1

Basic Water Chemistry

Discussion Topics
 Introduction

 Hydrologic Cycle & Water

Contaminants

 Properties of Water

 Units of Expression

 The Water Molecule

 Solubility

 Acid/Base Chemistry
 Introduction
 Water is the Raw Material Most Used in Nearly All
Industries.
 US Industry uses about 140 Billion Gallons per Day.

Refinery Water Use

Area %
Boiler Make Up 30%
Cooling Tower Make Up 60%
Process Make Up 1%
Desalter Make Up 4%
Sanitary & Lab 4%
4
5
Basic Water Chemistry
 7

Basic Water Chemistry

Hydrologic Cycle
Water Contaminants
Basic Water Chemistry
 WHAT’S INCycle
The Hydrologic WATER?

Air
Earth
Oxygen
Carbon Dioxide
Carbon Monoxide Clay
Calcium Silt
Magnesium Hydrogen Sulfide
Sand
Sodium
Iron

Dissolved Solids Dissolved Gases Suspended Matter

 The Hydrologic Cycle
Contaminants
WHAT’S IN WATER?

SURFACE WATER (Rivers & Lakes)

 Lower in dissolved solids

 Higher in suspended solids

 Quality can change quickly with seasons

and weather
 The Hydrologic Cycle
Contaminants
WHAT’S IN WATER?

GROUND WATER (Wells)

 Higher in dissolved solids
 Lower in suspended solids
 Higher in iron and manganese
 Low in oxygen, may contain sulfide gas
 Relatively constant quality and temperature
 The Bad Properties of Water

Industrial users
have sought ways
to predict when
deposit or
corrosion problems
might develop.
 13

Basic Water Chemistry

Properties of Water
Properties of Water
 Units of Expression
Expressing the Levels of Dissolved Solids:
 Percent - used for Concentrated Solutions
 ppm - a Weight Relationship
 ppm as CaCO3 - an Equivalent Weight Relationship
 mg/l - same as mg/ml - in Dilute Waters, same as ppm
 Grains per Gallon - used primarily in Ion Exchange
Applications
 Properties of Water

 A Series of Predictive Models for Corrosion and

Deposition have evolved:

 Langelier Index
 Ryznar Index
 Computer Models
 Water - the Universal Solvent

 Langelier Index pH - pHs

< 0 = Corrosive
> 0 = Scale Forming

 Ryznar Index 2pHs - pH

< 6 = Scale Forming
> 6 = Corrosive
 Units of Expression

Expressing the Levels of Organics in Water

Dissolved Organic Carbon - DOC

Adds color to water
 Units of Expression

Total Organic Carbon - TOC

Condensate Measure
 Units of Expression

Biological Oxygen Demand - BOD

 Units of Expression

Chemical Oxygen Demand - COD

 The Water Molecule
The simplest of all the ALCOHOLS!
 Alcohol = R-OH
 Water = H-OH
 The Electrons are not shared
equally.

 Oxygen has a higher electron

affinity.

 This results in Highly Polar

Charges on the water molecule

 This is not your average alcohol!

 The Water Molecule

 Polar Sites Create

Weak Bonds
between Water
Molecules
 These are called
Hydrogen Bonds.
 The Water Molecule
From 0oC to 4oC, the Water Molecules Close
Pack and the Density Peaks.
The Water Molecule
 The Water Molecule

At 0oC, there is so little It takes 144 BTUs to break

energy, the Hydrogen the Hydrogen bonds in
one pound of ice.
bonds are rigid.
 The Water Molecule

 As More Energy is
Added, the bonds
elongate, and
water’s density
decreases.
The Chemical and Physical Properties of Water
Result from its Polar Charges.
Thermal Properties of Water and Similar Compounds

Substance Specific Freezing Boiling Heat of

Heat Point Point Vaporization
(0C) (0C) (cal/g)

H2O 1.0 0 100 540

H2S 0.24 -83 -62 132
CH3OH 0.57 -98 65 263
C2H5OH 0.54 -117 79 204
Benzene 0.39 6 80 94
 Water - the Universal Solvent
The polar charges on the water molecule
make it an exceptional solvent.
 Water - the Universal Solvent

 High Purity Water is

a Poor Conductor of
Electricity.
 As More Ions
Dissolve, Water
becomes a Better
Conductor.
 Water - the Universal Solvent
Monovalent ions are more soluble than divalent ions,
which are more soluble than trivalent ions.

Solubility Product Constants

for Commonly Encountered Salts

Compound Ksp

Na+ Cl -
1 High Ksp
2.5 x 10
-9 Decreasing
Ca ++ CO 3 = 2.8 x 10 Solubility
-22
Fe+++ PO 4 1.3 x 10 Low Ksp
 Water - the Universal Solvent
Temperature often Affects the Solubility of Salts.

Ca + CO3 + 3.16 Kcal/mole CaCO 3

As Heat is added, the Reaction proceeds farther to the Right

Na+ + Cl- NaCl + 1 Kcal/mole

As Heat is added, the Reaction proceeds farther to the Left

 Water - the Universal Solvent
The Solubility of Some Salts Vary with pH

As pH increases:
 Hydroxides Increase
 p
Bicarbonates become H
Carbonates I
N
 Phosphates become Divalent, C
R
then Trivalent E
A
 Bisilicates become Silicates S
E
 Water - the Universal Solvent
Some Ions become Less Soluble as the
Oxidation Potential Changes

O
X
Cu+1 Cu+2 I
D
A
T
Fe+2 Fe+3 I
O
N
Mn+2 Mn+4 P
O
T
E
Cr+6 Cr+3 N
T
I
A
L
 Acid - Base Chemistry
Dissociation

H2O H+ + OH-
In pure water, there are 0.0000001 (1x10 -7)
grams of H+ per liter.
Any compound, which consumes Hydrogen
or Hydroxides, acts as an acid or base.
 Acid - Base Chemistry

 Acids - Compounds that increase the

Hydrogen ion concentration in water.
 Bases - Compounds that decrease the
Hydrogen ion concentration in water.
 Acid Base Chemistry
 The pKw of Water is 14 at 24oC.

 pKw = -log10([H+] x [OH-]) = 14

 Water is said to be Neutral when the Moles of H+

equals the Moles of OH-, or pH = pOH = 7 @ 24oC.
 Acid - Base Chemistry

 If you have Ultra Pure Water at

exactly 25 oC, the pH will be 7.0
 If you have a pH of 7.0 in an
Industrial System, it is the Result
of Buffering.
 Acid - Base Chemistry
There is no (very little) relationship between the
concentration (ppm) of alkalinity and pH.

ppm CO2 ppm HCO3- pH

1 5 7.0
5 25 7.0
50 250 7.0
100 500 7.0
 Acid - Base Chemistry

Acids can be ...

 True Hydrogen Donors
HCl H+ + Cl-

 Hydroxide Consumers
Fe+3 + 3OH- Fe(OH)3
 Acid - Base Chemistry

Bases can be ...

 True Hydroxide Donors
NaOH Na+ + OH-

 Hydrogen Ion Consumers

NH3 + H+ NH4+
 Acid - Base Buffering Chemistry
Buffer - Any chemical which may act as an acid or
a base, depending on the system pH

_
Acid HCO3 H+ + CO3 =
HPO4 = PO4 + H+
_
HS H+ + S=
_
Base H +
+ HCO3 H2CO3
_
H +
+ HPO4 =
H2PO4
_
H +
+ HS H2S
 Acid - Base Chemistry
Carbonate Buffering System
1.00
0.90
0.80 Carbonic
Acid
Bicarbonate Carbonate
HCO3- CO3-2
Mole Fraction

0.70
H2CO3
0.60
0.50 O Alkalinity
0.40 M Alkalinity P Alkalinity Endpoint
Endpoint
0.30 Endpoint
0.20
0.10
0.00
4 5 6 7 8 9 10 11 12
pH
 Acid - Base Chemistry

Alkalinity pH
Measurement Indicator Endpoint Remarks

P Alkalinity Phenolphtalein 8.3 All Hydroxides, ½ Carbonates.

M Alkalinity Methyl Orange 4.3 All Bicarbonates,

Methyl Purple 4.3 All Carbonates, All
Hydroxides.

O or OH Methyl Orange 4.3 All Hydroxides.

Alkalinity Methyl Purple 4.3 Add Barium Chloride prior to
Titration to obtain a direct
measurement of Hydroxide
Alkalinity
 Acid - Base Chemistry

Alkalinity Bicarbonate Carbonate Hydroxide

P=0 M 0 0

2P < M M - 2P 2P 0

2P = M 0 2P 0

2P > M 0 2 (M - P) 2P - M
Basic Water Chemistry

QUESTIONS