Tables of Contents

- Ceneral properues of waLer

- lmpurlues ln waLer
- Pardness and alkallnlLy
- Solublllues
- pP and Cycles of concenLrauon
- Coollng waLer LreaLmenL
! Corroslon and Scale lnhlblLors
! 8locldes
- Cperauon and Lesung
General Properties of Water
- Some of Lhe properues of waLer whlch make lL ldeal
for lndusLrlal coollng processes are llsLed below:
! WaLer has Lhe capaclLy Lo sLore and LransporL heaL
! WaLer absorbs more heaL per pound Lhan any oLher
lnorganlc subsLance
! WaLer has Lhe followlng physlcal properues:
" Cne pound of waLer glves up 144 81u's upon freezlng
" AL aLmospherlc pressure, waLer freezes aL 32 deg l and bolls
aL 212 deg l
" WaLer ls mosL dense aL 40 deg l
" Cne pound of waLer, when Lransformed lnLo sLeam, releases
970 81u's
" ure waLer does noL exlsL ln naLure
General Properties of Water
- 1here are Lwo maln sources of waLer, noLe general
dlerences
! Wells and sprlngs are classled as ground waLer sources
! Low suspended sollds and dlssolved oxygen, hlgh dlssolved sollds
lncludlng lron, hardness, and alkallnlLy, and also hlgh carbon dloxlde
! 8lvers and lakes are classled as surface waLer sources
! Plgh suspended sollds and dlssolved oxygen, low dlssolved sollds
lncludlng lron, hardness, and alkallnlLy, and also low carbon dloxlde
Types of Impurities in Water
- Suspended sollds
! 1urbldlLy
" llnely dlvlded suspended or colloldal mauer
(clay, sllL, dlrL, organlc mauer)
! Color
" An arblLrary sLandard scale used Lo measure
soluble organlc maLerlals ln waLer
!"#$%&'
Ca
Mg
k
na
le, Al, Cu
Zn, Sl
"&$%&'
Cl
PCC
3
CC
3
SC
4
C
4
nC
3
Types of Impurities in Water (cont.)
- ulssolved sollds
! ulssolved mlneral sollds
" When raln falls, lL scrubs Lhe aLmosphere of carbon dloxlde
" Carbon dloxlde mlxes wlLh waLer Lo form a weak acld called
carbonlc acld
" 1he carbonlc acld dlssolves mlneral sollds conLalned ln naLure,
such as:
! LlmesLone (calclum carbonaLe), dolomlLe (magneslum carbonaLe),
epsom salL (magneslum sulfaLe), gypsum (calclum sulfaLe), sand
(slllca), and common salL (sodlum chlorlde).
" Mlnerals conLalnlng sodlum have a relauvely hlgh solublllLy
ln waLer
" Mlnerals conLalnlng calclum and magneslum have a relauvely
low solublllLy ln waLer
Types of Impurities in Water (cont.)
- ulssolved Cases
! Cxygen
" Corroslve Lo meLal aL elevaLed concenLrauons
" SolublllLy ln waLer depends on LemperaLure, surface area
and pressure
! Carbon uloxlde
" Wlll form carbonlc acld, a weak acld, when dlssolved ln waLer
" Carbonlc acld dlssoclaLes Lo form blcarbonaLe and carbonaLe
alkallnlLy whlch ls pP dependenL
" SolublllLy ln waLer depends on LemperaLure, surface area
and pressure
Types of Impurities in Water (cont.)
- Mlscellaneous lmpurlues
! 8acLerla LhaL requlre oxygen and produce carbon dloxlde are
aeroblc bacLerla
! 8acLerla LhaL do noL requlre oxygen and produce hydrogen
sulde are anaeroblc bacLerla
! Algae favors exposure Lo sunllghL
! lungl favors dark secluded areas
Hardness and Alkalinity
- Pardness (calclum and magneslum) and alkallnlLy
(blcarbonaLe and carbonaLe) boLh play a ma[or role ln
coollng waLer LreaLmenL:
" 1he weak acld, carbonlc acld, LhaL ls formed durlng ralnfall has
Lhe ablllLy Lo dlssolve mlnerals ln Lhe earLh's sLraLa
" 1he acld soluuon ls composed of hydrogen, Lhe posluvely
charged poruon of Lhe soluuon (acldlc poruon), and a negauvely
charged counLerparL
" lf Lhe earLh's sLraLa conLalns appreclable quanuues of llmesLone
and dolomlLe, Lhen Lwo of Lhe prlmary reacuons beLween Lhe
weak acld and Lhe sLraLa wlll be wlLh Lhe calclum carbonaLe and
magneslum carbonaLe
Hardness and Alkalinity (cont.)
- Pardness (calclum and magneslum) and alkallnlLy
(blcarbonaLe and carbonaLe) boLh play a ma[or role ln
coollng waLer LreaLmenL:
" As Lhe mlneral dlssolves, boLh Lhe calclum and carbonaLe (as
well as Lhe magneslum and carbonaLe), go lnLo soluuon
" Cnce dlssolved, boLh Lhe calclum and magneslum (Lhe posluvely
charged poruons of Lhe mlneral), Lend Lo favor reverung" back
Lo Lhelr naLural lnsoluble sLaLe
" When comblned wlLh oLher mlneral lmpurlues, calclum and
magneslum wlll preferenually preclplLaLe ouL of soluuon and
form an lnsoluble sludge
" 1he reacuon of calclum and magneslum ln waLer wlLh soaps and
deLergenLs creaLes an undeslrable sludge whlch can make
launderlng dlmculL. 1he dlmculLy or hard Lo wash condluon"
led Lo Lhe Lhe Lermlnology WaLer Pardness"
Solubilities
- 1he common mlneral subsLances can be
classled lnLo four caLegorles based on
solublllLy:
! Calclum and magneslum compounds rules
of Lhumb
" SolublllLy decreases when LemperaLure rlses,
alkallnlLy lncreases, and avallable carbon
dloxlde decreases
" 8ouom llne: hardness salLs are more llkely Lo
drop ouL aL hlgh LemperaLures and pP
! Sodlum compounds rules of Lhumb
" SolublllLy lncreases as LemperaLure lncreases. lf deposlLs
wlLh sodlum are found, lL can generally be aurlbuLed
Lo exLreme concenLrauons or evaporauon Lo dryness
" 8ouom llne: Sodlum compounds are rarely a problem
caused by waLer LreaLmenL)
!"#$%&'
Ca
Mg
k
na
le, Al, Cu
Zn, Sl
"&$%&'
Cl
PCC
3
CC
3
SC
4
C
4
nC
3
Solubilities (cont.)
- 1he common mlneral subsLances can be
classled lnLo four caLegorles based on
solublllLy !"#$%&' :
! Slllca dloxlde rule of Lhumb
" SolublllLy lncreases as alkallnlLy lncreases
! lron and manganese compounds rule of Lhumb
" SolublllLy decreases as waLer alkallnlLy lncreases
and as Lhe degree of oxldauon lncreases
(l.e. oxygen, chlorlne, bromlne)
!"#$%&'
Ca
Mg
k
na
le, Al, Cu
Zn, Sl
"&$%&'
Cl
PCC
3
CC
3
SC
4
C
4
nC
3
pH and Cycles of Concentration
- uened exacLly, pP ls Lhe logarlLhm of Lhe reclprocal of Lhe
hydrogen lon concenLrauon ln Lhe reacuon
- A more slmple explanauon ls LhaL pP ls a number beLween 0 and
14 LhaL denoLes varlous degrees of acldlLy and alkallnlLy, wlLh
neuLral waLer aL pP 7. 8elow 7 becomes lncreaslngly acldlc, whlle
above 7 becomes lncreaslngly alkallne
pH and Cycles of Concentration (cont.)
- pP ls a very lmporLanL parameLer ln waLer LreaLmenL, especlally ln
coollng waLer LreaLmenL. As waLer ls cycled, alkallnlLy
concenLraLes, so subsequenLly pP lncreases, example:
- We call Lhls example as belng 2 cycles of concenLrauon, where
mlneral concenLrauons, as well as conducuvlLy, are doubled
- AL uMC Shadyslde, Lowers average 3 cycles of concenLrauon
WaLer wlLh 100 ppm
alkallnlLy
WaLer wlLh 200 ppm
alkallnlLy, pP lncrease
Add heaL, lose x Lhe
volume of waLer
Lhrough evaporauon
Langelier Saturation Index (LSI)
- A numerlcal value for Lhe scallng poLenual of calclum
carbonaLe (CaCC
3
)
- 1he equauon ls a numerlcal comblnauon of:
! 1oLal dlssolved sollds
! 1emperaLure
! Calclum hardness
! AlkallnlLy
! pP
- A posluve LSl ls scale formlng, a negauve LSl ls
corroslve, and zero ls perfecL equlllbrlum
LSI/RSI Calculation
- LSl = pP - pP
s
- pP
s
= 9.3 + 1uS[)] + 1emp[)]
*!Ca[)] + Alk[)])

Methods of Treatment for High LSI
- Acld leed
! 8y reduclng pP ln coollng waLer, Lhe equauon
LSl = pP - pP
s

means LhaL LSl wlll be reduced, Lherefore calclum
carbonaLe scallng poLenual ls reduced
! roper dlluuon of acld ls crlucal Lo conLacL all polnLs
of Lhe sysLem. lL ls !"#$%&'(& &$ *+,!# &-* ./.&*" 0!&-
.'1*2,'%3. lf acld feed ls losL or lnemclenL
Methods of Treatment for High LSI #2
- Crganlc phosphonaLes comblned wlLh polymers can
wlLhsLand LSl Lo
+
3.0
- usually safe Lo malnLaln LSl aL
+
2.3
- AnoLher meLhod of conLrolllng LSl ls soened
make-up, buL requlres manhours for regenerauon
and malnLenance
Cooling Water Treatment
- Cb[ecuve of a coollng waLer LreaLmenL program:
! MalnLaln opumum heaL Lransfer ln process equlpmenL and
heaL exchangers
! lnsure equlpmenL rellablllLy and avallablllLy
! Mlnlmlze operaung cosLs
! rovlde predlcuve LreaLmenL recommendauons for sysLem
operaung changes and Lower conLamlnauon
! MalnLaln healLhy envlronmenL ln molsL areas around
perlmeLer of Lower
! Assure sysLem clrculauon Lo keep all areas wlLh
fresh ow on a regular basls
Cooling Water Treatment (cont.)
- Ma[or concern areas:
! Scale: lormauon of lnsoluble deposlLs on heaL Lransfer
surfaces, usually hardness salLs on Lhe mosL crlucal (or
houesL) areas
" Plgh poLenual wlLh hlgh LemperaLures, hlgh pP, excesslve
alkallnlLy, hlgh dlssolved sollds, and hlgh hardness
! Corroslon: Loss of meLal by reacuon wlLh Lhe envlronmenL
" lormauon aL Lhe anode or caLhode semng up an elecLrlcal
clrculL", or oxldauon of base meLal
! loullng: Mlcroblologlcal and suspended sollds deposluon
" Algae, fungl, or bacLerla dependlng upon locauon ln sysLem,
can acL as Lhe glue LhaL holds deposlLs LogeLher"
Changing Chemistries
Over the Years
- 1oxlc naLure of ChromaLe
- ueslre Lo LllmlnaLe Acld
- ueslre Lo CperaLe aL Plgh Cycles
- Lconomlc ressure
- More Lecuve lnhlblLors
Overview
- Carbon SLeel Corroslon rocess
- Pow Chemlcal 1reaLmenLs Work
- 1reaLmenL rograms: +,- ./0% 12 3-/40
- 1he luLure
Corrosion Process
AnCuL
le -le
+2
+ 2e
-

CA1PCuL
P
2
C + xC
2
+ 2e
-
- 2CP
-
Rust Formation
le
+2
hydraLed Lo le(CP)
2

le(CP)
2
oxldlzed Lo le(CP)
3
le(CP)
3
preclplLaLes

Anodic Inhibitors
lnhlblL oxldauon of lron
romoLe gamma - le
2
C
3
reclplLaLes ll volds

Anodic Inhibitors
- ChromaLe
- nlLrlLe
- MolybdaLe
- CrLhophosphaLe
Cathodic Inhibitors
lnhlblL CaLhodlc 8eacuon
lorm 8arrler lllms
Plgh surface pP causes preclplLaLes
P
2
C + xC
2
+ 2e
-
- 2CP
-
Cathodic Inhibitors
- olyphosphaLes
- hosphonaLes
- Zlnc
- Calclum CarbonaLe
Inorganic Phosphates
- CrLhophosphaLe
- yrophosphaLe
- 1rlpolyphosphaLe
- olyphosphaLe
Phosphates
- 1940's: olyphosphaLe Classes
- 1930's -1960's: Zlnc/oly Classes
- 1970's: hosphaLe LsLers
- 1980's: SLablllzed hosphaLes
Stabilized Phosphate
1sL SLablllzed hosphaLe rogram
56/$#76" 889
:0% ;<=/<6$- >%/?6<6@-7 A,#0B,/%- A4#C4/D
BE4--FG;H59

Calcium Phosphate Inhibition
$)*+,+-./0 "1234 5.0674
897:;<
=4/14)-
$)*+,+2.)
70/30 AA/AM 30 < 23
AA/PL 17 > 90
1:1 MA:SS 17 > 90
MA 30 < 20
olyasparuc Acld (Creen) 30 < 20
Calcium Phosphate Inhibition
$)*+,+-./0 >+)+9?9 @A41234 5.04
897:;<
=4/14)-
$)*+,+2.)
60/40 AA/AMS 7-8 >90
!+HI*1JJK ;H*LMNK I+*M2K ;"OD-4 1:22K PQNL*JR;>'
AA/AMS/18AM !;"OD-4 J:22' 7-8 > 90
AA/AMS/SS !F##746%- S*RTU' 7-8 > 90
AA/APSL 8 >90
73/23 AA/AMS 9-10 >90
!+HI*1JJ6K ;H*LMLK ;"OD-4 1222K PQN2*ML;>'
SulfonaLed AA olymer !;VO/%4-/% WA>' 9-10 > 90
All-Organic
- PLu/AM
- PLu/81C
- PLu/C81PC
- PLu/PA
Halogen Stabilizers
Cyanurlc Acld
Sulfamlc Acld
MonoeLhanolamlne

Chlorine Tolerant
8A?L8: 81C
8PCulA: MA

Zinc Products
Zlnc/olyphosphaLe
Zlnc/CrLho
Zlnc/AM
Zlnc/PLu
Zlnc/81C
WlLh olymer

High Calcite Saturation: 240X (LSI=2.8)
$)*+,+-./0 B $)*+)+2.)
861234 C.0674 97:;<
20 mg/L 30 mg/L
L 91 100
81C 72 76
PLu 38 33
AM - 31
PA 44
MA 46 39
MA 31
olyasparuc Acld - 39
Green Chemistry
Low/non-Zlnc
Low/non-hosphaLe
MA

Conclusion
- MosL lmporLanL uevelopmenL: lmproved olymers
- olymer of Cholce: 60/40 AA/AMS
- 8esL Plgh CalclLe SaLurauon lnhlblLor: naLcolene L
- luLure: More SLudles needed for Creen ChemlsLrles
Oxidizing Biocides
- Chlorlne based
! noL as eecuve above pP 7.3
" Sodlum hypochlorlLe
! 8leach" avallable aL 14
" P1P
! Calclum hypochlorlLe powder, rapld dlssolvlng
" Chlorlne lsocyanuraLe LableLs
! Crganlc chlorlne rapld dlssolvlng LableLs
" Chlorlne dloxlde
! Comblnauon of sulfurlc acld and hypochlorlLe
Oxidizing Biocides (cont.)
- 8romlne based
! Lecuve above pP 7.3
" SLablllzed bromlne
! 14 bromlne comblned wlLh sodlum hypochlorlLe
" 8romlne hydanLoln LableLs
! Slow dlssolvlng fed vla bromlnaLor
" 8romlne lsocyanuraLe
! 8apld dlssolvlng bromlne LableLs
Non-Oxidizing Biocides
- Llquld blocldes used Lo supplemenL
an oxldlzlng bloclde program
! led vla pumps on 7 day umer
! AcLs as a polson Lo klll bacLerla/algae/fungl/mold
" WSC (142L) - algae, bacLerla, fungl
" CarbamaLe - bacLerla, sulfaLe reducers, fungl
" M81 -bacLerla, sulfaLe reducers, fungl
" 1erbuLhylazlne - algae
" lsoLhlazollne - bacLerla, sulfaLe reducers, fungl
" u8nA - bacLerla
" CluLaraldehyde - bacLerla, sulfaLe reducers, fungl
" 1hlone - bacLerla, fungl
" 1rlazlne - algae
" uCP - bacLerla, sulfaLe reducers, fungl
Operation and Testing
- MolybdaLe 1esL
1. Add 1.3 mL of Lower waLer Lo each vlewlng Lube
2. Add Lap waLer Lo 1sL mark of each vlewlng Lube (3 mL mark)
3. Add one Molybdenum 1 8eagenL owder lllow Lo one of Lhe
Lubes
4. Add elghL drops of Molybdenum 2 8eagenL Lo Lhe same
Lube used ln SLep 3
3. lnserL Lhe Lube from SLep 4 lnLo Lhe rlghL openlng of
Lhe color comparaLor
6. lace Lhe blank lnLo Lhe le openlng, and hold up
Lo naLural llghL
7. 1he conLrol dlsplay range ls 1.1 mg/L Lo 1.8 mg/L
Operation and Testing (cont.)
- 1oLal and lree Palogen 1esL
1. llll a vlewlng Lube Lo Lhe rsL llne (3 mL) wlLh sample waLer
2. Add elLher LoLal or free chlorlne powder plllow Lo Lhe sample
3. lor LoLal chlorlne LesL, allow 3 mlnuLe reacuon ume before
readlng resulL
4. vlew sample ln comparaLor, conLrol free chlorlne 0.1 -0.3 mg/L and
LoLal chlorlne < 1.0 mg/L.
- ConducuvlLy
! ConLrol 1600 -2000 umhos conducuvlLy
- Sanlcheck 1esL klL
! ConLrol < 10
3
bacLerla/mL
Review Quiz
- WhaL ls Lhe scale LhaL we are mosL concerned wlLh ln
reclrculaung coollng waLer sysLems?
- lf Lhe makeup waLer ls 400 conducuvlLy, and Lhe Lower
waLer ls aL 2000 conducuvlLy, whaL are Lhe cycles
of concenLrauon?
- WhaL are ways Lo conLrol leglonella bacLerla ln a
coollng Lower?
- Where ls hardness mosL llkely Lo drop ouL of Lhe waLer
soluuon ln a coollng waLer sysLem?
- WhaL safeLy equlpmenL ls necessary when handllng
LreaLmenL chemlcals?