Chapter 3

TABLE OF CONTENTS
pH
Page
Section 1: pH Introduction.................................................................................................................... 2
Section 2: Application of pH................................................................................................................. 2
Section 3: Glossary.............................................................................................................................. 3
Section 4: pH Determination - Application Metods............................................................................. 3
Section !: Safety and Hy"iene............................................................................................................. 4
Section #: Samplin"............................................................................................................................. 4-!
Section $: Interpretations..................................................................................................................... #
%ui& 3.1................................................................................................................................................ #
Section ': Determination of pH............................................................................................................ $-(
%ui& 3.2................................................................................................................................................ (
Section (: %A)%*................................................................................................................................ 1+
Ans,ers to %ui&&es.............................................................................................................................. 11-12
Appendi- A: .eferences
Appendi- /: 0reparation of /uffer Solutions
Appendi- *: Sample *ali1ration /enc Seet
Appendi- D: Metod *ec2list pH
*apter 3 - 1
Chapter 3
pH
Section 1: pH INTRODUCTION
pH is a matematical e-pression of te intensity of te acid or al2aline condition of a sample. 3e term
4pH5 is defined as te ne"ati6e lo"aritm of te ydro"en ion concentration7 and is "enerally represented
,it a scale from + to 14 pH units.
8ater is made up of 1ot ydro"en ions 9H
:
; and ydro-yl ions 9<H
-
;. 3e usual cemical sym1ol of
,ater is H
2
<7 o,e6er7 it can also 1e ,ritten as H
:
<H
-
so,in" tat tese t,o different ions are al,ays
present. /ecause ,ater is made up of tese t,o ions7 any solution ,ic contains ,ater 9called an
a=ueous solution; al,ays as 1ot ydro"en ions and ydro-yl ions. 3e pH scale is a means of
so,in" ,ic ion as te "reater intensity.
At a pH of $.+7 te intensities of ydro"en and ydro-yl ions are e=ual and te solution is said to 1e pH
neutral. 8en te pH is less tan $.+7 te intensity of te ydro"en ions is "reater tan tat of te
ydro-yl ions and te solution is said to 1e acidic. 8en te pH is "reater tan $.+7 te ydro-yl ions
a6e te "reater intensity and te solution is referred to as al2aline or 1asic.
Section : APPLICATION OF pH
pH monitorin" and control is important in te operation of tose municipal ,aste,ater treatment plants
tat use 1iolo"ical metods of secondary treatment and tose usin" cemical treatment processes suc
as clorination. 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 oter analyses includin"
al2alinity and acidity.
All treatment processes a6e teir o,n optimum ran"e of pH. 3e pH analysis is used to determine if
te process is operatin" ,itin te accepta1le ran"e of pH. Altou" 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
sould 1e maintained at a 6alue close to $.+.
*apter 3 - 2
Section 3: !LOSSAR"
B#$$er: Any su1stance in a solution ,ic reduces te can"e of pH upon te addition of a stron" acid
or 1ase.
B#$$er Capacit%: 3e amount of stron" acid or 1ase needed to can"e te pH 6alue of a 1 liter sample
1y one pH unit. It is a measure of te capacity of ,ater or ,aste,ater to resist can"es in pH.
Har&ne'': 3e concentration of calcium and ma"nesium salts in ,ater. Hardness is a term ori"inally
referrin" to te soap-consumin" po,er of ,ater. As suc7 it is sometimes also ta2en to include iron and
man"anese.
pH: A measure of te de"ree of acidity or al2alinity of a sample. pH is te ne"ati6e lo"aritm of te
ydro"en ion concentration e-pressed in pH units from + to 14.
Section (: pH DETER)INATION * APPRO+ED )ETHODS
Altou" a rou" measure of pH can 1e o1tained trou" te use of color indicators7 te only metod
appro6ed for use in all ,aste,ater treatment plants is te "lass electrode metod ,it a pH meter.
*apter 3 - 3
Section ,: SAFET" AND H"!IENE
8en doin" te pH test7 te concerns for safety in6ol6e ,aste,ater a&ards7 1ro2en "lass and electrical
soc2.
0recautions related to ,aste,ater a&ards include te follo,in":
1. *o6er all cuts and ,ear "ood =uality late- "lo6es ,en in direct contact ,it ra, ,aste,ater.
2. 8as ands fre=uently7 and al,ays ,as ands prior to eatin" or smo2in".
3. *lean up all spills of ,aste,ater or 1uffers immediately.
4. 8ear a protecti6e smoc27 apron7 or la1 coat7 and sur"ical or ru11er "lo6es ,en ,or2in" in te
la1oratory to protect clotes and s2in.
!. Dispose of all 1ro2en or crac2ed "lass,are immediately. 3is material sould 1e deposited in a
separate container la1eled 4sarps5 tat cannot 1e punctured and pre6ents oters from reacin"
into te container.
#. 8en collectin" sample7 remem1er 1asic ,ater safety rules. Al,ays ,ear an appro6ed 0>D
especially around mo6in" ,ater.
$. Generally7 "ood ouse 2eepin" practices elp to 2eep te ,or2 en6ironment safer.
Section -: SA)PLIN!
<nly "ra1 samples may 1e ta2en for pH measurement. *omposite samples are not accepta1le due to
te time delay in te compositin" process. It is 6ery important tat samples 1e ,ell mi-ed and
representati6e of te plant flo,.
SA)PLE PRESER+ATION
/ecause te pH can can"e after te sample as 1een collected7 te pH must 1e measured as soon
after collection as possi1le. 3ere is no appro6ed metod of sample preser6ation for pH samples. If te
time la" 1et,een sample collection and testin" e-ceeds 3+ minutes7 te samples sould 1e discarded
and fres samples collected.
*apter 3 - 4
SA)PLE CONTAINERS
Special samplin" de6ices or containers are not re=uired for te pH test. Ho,e6er7 te type of container
used sould 1e capa1le of collectin" samples from ,ell-mi-ed areas of tan2s and)or pipes and 1e made
of resistant materials tat ,ill not rust or corrode7 and ,ic can 1e easily cleaned. 0olyetylene7
polypropylene or "lass are typical of te types of containers used.
A lon" andled aluminum dipper attaced to a ,ooden andle7 or an e=ui6alent de6ice7 is accepta1le for
collectin" samples. Do not use containers suc as coffee cans tat can corrode or rust.
SA)PLE CONTAINER PREPARATION
All sample collection containers sould 1e cleaned torou"ly ,it soap and ,ater on a re"ular 1asis
9prefera1ly at te end of eac day; and rinsed ,ell. It is recommended tat eac samplin" point a6e its
o,n samplin" de6ice in order to pre6ent cross-contamination. >or e-ample7 influent and effluent
samples sould not 1e collected in te same container. /et,een sample collections7 te sample
containers sould 1e rinsed torou"ly and allo,ed to dry.
*apter 3 - !
Section .: INTERPRETATIONS
In "eneral7 te most effecti6e ran"e of pH 6alues for 1iolo"ical treatment process ,astes are #.'-$.2.
3e 4?ormal5 ran"e for pH 6alues7 o,e6er7 is 1et,een #.! and '.+7 dependin" on suc factors as te
pH of te municipality@s ,ater supply and te discar"es of industries contri1utin" to te system. It
sould 1e noted tat ,at is 4?ormal5 for one plant is not necessarily 4?ormal5 for anoter7 and eac
operator must determine ,ic ran"e ,or2s 1est for is)er plant and adAust accordin"ly.
Balues outside te esta1lised 4?ormal5 ran"e indicate tat a condition e-ists ,ic can yield poor
effluent =uality. In addition7 can"es in pH can indicate impendin" pro1lems. Attention to te pH 6alues
o6er time and to te presence of any si"nificant can"es made on fre=uently collected samples from
desi"nated and esta1lised locations in te 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
can"e form 9and pysical caracteristics; 1ased on can"es in solution pH7 suc as ydro"en sulfide
9H
2
S;. It as 1een so,n tat reduced sulfides ,ill remain as uno1Aectiona1le HS
-
at a 1asic pH7 1ut ,ill
1e con6erted to te o1Aectiona1le and dan"erous H
2
S as pH 6alues decrease.
3e effecti6eness of many cemical treatment processes depends ea6ily on pH control. 3e remo6al
of metals 1y industrial ,aste operators is 1ased on pH adAustment and metal-ydro-ide precipitation.
3e addition of clorine for te disinfection of ,aste,ater effluent is more efficient at lo,er pH 6alues.
/#i0 311
1. A pH of !.! ,ould indicate tat te sample is CCCCCCCCCCCCC.
2. 8at is te accepta1le ran"e of pH 6alues for ,aste,ater to 1e treated 1y 1iolo"ical
metodsD
3. 8at type of sample must 1e used for pH measurementsD
4. 8at is te recommended oldin" time for pH samplesD
!. 8at is te appro6ed metod for pH measurement for compliance ,it ?0DES permit
re=uirementsD
*apter 3 - #
Section 2: DETER)INATION OF pH
DESCRIPTION OF )ETHOD
Altou" te analysis of pH 1y te electrometric procedure is one of te simplest tests performed in te
,aste,ater la1oratory7 tere are many possi1le sources of error in te analysis. 3e metod steps
include cali1ratin" te meter7 placin" te electrodes in a ,ell-mi-ed sample and readin" te results
directly from te pH meter.
E/UIP)ENT AND REA!ENTS
E/UIP)ENT
1. /ea2ers7 polyetylene or 3eflon preferred
2. pH meter7 reada1le to at least +.1 pH unit
3. electrodes: one "lass and one calomel reference or one com1ination electrode
4. ma"netic stirrer and stirrin" 1ars
!. 3ermometer if pH meter cannot measure temperature
REA!ENTS
1. Distilled 8ater
2. pH 1uffer solutions: pH 47 $7 and 1+
3e pH tests do not re=uire a lar"e num1er of cemicals to 1e prepared and all of tese rea"ents can 1e
purcased from scientific suppliers in ready-to-use form. If te 1uffer solutions must 1e prepared from
scratc7 te procedures descri1ed in Appendi- / are recommended for pH $7 pH 47 and pH 1+ 1uffer
solution preparation.
LABORATOR" PROCEDURE
/ecause of te 6ariation in procedure 1et,een te numerous ma2es and models of pH meters currently
a6aila1le7 it is impossi1le to pro6ide specific instructions for te correct operation of all instruments. In
eac case7 follo, te manufacturer@s instructions for preparin" te electrodes and operatin" te
instrument.
!ENERAL 3CO))ON4 PROCEDURAL STEPS
Ca5i6ration
1. 3urn pH meter on and allo, instrument to ,arm up.
2. Measure te temperature of te standard 1uffer solutions and adAust te meter temperature
compensation dial as necessary. .ecord temperatures. If an automatic temperature compensatin"
electrode is used7 disre"ard tis step as ,ell as step 1+.
3. .emo6e electrode9s; from stora"e solution7 rinse ,it distilled ,ater and carefully 1lot electrode9s;
dry ,it a i" =uality la1oratory tissue.
4. 0lace electrode9s; in pH $.+ 1uffer solution and measure te pH of te 1uffer ,ile "ently stirrin"
solution. A ma"netic stirrin" de6ice is elpful7 1ut not re=uired.
!. AdAust te pH meter readin" to $.+7 if necessary7 ten place te instrument in stand1y mode.
*apter 3 - $
#. .emo6e te electrode9s; from te pH $.+ 1uffer solution7 rinse torou"ly ,it distilled ,ater and
1lot dry.
$. 0lace te electrode9s; in a second 1uffer ,it a pH 6alue at least 2 pH units i"er or lo,er tan te
pH $.+ 1uffer solution. Fsually pH 4.+ and pH 1+.+ 1uffers are used for tis part of te cali1ration.
NOTE: 3e second 1uffer solution sould 1e cosen so tat te e-pected pH of te sample falls
1et,een te first and second 1uffers.
'. Measure te pH of te second 1uffer solution ,ile stirrin"7 adAust meter readin" as necessary and
place instrument in stand1y mode. 3is is "enerally called te 4slope5.
(. .emo6e te electrode9s; from te second 1uffer solution7 rinse torou"ly ,it distilled ,ater and
1lot dry.
Sa7p5e Ana5%'i'
1+. Determine sample temperature7 record and adAust te meter temperature compensation dial7 as
necessary.
11. 0lace electrode9s; in sample7 ten measure and record sample pH ,ile stirrin" te sample.
12. 0lace instrument in stand1y mode and remo6e electrode9s; from sample7 rinse torou"ly ,it
distilled ,ater and carefully 1lot dry.
13. 8en all samples a6e 1een tested7 place electrode9s; in tap ,ater or pH $.+ 1uffer solution for
stora"e and sut 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 fresly prepared 1uffer
solutions. 0repare fres stoc2 1uffer solutions at least once e6ery four ,ee2s. >or 1est results7
1uffer solutions sould 1e discarded after eac use.
2. If possi1le7 pH meter7 1uffer solutions7 and samples sould all 1e te same temperature since
e-treme temperature 6ariations can "i6e erroneous results.
3. 8atc for erratic results arisin" from crac2ed electrodes7 faulty connections or foulin" of electrodes
,it "rease and)or solids residue. 3e t,o point cali1ration ,ill elp detect a faulty electrode. If a
reasona1ly accurate 6alue for te second 1uffer cannot 1e o1tained after te meter as 1een
standardi&ed a"ainst te first 1uffer7 ten it is li2ely tat one7 if not 1ot7 of te electrodes is faulty
and must 1e replaced.
INTERFERENCES
3e "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. 3is error at a pH a1o6e 1+ may 1e
reduced 1y usin" special 4lo, sodium error5 electrodes.
Since 1ot pH7 itself7 as ,ell as te measurement of pH are temperature dependent7 it is important tat
temperature compensation 1e performed on all samples and tat temperatures of 1uffers and samples
1e as similar as possi1le.
*apter 3 - '
PRECISION AND ACCURAC"
3e precision and accuracy attaina1le ,it any "i6en pH meter ,ill depend on te type and condition of
te instrument and te 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
acie6ed ,it many models of pH meter. Ho,e6er7 :)- +.1 pH unit represents te limit of accuracy under
normal conditions. >or tis reason7 report pH 6alues to te nearest +.1 pH unit.
/#i0 31
1. 8at rea"ents are re=uired to perform pH measurement usin" te electrometric
metodD
2. 8at e=uipment7 apparatus or instrumentation is re=uired to perform pH measurement
usin" te electrometric metodD
3. 8at interferences7 if any7 are tere in te electrometric pH procedureD
*apter 3 - (
Section 8: /A9/C
A %uality Assurance)%uality *ontrol pro"ram is re=uired 1y te ?0DES permit. %uality Assurance 9%A;
is a set of operatin" principles tat must 1e follo,ed durin" sample collection and analysis. Ga1 1enc
seets must 1e maintained tat document ,en te sample ,as collected7 o, it ,as preser6ed7 and
,at results ,ere o1tained.
%uality *ontrol 9%*; includes any testin" ,ic is done to pro6e tat te results are relia1le. <ne of
e6ery ten samples analy&ed sould 1e a %uality *ontrol cec2. 3is may include duplicate samples7
spi2e samples7 rea"ent 1lan2 analyses and 2no,n %* samples o1tained from outside sources.
Duplicate sample analysis in6ol6es analy&in" te same sample t,ice and comparin" te results. 3e
closer te results7 te more accurate te analysis. .esults sould not differ 1y more tan 1+H. Spi2e
sample analysis in6ol6es addin" 2no,n amounts of analyte to a sample and calculatin" te percent
reco6ery. 3ese are discussed furter in *apter 1+.
In pH testin"7 1uffers must 1e cec2ed daily and duplicate samples sould 1e run on e6ery tent sample.
%uality *ontrol samples ,it a 2no,n pH are a6aila1le from cemical manufacturers. A sample
cali1ration 1enc seet is included in Appendi- *.
*apter 3 - 1+
An':er' to /#i00e'
/#i0 311
1. A pH of !.! ,ould indicate tat te sample is CCCCCCCCCCC.
Aci&ic
2. 8at is te accepta1le ran"e of pH 6alues for ,aste,ater to 1e treated 1y 1iolo"ical metodsD
-12 * .1
3. 8at type of sample must 1e used for pH measurementsD
!ra6 'a7p5e
4. 8at is te 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
!. 8at is te appro6ed metod for pH measurement for compliance ,it ?0DES permit
re=uirementsD
E5ectro7etric 37eter4 7etho&1
/#i0 31
1. 8at rea"ents are re=uired to perform pH measurement usin" te electrometric metodD
Di'ti55e& <ater an& pH 6#$$er 'o5#tion': pH (= .= an& 1;
2. 8at e=uipment7 apparatus or instrumentation is re=uired to perform pH measurement usin" te
electrometric metodD
a1 Bea>er'= po5%eth%5ene or Te$5on pre$erre&
61 pH 7eter= rea&a65e to at 5ea't ;11 pH #nit
c1 e5ectro&e': one g5a'' an& one ca5o7e5 re$erence or one co76ination e5ectro&e
&1 7agnetic 'tirrer an& 'tirring 6ar'
e1 Ther7o7eter i$ pH 7eter cannot 7ea'#re te7perat#re
3. 8at interferences7 if any7 are tere in te electrometric pH procedureD
So&i#7 error at a high pH1 Thi' error at a pH a6o?e 1; 7a% 6e re&#ce& 6% #'ing 'pecia5
@5o: 'o&i#7 errorA e5ectro&e'1 Te7perat#re co7pen'ation 7#'t 6e per$or7e& on a55
'a7p5e'= an& te7perat#re' o$ 6#$$er' an& 'a7p5e' 'ho#5& 6e a' 'i7i5ar a' po''i65e1
*apter 3 - 11
*apter 3 - 12
APPENDIB A
Re$erence'
Standard Metods for te E-amination of 8ater and 8aste,ater7 A0HA-A88A-8E>7 1'
t
Edition7
1((27 Metod 4!++-H.
Metods for *emical Analysis of 8ater and 8astes7 F.S. E0A-#++)4-$(-+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 diydro"en pospate 9IH
2
0<
4
; and 3.!33 " disodium
ydro"en pospate 9?a
2
H0<
4
; in fresly 1oiled and cooled distilled ,ater and dilute to 1+++ mG.
pH (1;; B#$$er So5#tion
0repare 1y dissol6in" 1+.12 " potassium ydro"en ptalate 9IH*
'
H
4
<
4
; in distilled ,ater and
dilute to 1+++ mG.
pH 1;1;1 B#$$er So5#tion
0repare 1y dissol6in" 2.+(2 " sodium 1icar1onate 9?aH*<
3
; and 2.#4+ " sodium car1onate
9?a
2
*<
3
; in distilled ,ater and dilute to 1+++ mG.
3e ,ide-ran"e pH indicator solution used in te Hac Model 1$-? pH test 2it may 1e purcased
from te Hac *ompany at te follo,in" address:
Hac *ompany
0.<. /o- 3'(
Go6eland7 *olorado '+!3(
1-'++-22$-4224
NOTES:
*apter 3 ) Appendi- / ) 0a"e 1
APPENDIB C
Sa7p5e Ca5i6ration Bench Sheet
Dai5% Ca5i6ration /#a5it% Contro5 3$or the )onth9"ear4
*al. Slope *ec2 *ec2
Date Std. Std. Std. .esult 3emp. 3ec. 3ime
1 1+.++ $.++ 4.++
2 1+.++ $.++ 4.++
3 1+.++ $.++ 4.++
4 1+.++ $.++ 4.++
! 1+.++ $.++ 4.++
# 1+.++ $.++ 4.++
$ 1+.++ $.++ 4.++
' 1+.++ $.++ 4.++
( 1+.++ $.++ 4.++
1+ 1+.++ $.++ 4.++
11 1+.++ $.++ 4.++
12 1+.++ $.++ 4.++
13 1+.++ $.++ 4.++
14 1+.++ $.++ 4.++
1! 1+.++ $.++ 4.++
1# 1+.++ $.++ 4.++
1$ 1+.++ $.++ 4.++
1' 1+.++ $.++ 4.++
1( 1+.++ $.++ 4.++
2+ 1+.++ $.++ 4.++
21 1+.++ $.++ 4.++
22 1+.++ $.++ 4.++
23 1+.++ $.++ 4.++
24 1+.++ $.++ 4.++
2! 1+.++ $.++ 4.++
2# 1+.++ $.++ 4.++
2$ 1+.++ $.++ 4.++
2' 1+.++ $.++ 4.++
2( 1+.++ $.++ 4.++
3+ 1+.++ $.++ 4.++
31 1+.++ $.++ 4.++
*apter 3 ) Appendi- * ) 0a"e 1