." Trace concentrations of fons tly make negligible contribution ro tke overall consbetie- eA temperature coeficient of OO2HGee is apicable wall ies escept H (0.01 39ideg) ara OW (0.018 Gn concentrations, s opposed 10 infinite dilation, con- ductivity per equivalent decreases with intcasing coment {Gee Table 25104), For solutions composed of one anion (ye ser ane eatin type-e.g.. KCl as in Table 25101, the decrease in are tivity per equivalent with concentration can be caleslated, STILT using an fonic-stengit-based theory of Onsager.” When snived safes are present as is nearly abvays the eage with ¢wural tind wastewaters. the theory is quite complicated." The ing senviempirical procedure can be used ty calle es ity for naturally occurring waters: setiv- rani 251001, Ey atnst Conon ta Hs oe W 1 95 Vty!* si Nat so. ce 15 NH" 738 Hare ot UBRe'* os First, ealeulate infinite dilution co Column 4) gee Shad mit + Sal tt, A,X, = equivalent conductance of the If mM is. used to express concen (df) or (A )imAt, correets the units from ti anew a1 2800C on ICO, waco? 1280 F Nos onductivity (Table 25100, loa ult) solute value of the charge of the th ion, iimolae goncentrtion ofthe eh in, ad ‘ah ton nation, the product. (N,) >t eu this Cave f° is $78.2 pumbovem (Table 25101, Column 4) Next, calculate ionic strength (5 i Ws nv molar nits St, y20080 rhe jonie strength ix 15.4¥3/2000 = 0.00767 M (Tate 25 10:1 Column 5). ‘Calculate the monovalent ion activ Davies equation for IS 5 0.5 AP 3nd ore" iay coefficiens, y. using the for temperatargs from 20 t0 In the present example £5 = 0.00767 Af and y = 0.91 Finally, obtain the calculated value of conductivity, Ayu fom: eke In the example being comsidered. 478.8 prmhoderm versus the reported USGS of 477 pinholem. For 39 anal ties ealeulted within 2%, 3, References + of naturally occurring waters, kaye = 578.2 x OOP = value as measured by the fs manner agreed wih the nveasured vals (0 1 Waraen, Heth, LiL, Moanurr & JA. Drax, 1974: Tostrumental Methor's of Analysis, Sit ed D. Vs York, KY 2. War Ye, WEP Koen, W2. Hanne Ra clecirolvtie conductance standards. fan Nostransl Company, New a. 1987. Review of ‘Solution Chem. W:N0.12.CONDUCTMTY (2510)Laboratory Method 4. Insinin, WS. 1988, Secondary Standard Potassiuns Chloride Con ductivity Solutions at 25°C. Corporate Metrology Laboratory, YSI Inc, Yellow Springs, Ohio. 4, Oncrstsation IeTeRNaTiONALe be Merwonccir Least: 1981, Stan dard Solutions Reproducing the Conductivity of Elctolyts, Inter rational Recommendation No. 56, Ist ed, Jane 1980, Bur. Interns tional de Métologie Léyale, Pais, France 5. Awenicay Socury ron Tesrine ao Mareaias 1982. Sinan tes ‘methods for electrical conductivity and resistivity of water. ASTM. Designation DU2S. 6, Scuotsianes, D.S., CW. Gartaso & JW. Nuts, 1989, Exper ‘ments in Physical Chemisty, Sth ed. McGraw-Hill Book Co. New ‘York, N.Y. 2a7 7, Havenrox, CE. 1978. Manual on Water, ASTM Spee Tech, Publ 2A, dthed, American Soc. Testing & Materials, Philadelphia, Pa 8, Deas. LA. 1983, Lange's Handbook of Chemistry, 13th” ed McGraw-Hill Book Co, New York, N.Y. 9, Rowson, BA. & RAT Stoxts, 1939, Eletrlyte Solutions, 2nd ed Academic Press, New York, NY. 10. Haein, HS. & BB. Owen. 1958. ‘The Physical Chemistry of Blectolyie Solutions, 3rd ed, Reinhold Publishing Corp., New York, NY. 11, Dowits, CW, 1962, fou Assed “The Netherlands 12, Tewoeasootous, G. & ED. Semmocoen, 1985, Water Quality, Val. 1, Addison-Wesley Publishing Company, Reading, Mass. jon, Blevier Press, Amsterdam, 2510 B. Laboratory Method Section 25104, LA Apparatus 1 Selfcomained conductivity instruments: Use 2m instrument capable of| conductivity with an error 10 14 or 1 wmholem, whichever is res b, Thermometer, capable of being real 10 the newest 01°C and covering the range 23 to 27°C. Many conductivity meter ‘equipped to read an automatic temperature sensor ¢. Conductivity cet: 1) Platinum-electrode type—Conductivty ectls containing plat inized electrodes are available in either pipet oF immersion fon Cell choice depends on expected range of conductivity. Experi tally check instrament by comparing instrumental result conlucivies ofthe KCl solaons led in Tale 25101, Clean new cells, not already coated and ready for use, with chromic- sulfuric acid cleaning mixture [see Section 258018 362)] and plat nize the electrodes before use. Subsequently, clean and replatinize et the readings become esratic, when 3 sharp end point cannot be obtained, oF when inspection shows that any platinum black has faked off. To platinize, prepare a solution of | g chloro- Platinic acid, H,PtCl, + 6H,0, and 12 mg lead acetate in 100 mi. istlled water. A more concentrated solution reduces the requited to platinize electrodes and may be used when time is 2 factor, eg., when the cell constant is 1.0/em or more. Immerse ‘electrodes inthis solution and connect both to the negative terminal of a 1.5-V dry cell battery. Connect positive side of battery to 2 iece of platinum wire and dip wire into the solution. Use a current such that only a small quantity of gas is evolved. Continue elec- ‘wolysis until both cell electrodes are coated with platinum black. ‘Save platinizing solution for subsequent use. Rinse electrodes thor- ‘oughly and when not in use keep immersed in distilled water. 2) Nonplatinum-electrode type—Use conductivity cells contain- ing electrodes constructed from durable common metals (stainless steel among others) for continuous monitoring and field studies. Calibrate such cells by comparing sample conductivity with resalts ‘obtained with a laboratory instrument. Use properly designed and ‘mated cell and instrument to minimize errors in cell constant. Very exceeding oe long meter leads can affect performance of a conductivity meter. Under such cireum ctures"s minal for propriate correction Factors if necessary 3. Reagents 4 Conductivity water: Any of several methods can be used + prepare weagent-grade water. The methods discussed in Sects 1080 are recommended. The conductivity should be small co pared to the value being measured: 1h Standard potassium chloride soluion, KC, OOOOM: Dis. solve 745.6 mig anhydeos KCL in conductivity water and didute 10 1000 mi. in a class A. volumetic Husk at 25°C and store in a CO,-fiee atmosphere. This isthe standard reference solution, which st 25°C has a conductivity of 1412 amhovlem. ICs satisfactory for ‘most samples when the cell has a constant between-l and 2 em" Forcier cell constants, use stwonger or weaker KCI solutions listed in Table 25103. Care must be taken when using, KCI solutions tess than 0.0014, which can be unstable because of the influence of ‘carbon dioxide on pure water, For low conductivity standards, Standard Reference Material 3190, with a certified conductivity of 2500 Siem * 0.3 4sSlem, may be obtained from NIST. Store in a tlass-stoppered borosilicate glass bot, 4, Procedure 4, Determination of cell constant: Rinse conductivity cell with, atleast three portions of 0.01M KCI solution. Adjust temperatu of a fourth portion to 25,0 0.1°C. If a conduetivity meter displays resistance, R, ohms, measure resistance of this portion and note temperature. Compute cell constant, C: = @.001412) gel) + BO19KE ~ 2591 where: ci measured resistance, ohms, and 7 = observed temperature, °C. Conductivity meters often indicate conductivity directly, Commercial probes commonly contain a temperature sensor. ‘With such instruments, rinse probe three times with 0.0100M KCI, as above. Adjust temperature compensation dial to 0.0191