Chapter 3

TABLE OF CONTENTS pH
Page

Section 1: pH Introduction.................................................................................................................... Section 2: Application of pH................................................................................................................. Section 3: Glossary.............................................................................................................................. Section 4: pH Determination - Application Met ods............................................................................ Section !: Safety and Hy"iene............................................................................................................. Section #: Samplin"............................................................................................................................. Section $: Interpretations..................................................................................................................... %ui& 3.1................................................................................................................................................ Section ': Determination of pH............................................................................................................ %ui& 3.2................................................................................................................................................ Section (: %A)%*................................................................................................................................

2 2 3 3 4 4-! # # $-( ( 1+

Ans,ers to %ui&&es.............................................................................................................................. 11-12 Appendi- A: .eferences Appendi- /: 0reparation of /uffer Solutions Appendi- *: Sample *ali1ration /enc S eet Appendi- D: Met od * ec2list pH

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Chapter 3
pH
Section 1: pH INTRODUCTION pH is a mat ematical e-pression of t e intensity of t e acid or al2aline condition of a sample. 3 e term 4pH5 is defined as t e ne"ati6e lo"arit m of t e ydro"en ion concentration7 and is "enerally represented ,it a scale from + to 14 pH units. : ydro"en ions 9H ; and ydro-yl ions 9<H ;. 3 e usual c emical sym1ol of : ,ater is H2<7 o,e6er7 it can also 1e ,ritten as H <H s o,in" t at t ese t,o different ions are al,ays present. /ecause ,ater is made up of t ese t,o ions7 any solution , ic contains ,ater 9called an a=ueous solution; al,ays as 1ot ydro"en ions and ydro-yl ions. 3 e pH scale is a means of s o,in" , ic ion as t e "reater intensity. 8ater is made up of 1ot At a pH of $.+7 t e intensities of ydro"en and ydro-yl ions are e=ual and t e solution is said to 1e pH neutral. 8 en t e pH is less t an $.+7 t e intensity of t e ydro"en ions is "reater t an t at of t e ydro-yl ions and t e solution is said to 1e acidic. 8 en t e pH is "reater t an $.+7 t e ydro-yl ions a6e t e "reater intensity and t e solution is referred to as al2aline or 1asic. Section : APPLICATION OF pH pH monitorin" and control is important in t e operation of t ose municipal ,aste,ater treatment plants t at use 1iolo"ical met ods of secondary treatment and t ose usin" c emical treatment processes suc as c lorination. In addition7 pH control of se,a"e in collection systems and in certain slud"e treatment processes is essential. pH measurement is also re=uired as part of many ot er analyses includin" al2alinity and acidity. All treatment processes a6e t eir o,n optimum ran"e of pH. 3 e pH analysis is used to determine if t e process is operatin" ,it in t e accepta1le ran"e of pH. Alt ou" different processes a6e 6aryin" ran"es7 "enerally ,aste,ater or"anisms in 1iolo"ical treatment systems function 1est at pH 6alues of from #.! to '.+. * lorination is most effecti6e at lo, pH7 and ,aste,ater in se,a"e collection systems s ould 1e maintained at a 6alue close to $.+.

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Section 3: !LOSSAR" B#$$er: Any su1stance in a solution , ic reduces t e c an"e of pH upon t e addition of a stron" acid or 1ase. B#$$er Capacit%: 3 e amount of stron" acid or 1ase needed to c an"e t e pH 6alue of a 1 liter sample 1y one pH unit. It is a measure of t e capacity of ,ater or ,aste,ater to resist c an"es in pH. Har&ne'': 3 e concentration of calcium and ma"nesium salts in ,ater. Hardness is a term ori"inally referrin" to t e soap-consumin" po,er of ,ater. As suc 7 it is sometimes also ta2en to include iron and man"anese. pH: A measure of t e de"ree of acidity or al2alinity of a sample. pH is t e ne"ati6e lo"arit m of t e ydro"en ion concentration e-pressed in pH units from + to 14.

Section (: pH DETER)INATION * APPRO+ED )ETHODS Alt ou" a rou" measure of pH can 1e o1tained t rou" t e use of color indicators7 t e only met od appro6ed for use in all ,aste,ater treatment plants is t e "lass electrode met od ,it a pH meter.

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Section ,: SAFET" AND H"!IENE 8 en doin" t e pH test7 t e concerns for safety in6ol6e ,aste,ater a&ards7 1ro2en "lass and electrical s oc2. 0recautions related to ,aste,ater a&ards include t e follo,in": 1. 2. 3. 4. !. *o6er all cuts and ,ear "ood =uality late- "lo6es , en in direct contact ,it ra, ,aste,ater. 8as ands fre=uently7 and al,ays ,as ands prior to eatin" or smo2in".

*lean up all spills of ,aste,ater or 1uffers immediately. 8ear a protecti6e smoc27 apron7 or la1 coat7 and sur"ical or ru11er "lo6es , en ,or2in" in t e la1oratory to protect clot es and s2in. Dispose of all 1ro2en or crac2ed "lass,are immediately. 3 is material s ould 1e deposited in a separate container la1eled 4s arps5 t at cannot 1e punctured and pre6ents ot ers from reac in" into t e container. 8 en collectin" sample7 remem1er 1asic ,ater safety rules. Al,ays ,ear an appro6ed 0>D especially around mo6in" ,ater. Generally7 "ood ouse 2eepin" practices elp to 2eep t e ,or2 en6ironment safer.

#. $.

Section -: SA)PLIN! <nly "ra1 samples may 1e ta2en for pH measurement. *omposite samples are not accepta1le due to t e time delay in t e compositin" process. It is 6ery important t at samples 1e ,ell mi-ed and representati6e of t e plant flo,. SA)PLE PRESER+ATION /ecause t e pH can c an"e after t e sample as 1een collected7 t e pH must 1e measured as soon after collection as possi1le. 3 ere is no appro6ed met od of sample preser6ation for pH samples. If t e time la" 1et,een sample collection and testin" e-ceeds 3+ minutes7 t e samples s ould 1e discarded and fres samples collected.

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SA)PLE CONTAINERS Special samplin" de6ices or containers are not re=uired for t e pH test. Ho,e6er7 t e type of container used s ould 1e capa1le of collectin" samples from ,ell-mi-ed areas of tan2s and)or pipes and 1e made of resistant materials t at ,ill not rust or corrode7 and , ic can 1e easily cleaned. 0olyet ylene7 polypropylene or "lass are typical of t e types of containers used. A lon" andled aluminum dipper attac ed to a ,ooden andle7 or an e=ui6alent de6ice7 is accepta1le for collectin" samples. Do not use containers suc as coffee cans t at can corrode or rust. SA)PLE CONTAINER PREPARATION All sample collection containers s ould 1e cleaned t orou" ly ,it soap and ,ater on a re"ular 1asis 9prefera1ly at t e end of eac day; and rinsed ,ell. It is recommended t at eac samplin" point a6e its o,n samplin" de6ice in order to pre6ent cross-contamination. >or e-ample7 influent and effluent samples s ould not 1e collected in t e same container. /et,een sample collections7 t e sample containers s ould 1e rinsed t orou" ly and allo,ed to dry.

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Section .: INTERPRETATIONS In "eneral7 t e most effecti6e ran"e of pH 6alues for 1iolo"ical treatment process ,astes are #.'-$.2. 3 e 4?ormal5 ran"e for pH 6alues7 o,e6er7 is 1et,een #.! and '.+7 dependin" on suc factors as t e pH of t e municipality@s ,ater supply and t e disc ar"es of industries contri1utin" to t e system. It s ould 1e noted t at , at is 4?ormal5 for one plant is not necessarily 4?ormal5 for anot er7 and eac operator must determine , ic ran"e ,or2s 1est for is) er plant and adAust accordin"ly. Balues outside t e esta1lis ed 4?ormal5 ran"e indicate t at a condition e-ists , ic can yield poor effluent =uality. In addition7 c an"es in pH can indicate impendin" pro1lems. Attention to t e pH 6alues o6er time and to t e presence of any si"nificant c an"es made on fre=uently collected samples from desi"nated and esta1lis ed locations in t e plant ,ill elp to ensure maintenance of efficient 1iolo"ical treatment and a ,ell sta1ili&ed final effluent. pH is also useful in maintainin" safe conditions in a ,aste,ater collection system. Many compounds c an"e form 9and p ysical c aracteristics; 1ased on c an"es in solution pH7 suc as ydro"en sulfide 9H2S;. It as 1een s o,n t at reduced sulfides ,ill remain as uno1Aectiona1le HS at a 1asic pH7 1ut ,ill 1e con6erted to t e o1Aectiona1le and dan"erous H2S as pH 6alues decrease. 3 e effecti6eness of many c emical treatment processes depends ea6ily on pH control. 3 e remo6al of metals 1y industrial ,aste operators is 1ased on pH adAustment and metal- ydro-ide precipitation. 3 e addition of c lorine for t e disinfection of ,aste,ater effluent is more efficient at lo,er pH 6alues.

/#i0 311 1. A pH of !.! ,ould indicate t at t e sample is CCCCCCCCCCCCC. 2. 8 at is t e accepta1le ran"e of pH 6alues for ,aste,ater to 1e treated 1y 1iolo"ical met odsD 3. 8 at type of sample must 1e used for pH measurementsD 4. 8 at is t e recommended oldin" time for pH samplesD !. 8 at is t e appro6ed met od for pH measurement for compliance ,it ?0DES permit re=uirementsD

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Section 2: DETER)INATION OF pH DESCRIPTION OF )ETHOD Alt ou" t e analysis of pH 1y t e electrometric procedure is one of t e simplest tests performed in t e ,aste,ater la1oratory7 t ere are many possi1le sources of error in t e analysis. 3 e met od steps include cali1ratin" t e meter7 placin" t e electrodes in a ,ell-mi-ed sample and readin" t e results directly from t e pH meter. E/UIP)ENT AND REA!ENTS E/UIP)ENT 1. 2. 3. 4. !. /ea2ers7 polyet ylene or 3eflon preferred pH meter7 reada1le to at least +.1 pH unit electrodes: one "lass and one calomel reference or one com1ination electrode ma"netic stirrer and stirrin" 1ars 3 ermometer if pH meter cannot measure temperature

REA!ENTS 1. 2. Distilled 8ater pH 1uffer solutions: pH 47 $7 and 1+

3 e pH tests do not re=uire a lar"e num1er of c emicals to 1e prepared and all of t ese rea"ents can 1e purc ased from scientific suppliers in ready-to-use form. If t e 1uffer solutions must 1e prepared from scratc 7 t e procedures descri1ed in Appendi- / are recommended for pH $7 pH 47 and pH 1+ 1uffer solution preparation. LABORATOR" PROCEDURE /ecause of t e 6ariation in procedure 1et,een t e numerous ma2es and models of pH meters currently a6aila1le7 it is impossi1le to pro6ide specific instructions for t e correct operation of all instruments. In eac case7 follo, t e manufacturer@s instructions for preparin" t e electrodes and operatin" t e instrument. !ENERAL 3CO))ON4 PROCEDURAL STEPS Ca5i6ration 1. 2. 3urn pH meter on and allo, instrument to ,arm up. Measure t e temperature of t e standard 1uffer solutions and adAust t e meter temperature compensation dial as necessary. .ecord temperatures. If an automatic temperature compensatin" electrode is used7 disre"ard t is step as ,ell as step 1+. .emo6e electrode9s; from stora"e solution7 rinse ,it distilled ,ater and carefully 1lot electrode9s; dry ,it a i" =uality la1oratory tissue. 0lace electrode9s; in pH $.+ 1uffer solution and measure t e pH of t e 1uffer , ile "ently stirrin" solution. A ma"netic stirrin" de6ice is elpful7 1ut not re=uired. AdAust t e pH meter readin" to $.+7 if necessary7 t en place t e instrument in stand1y mode.

3. 4. !.

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#. $.

.emo6e t e electrode9s; from t e pH $.+ 1uffer solution7 rinse t orou" ly ,it distilled ,ater and 1lot dry. 0lace t e electrode9s; in a second 1uffer ,it a pH 6alue at least 2 pH units i" er or lo,er t an t e pH $.+ 1uffer solution. Fsually pH 4.+ and pH 1+.+ 1uffers are used for t is part of t e cali1ration.

NOTE: 3 e second 1uffer solution s ould 1e c osen so t at t e e-pected pH of t e sample falls 1et,een t e first and second 1uffers. '. (. Measure t e pH of t e second 1uffer solution , ile stirrin"7 adAust meter readin" as necessary and place instrument in stand1y mode. 3 is is "enerally called t e 4slope5. .emo6e t e electrode9s; from t e second 1uffer solution7 rinse t orou" ly ,it distilled ,ater and 1lot dry.

Sa7p5e Ana5%'i' 1+. Determine sample temperature7 record and adAust t e meter temperature compensation dial7 as necessary. 11. 0lace electrode9s; in sample7 t en measure and record sample pH , ile stirrin" t e sample. 12. 0lace instrument in stand1y mode and remo6e electrode9s; from sample7 rinse t orou" ly ,it distilled ,ater and carefully 1lot dry. 13. 8 en all samples a6e 1een tested7 place electrode9s; in tap ,ater or pH $.+ 1uffer solution for stora"e and s ut off meter. PRECAUTIONS 1. .eplace 1uffer solutions daily. 3o a6oid faulty instrument cali1ration7 replace ,or2in" 1uffer solutions at least once per ,ee2 ,it commercially prepared stoc2 1uffer or fres ly prepared 1uffer solutions. 0repare fres stoc2 1uffer solutions at least once e6ery four ,ee2s. >or 1est results7 1uffer solutions s ould 1e discarded after eac use. If possi1le7 pH meter7 1uffer solutions7 and samples s ould all 1e t e same temperature since e-treme temperature 6ariations can "i6e erroneous results. 8atc for erratic results arisin" from crac2ed electrodes7 faulty connections or foulin" of electrodes ,it "rease and)or solids residue. 3 e t,o point cali1ration ,ill elp detect a faulty electrode. If a reasona1ly accurate 6alue for t e second 1uffer cannot 1e o1tained after t e meter as 1een standardi&ed a"ainst t e first 1uffer7 t en it is li2ely t at one7 if not 1ot 7 of t e electrodes is faulty and must 1e replaced. INTERFERENCES 3 e "lass electrode is relati6ely free from interferences due to color7 tur1idity7 colloidal matter7 o-idants7 reductants or i" salinity7 e-cept for a sodium error at a i" pH. 3 is error at a pH a1o6e 1+ may 1e reduced 1y usin" special 4lo, sodium error5 electrodes. Since 1ot pH7 itself7 as ,ell as t e measurement of pH are temperature dependent7 it is important t at temperature compensation 1e performed on all samples and t at temperatures of 1uffers and samples 1e as similar as possi1le.

2. 3.

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PRECISION AND ACCURAC" 3 e precision and accuracy attaina1le ,it any "i6en pH meter ,ill depend on t e type and condition of t e instrument and t e care used in standardi&ation and operation. 8it proper care and use7 a precision of :)-+.+1 pH unit and an accuracy of :)-+.+! pH unit can 1e ac ie6ed ,it many models of pH meter. Ho,e6er7 :)- +.1 pH unit represents t e limit of accuracy under normal conditions. >or t is reason7 report pH 6alues to t e nearest +.1 pH unit.

/#i0 31 1. 8 at rea"ents are re=uired to perform pH measurement usin" t e electrometric met odD 2. 8 at e=uipment7 apparatus or instrumentation is re=uired to perform pH measurement usin" t e electrometric met odD 3. 8 at interferences7 if any7 are t ere in t e electrometric pH procedureD

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Section 8: /A9/C A %uality Assurance)%uality *ontrol pro"ram is re=uired 1y t e ?0DES permit. %uality Assurance 9%A; is a set of operatin" principles t at must 1e follo,ed durin" sample collection and analysis. Ga1 1enc s eets must 1e maintained t at document , en t e sample ,as collected7 o, it ,as preser6ed7 and , at results ,ere o1tained. %uality *ontrol 9%*; includes any testin" , ic is done to pro6e t at t e results are relia1le. <ne of e6ery ten samples analy&ed s ould 1e a %uality *ontrol c ec2. 3 is may include duplicate samples7 spi2e samples7 rea"ent 1lan2 analyses and 2no,n %* samples o1tained from outside sources. Duplicate sample analysis in6ol6es analy&in" t e same sample t,ice and comparin" t e results. 3 e closer t e results7 t e more accurate t e analysis. .esults s ould not differ 1y more t an 1+H. Spi2e sample analysis in6ol6es addin" 2no,n amounts of analyte to a sample and calculatin" t e percent reco6ery. 3 ese are discussed furt er in * apter 1+. In pH testin"7 1uffers must 1e c ec2ed daily and duplicate samples s ould 1e run on e6ery tent sample. %uality *ontrol samples ,it a 2no,n pH are a6aila1le from c emical manufacturers. A sample cali1ration 1enc s eet is included in Appendi- *.

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An':er' to /#i00e' /#i0 311 1. A pH of !.! ,ould indicate t at t e sample is CCCCCCCCCCC. Aci&ic 2. 8 at is t e accepta1le ran"e of pH 6alues for ,aste,ater to 1e treated 1y 1iolo"ical met odsD -12 * .1 3. 8 at type of sample must 1e used for pH measurementsD !ra6 'a7p5e 4. 8 at is t e recommended oldin" time for pH samplesD Sa7p5e' 'ho#5& ana5%0e& i77e&iate5% a$ter co55ection1 In no ca'e 'ho#5& the pH ana5%'i' 6e &one a$ter 3; 7in#te' ho5&ing ti7e1 !. 8 at is t e appro6ed met od for pH measurement for compliance ,it ?0DES permit re=uirementsD E5ectro7etric 37eter4 7etho&1 /#i0 31 1. 8 at rea"ents are re=uired to perform pH measurement usin" t e electrometric met odD Di'ti55e& <ater an& pH 6#$$er 'o5#tion': pH (= .= an& 1; 2. 8 at e=uipment7 apparatus or instrumentation is re=uired to perform pH measurement usin" t e electrometric met odD a1 61 c1 &1 e1 3. Bea>er'= po5%eth%5ene or Te$5on pre$erre& pH 7eter= rea&a65e to at 5ea't ;11 pH #nit e5ectro&e': one g5a'' an& one ca5o7e5 re$erence or one co76ination e5ectro&e 7agnetic 'tirrer an& 'tirring 6ar' Ther7o7eter i$ pH 7eter cannot 7ea'#re te7perat#re

8 at interferences7 if any7 are t ere in t e electrometric pH procedureD So&i#7 error at a high pH1 Thi' error at a pH a6o?e 1; 7a% 6e re&#ce& 6% #'ing 'pecia5 @5o: 'o&i#7 errorA e5ectro&e'1 Te7perat#re co7pen'ation 7#'t 6e per$or7e& on a55 'a7p5e'= an& te7perat#re' o$ 6#$$er' an& 'a7p5e' 'ho#5& 6e a' 'i7i5ar a' po''i65e1

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APPENDIB A Re$erence' t Standard Met ods for t e E-amination of 8ater and 8aste,ater7 A0HA-A88A-8E>7 1' Edition7 1((27 Met od 4!++-H. Met ods for * emical Analysis of 8ater and 8astes7 F.S. E0A-#++)4-$(-+2+7 Marc 1($(. NOTES:

* apter 3 ) Appendi- A ) 0a"e 1

APPENDIB B Preparation o$ B#$$er So5#tion' pH -12- B#$$er So5#tion 0repare 1y dissol6in" 3.3'$ " potassium di ydro"en p osp ate 9IH 20<4; and 3.!33 " disodium ydro"en p osp ate 9?a2H0<4; in fres ly 1oiled and cooled distilled ,ater and dilute to 1+++ mG. pH (1;; B#$$er So5#tion 0repare 1y dissol6in" 1+.12 " potassium ydro"en p t alate 9IH* 'H4<4; in distilled ,ater and dilute to 1+++ mG. pH 1;1;1 B#$$er So5#tion 0repare 1y dissol6in" 2.+(2 " sodium 1icar1onate 9?aH*< 3; and 2.#4+ " sodium car1onate 9?a2*<3; in distilled ,ater and dilute to 1+++ mG. 3 e ,ide-ran"e pH indicator solution used in t e Hac Model 1$-? pH test 2it may 1e purc ased from t e Hac *ompany at t e follo,in" address: Hac *ompany 0.<. /o- 3'( Go6eland7 *olorado '+!3( 1-'++-22$-4224 NOTES:

* apter 3 ) Appendi- / ) 0a"e 1

APPENDIB C Sa7p5e Ca5i6ration Bench Sheet Dai5% Ca5i6ration /#a5it% Contro5 3$or the )onth9"ear4 Date 1 2 3 4 ! # $ ' ( 1+ 11 12 13 14 1! 1# 1$ 1' 1( 2+ 21 22 23 24 2! 2# 2$ 2' 2( 3+ 31 *al. Std. 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ 1+.++ Slope Std. $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ $.++ * ec2 Std. 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ 4.++ * ec2 .esult 3emp. 3ec . 3ime

* apter 3 ) Appendi- * ) 0a"e 1