CHAPTER
4A Basic Chemistry
Introduction
Mud engineers deal with chemistry
Chemistry is every day. Chemistry is the study of
the study of matter, including its composition, its
properties, and its transformation
matter… into, or reaction with, other sub-
stances (chemical reactions). Matter
is something that has mass and
occupies space.
Mass is a measure of the quantity
of matter or the amount of material
something contains. Mass is one of
the fundamental quantities upon
which all physical measurements are
based. Mass causes matter to have
weight in a gravitational field and
inertia when in motion. The weight
of something is the force of gravity
acting on a given mass and is directly
proportional to the mass times the
gravitational force (acceleration).
Common units for mass are grams
(g) and pounds-mass.
Classification of Matter
All substances fall into one of three
_______________________ physical states:
• Solid
_______________________
• Liquid
_______________________ • Gas
_______________________ Solids usually have higher density
_______________________ than liquids and gases. They are sub-
stances which are not fluid and, there-
_______________________
fore, do not flow when force is applied.
_______________________ Solids do not readily conform to the
_______________________ shape of their container.
Liquids usually have a density less
_______________________
than solids, but greater than gases.
_______________________ Liquids will readily conform to the
_______________________ shape of their container. Both liquids
_______________________
and gases are fluids which “flow”
when a force is applied.
_______________________
Gases not only conform to, but
_______________________ expand, to fill their container.
_______________________ All substances can also be separated
into one of two categories:
Basic Chemistry 4A.1
Volume is a measure of the quantity
of space occupied by matter. Common
oilfield units of volume are gallons (gal),
barrels (bbl), cubic feet (ft3), liters (l) and
cubic meters (m3).
Density is defined as the ratio of mass
divided by volume. Common oilfield
units of density are pounds per gallon
(lb/gal), pounds per cubic foot (lb/ft3),
kilograms per cubic meter (kg/m3) and
grams per cubic centimeter (g/cm3).
Specific gravity is a special expression
of density often used for liquids and
solids. It is the ratio of a substance’s
density divided by the density of pure
water at a stated temperature, usually
4°C. Likewise, the density of gases is
often expressed as a “gas gravity,” or
the ratio of the density of a particular
gas divided by the density of pure air
at standard conditions.
• Homogeneous (pure substances)
• Heterogeneous (mixtures
of substances)
An example of a homogeneous
material would be table salt, wherein
each grain is identical in chemical
composition. An example of a hetero-
geneous (non-uniform) material would
be riverbed gravel; it is a mixture of
rocks — from a variety of sources —
having different chemical composi-
tion, appearance and properties.
Drilling fluids and most materials
found in nature are mixtures.
Homogeneous materials (pure sub-
stances) are occasionally found in
nature, but more often are manufac-
tured by processing to separate dissimi-
lar materials or to remove impurities.
Pure substances can be identified
because they are homogeneous and
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4A Basic Chemistry

have uniform composition, no matter elements). A pure substance is a com-

how they are subdivided or where they pound if it can be subdivided into at
are found. least two elements. All compounds are
Pure substances can be separated formed by the combination of two or
into one of two distinct categories: more elements. If a pure substance
• Elements cannot be separated into two or more
• Compounds elements, it must be an element.
Elements Elements cannot be broken down It is convenient to refer to an ele-
(decomposed) or subdivided into sim- ment with an abbreviation called a
cannot be symbol rather than the full name.
pler substances by ordinary chemical
broken methods. Elements are the basic build- Table 1 contains the chemical name,
down or ing blocks of all substances and have symbol, atomic weight and common
unique properties. Compounds can be valence (electrical charge) of the ele-
subdivided ments of most interest to the drilling
reduced into two or more simpler sub-
into simpler stances (either elements or groups of fluid industry.
substances…
Element (Latin) Symbol Atomic Weight Common Valence
Aluminum Al 26.98 3+
Arsenic As 74.92 5+
Barium Ba 137.34 2+
Boron B 10.81 3+
Bromine Br 79.90 1-
Cadmium Cd 112.40 2+
Calcium Ca 40.08 2+
Carbon C 12.01 4+
Cesium Cs 132.91 1+
Chlorine Cl 35.45 1-
Chromium Cr 52.00 6+
Copper (cuprium) Cu 63.55 2+
Fluorine F 19.00 1-
Hydrogen H 1.01 1+
Iodine I 126.90 1-
_______________________
Iron (ferrum) Fe 55.85 3+
_______________________ Lead (plumbum) Pb 207.19 2+
Lithium Li 6.94 1+
_______________________
Magnesium Mg 24.31 2+
_______________________ Manganese Mn 54.94 2+
_______________________ Mercury (hydrargyrum) Hg 200.59 2+
Nickel Ni 58.71 2+
_______________________ Nitrogen N 14.00 5+
_______________________ Oxygen O 16.00 2-
Phosphorus P 30.97 5+
_______________________
Potassium (kalium) K 39.10 1+
_______________________ Silicon Si 28.09 4+
Silver (argentum) Ag 107.87 1+
_______________________
Sodium (natrium) Na 22.99 1+
_______________________ Sulfur S 32.06 2-
_______________________ Tin (stannum) Sn 118.69 2+
Titanium Ti 47.90 4+
_______________________
Zirconium Zr 91.22 4+
_______________________ Zinc Zn 65.37 2+

_______________________ Table 1: Common elements.

Basic Chemistry 4A.2 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER

4A Basic Chemistry

Atomic Structure

Diffuse cloud of light electrons (–) orbiting the nucleus in

structured shells.

All matter is composed of discrete

units called atoms. The atom is the
smallest unit into which an element
can be divided and still retain the ele-
ment’s unique chemical properties.
Atoms are Atoms are the basic building blocks for
the basic all matter; they are the smallest units
of an element that can combine with
building atoms from another element. Atoms of
blocks for different elements have different prop-
all matter… erties. Atoms are neither created nor
destroyed in chemical reactions.
Atoms contain three subatomic
particles:
• Protons
• Neutrons
• Electrons
The atom has two distinct zones: a Nucleus is compact and dense, containing heavy protons (+) and
neutrons (neutral).
small, dense nucleus, which contains
the protons and neutrons, surrounded Figure 1: Atomic structure.
by a diffuse cloud of electrons. The size
of an atom depends almost entirely on (no valence), the number of electrons is
the amount of volume occupied by equal to the number of protons so that
the electron cloud of the atom, while the net charge of the atom is neutral.
virtually all the mass is located in the Some atoms can gain or lose electrons
nucleus (see Figure 1). so that a charged atom, called an ion, is
The nucleus is approximately spheri- formed. When an electron is lost, a pos-
cal, 10 – 4 angstrom (Å) or 10–14 m in itive charge results. A positively charged
diameter and contains protons and ion is called a cation. Similarly, when an
neutrons only. A proton has a positive electron is gained, a negatively charged
charge while a neutron has no charge. “anion” is formed.
The mass The electron cloud, or shell, also is The mass of either a proton or a neu-
of either a approximately spherical, 1 Å or 10 –10 m tron is roughly 1,837 times greater than
in diameter and contains only elec- the mass of an electron. Due to this
proton or huge difference in mass, the mass of
trons, which orbit the nucleus much
a neutron like a miniature solar system. An elec- the protons and neutrons in the nucleus
is roughly tron has a negative charge equal in account for the approximate total
mass of the atom (see Table 2).
1,837 times strength to the positive charge of a
proton. In neutrally charged atoms
greater than Particle Charge Mass (g)
Proton Positive (1+) 1.6724 X 10 – 24
the mass of Neutron None (neutral) 1.6757 X 10 – 24
an electron. Electron Negative (1-) 0.000911 X 10 – 24

Table 2: Mass and charge of subatomic particles.

Basic Chemistry 4A.3 Revision No: A-1 / Revision Date: 02·28·01

 CHAPTER
4A Basic Chemistry
The nucleus of an atom is very
dense; approximately 1,770 tons/in.3
(98,000 kg/cm3). The electron cloud
has a diameter 10,000 times larger
than the nucleus. The larger volume
of the low-density electron cloud bal-
ances the high density of the nucleus
to an average density of 2 to 20 g/cm3.
The lightest The lightest and simplest element is
and simplest hydrogen, which has only one proton
in each nucleus. Naturally occurring
element is atoms contain between 1 and 93 pro-
hydrogen… tons in their nucleus. Heavier atoms,
with even more protons, have been cre-
ated in laboratories, but are unstable
and do not occur naturally. All atoms
that have the same number of protons
in their nuclei have identical chemical
properties and are called elements.
There are 92 naturally occurring ele-
ments which, in various combinations,
form the physical world.
The number of protons (p+) in the
nucleus is used to define each element
and is called the “atomic number” (z).
Hydrogen, with just one proton, has an
atomic number of 1. The sum of the
number of protons and neutrons (n) in
the nucleus of an atom is called the
“atomic mass number” (a), a = p+ + n.
Each element Each element may have several
may have atomic structures called isotopes, each
with a different number of neutrons in
several its nucleus, giving each a different
atomic atomic weight. Although these isotopes
structures of an element will have different atomic
weights, they will have identical chemi-
called cal properties, and form compounds
isotopes… with the same properties. Isotopes are
written with the atomic number (z) as
a subscript before the chemical symbol
and the atomic mass number (a) as a
superscript ( zaX). Hydrogen has three
isotopes. The most common isotope of
hydrogen has no neutron in its nucleus
(11H), the second most common isotope
has one neutron (21H) and the third iso-
tope contains two neutrons (31H). All
Basic Chemistry 4A.4
three of these isotopes contain only one
proton in the nucleus.
The atomic mass scale is a relative
mass scale based on the mass of the
carbon isotope, 126 C, which has a mass
of exactly 12.0 atomic mass units (amu).
This scale is used to simplify expressing
such small values of mass for each iso-
tope of each element. The mass of one
neutron, or one proton, is roughly
equal to 1 atomic mass unit (amu).
The atomic weight of an element is
equal to the weighted average mass of
all the isotopes of the element on the
atomic weight scale. For example, the
three hydrogen isotopes, 11H, 21H and
3
1H, have masses of 1.0078, 2.0140 and
3.01605 atomic mass units, respectively.
The fraction of each isotope that occurs
in nature are 0.99985, 1.5 x 10 – 4 and
10 –11. The atomic weight of hydrogen,
therefore, is: (0.99985) 1.0078 + (1.5 x
10 –4) 2.0140 + 10 –11 (3.01605) = 1.0079.
Some combinations of neutrons and
protons are not stable in the nucleus
of an atom. These unstable nuclei will
break apart naturally, or “decay,” to
form atoms of entirely different ele-
ments. This “decay” is a nuclear (phys-
ical) reaction which involves neither a
chemical reaction with oxygen nor a
biological activity normally associated
with chemical decay. Isotopes that are
subject to nuclear decay are said to be
radioactive. When an atom decays, it
releases subatomic particles and energy
(radioactivity). Radioactivity is widely
used for laboratory analytical evalua-
tions of chemicals and minerals. Some
wellbore evaluation logs use either a
radioactive source or natural back-
ground radiation to identify and evalu-
ate formations and formation fluids.
Atoms of one element bond with
atoms of other elements to form com-
pounds either by transferring elec-
trons (ionic bonding) or by sharing
electrons (covalent bonding). Bonding
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4A Basic Chemistry

is the combination of attractive forces Molecules are composed of two or more

between atoms which make them act chemically bonded atoms. Atoms in a
as a compound or unit. The manner molecule always combine in particular
in which bonding occurs has impor- ratios and with specific orientations.
tant implications for a compound’s Molecules cannot be divided into any
physical properties. smaller unit and still retain the com-
Two or more Two or more elements can combine pound’s unique chemical properties.
elements can to form a compound. Elements in a The composition of a compound
compound are bound together by can be described by a simple chemical
combine shared electrons. Compounds have formula using the atomic symbols and
to form a different chemical and physical prop- subscript numbers which show how
compound. erties than the elements from which many of each atom are in the simplest
they are formed. For instance, both molecule. For example, the smallest
hydrogen and oxygen are gases at particle of carbon dioxide is one mole-
standard conditions, but when com- cule with one carbon atom bonded to
bined to form water, they exist as a two oxygen atoms and can be repre-
liquid. Table 3 lists the chemical sented by the chemical formula CO2.
name, formula and common name Groups of atoms bonded together
for the most common compounds of also can be ions (polyatomic ions). For
interest to the drilling fluids industry. example, the hydroxyl ion, OH–, is an
The smallest unit into which a com- anion with a net 1- charge, or one extra
pound can be divided is a molecule, a electron. The ammonium ion, NH4+, is a
combination of tightly bound atoms. polyatomic cation with a 1+ charge.
Name Formula Common Name Name Formula Common Name
Silver nitrate AgNO3 — Magnesium oxide MgO Mag ox
Aluminum oxide Al2O3 Alumina Magnesium Mg(OH)2 —
Barium sulfate BaSO4 Barite hydroxide
Barium carbonate BaCO3 Mineral witherite Nitric acid HNO3 Aqua fortis
Barium hydroxide Ba(OH)2 — Potassium chloride KCl Muriate of potash
Calcium Sodium hydroxide NaOH Caustic soda
hydroxide Ca(OH)2 Hydrated lime Sodium
_______________________ bicarbonate NaHCO3 Baking soda
Calcium sulfate CaSO4 Anhydrite
_______________________ (anhydrous) Sodium chloride NaCl Salt
Calcium sulfate CaSO4 • 2H2O Gypsum Sodium carbonate Na2CO3 Soda ash
_______________________ (hydrous) Sodium sulfate Na2SO4•10H2O Salt cake,
_______________________ Calcium carbonate CaCO3 Limestone, Glauber’s salt
marble, calcite Sodium acid Na2H2P2O7 SAPP
_______________________ Calcium chloride CaCl2 — pyrophosphate
_______________________ Calcium oxide CaO Quick lime, Sodium Na6P4O13 Phos
hot lime tetraphosphate
_______________________ Hydrochloric acid HCl Muriatic acid Silicon dioxide SiO2 Quartz, silica
Hydrogen oxide H2O Water Zinc carbonate ZnCO3 —
_______________________
Sulfuric acid H2SO4 — Zinc sulfide ZnS —
_______________________ Hydrogen sulfide H2S — Zinc oxide ZnO —
_______________________ Table 3: Common compounds.
_______________________

_______________________

_______________________

_______________________

_______________________

Basic Chemistry 4A.5 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER

4A Basic Chemistry

Valence
The valence of an element or ion is compound Ca(OH)2. Many elements,
the number of electrons it can gain, such as iron, chrome, nickel, chlorine
lose or share in order to become a sta- and sulfur, can have several valences.
ble, neutrally charged compound. The Valence also is often referred to as the
hydrogen atom is selected as the refer- “oxidation state” (as it is listed later in
ence and has one positive bond, or a Table 5). Table 4 is a list of common
Valence valence of 1+. Valence determines elements and ions (groups) with their
determines which elements or ions will combine respective symbols and valences.
and in what ratio they will combine.
which For example, one atom of chlorine Element Symbol Valence
elements (Cl) combines with one atom of hydro- Hydrogen H 1+
Oxygen O 2-
or ions will gen (H, 1+ valence) to form hydro-
Potassium K 1+
chloric acid (HCl), so chlorine must
combine and have a 1- valence. One oxygen atom
Sodium Na 1+
Calcium Ca 2+
in what ratio (O) combines with two hydrogen atoms Magnesium Mg 2+
they will to form water (H2O), so oxygen has Aluminum Al 3+
a 2- valence. One sodium atom (Na) Zinc Zn 2+
combine. combines with one chlorine atom Iron Fe 3+, 2+
(Cl, 1- valence) to form salt (NaCl), so Silver Ag 1+
sodium must have a valence of 1+. One Carbon C 4+
atom of calcium (Ca) combines with Phosphorus P 5+
two atoms of chlorine to form calcium Sulfur S 2+,4+,6+
Chlorine Cl 1-,1+,3+,5+,7+
chloride (CaCl2), so calcium must have
Ion or Group Symbol Valence
a 2+ valence. Following the same line
Hydroxide OH 1-
of reasoning, the valence of K in KCl Oxide O 2-
must also be 1+. If we consider the Carbonate CO3 2-
compound H2SO4, we see that the Bicarbonate HCO3 1-
valence of the sulfate group or ion Sulfate SO4 2-
_______________________ (SO4) must be 2- since there are two Sulfite SO3 2-
_______________________ hydrogen atoms. The sulfate ion (SO42–) Sulfide S 2-
is taken as a complete unit. In the case Nitrate NO3 1-
_______________________
of caustic soda (NaOH), since Na has a Nitrite NO2 1-
_______________________ valence of 1+, then the hydroxyl ion Phosphate PO4 3-
(OH) must have a valence of 1-. For Ammonium NH4 1+
_______________________
Acetate C2H3O2 1-
calcium hydroxide (lime), since cal-
_______________________ Formate CHO2 1-
cium has a valence of 2+ and the
Thiocyanate SCN 1-
_______________________ hydroxyl ion has a valence of 1-, then
_______________________ there must be two hydroxyl ions in the Table 4: Common symbols and valence.

_______________________

_______________________

_______________________

_______________________

_______________________

_______________________

_______________________

Basic Chemistry 4A.6 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER

4A Basic Chemistry

Electron Shell
Electrons orbit the nucleus of an atom
in orderly arrangements called electron
shells. Each shell can hold only a spe-
cific maximum number of electrons.
The outer- The first orbital or shell must not con-
most orbit is tain more than two electrons and, in
general, each succeeding shell cannot
designated as contain more than eight electrons. Each
the valence subsequent shell has an orbit of larger
electron orbit diameter. Completely filled shells form
stable (less reactive) structures, i.e., they
(valence tend not to accept or give up electrons.
shell)…
Individual atoms generally begin by
having a balanced electrical charge
(with the same number of electrons as
protons), but can give up or accept elec-
trons to fill shells. The outermost orbit is
designated as the valence electron orbit
(valence shell) because it determines the
valence an atom will have. The arrange-
ment of elements called the “Periodic
Table” lines up elements with the same
number of electrons in the “valence-
shell” into columns (see Table 5).

Ionic Bonding
As shown in Figure 2, sodium and Sodium atom Chlorine atom
chlorine form the sodium chloride com-
pound by sodium losing and chlorine
gaining an electron (called ionic bond-
ing) to form filled outer electron shells. 11+ 17+

The sodium atom (atomic number 11)

has 11 protons and 11 electrons; there-
fore, the 11 electrons are arranged with
1 electron 7 electrons
two in the first shell, eight in the sec- outer shell outer shell
Neutral atoms
ond shell and only one electron in the
third shell. The one electron in the out-
_______________________ ermost “valence-shell” makes sodium
want to give up one electron when
_______________________
combining with other atoms to form a 11+ 17+
_______________________ stable structure with its last shell filled.
_______________________ If one electron is lost (1- charge), sodium
would become an ion with a 1+ charge, Transfer of an electron
_______________________
or valence.
_______________________ The chlorine atom (atomic number
17) has 17 protons and 17 electrons.
+ –
_______________________
Ionic bond
The electrons are arranged with two in
_______________________ 11+ Transfered 17+
the first shell, eight in the second shell electron
_______________________ and seven in the third shell. The seven
_______________________ electrons in the outermost “valence-
_______________________
shell” make chlorine want to gain one Na+ ion Cl– ion
electron to fill its last shell. If one elec- Each has 8 electrons outer shell
_______________________ Sodium chloride compound
tron is gained, chlorine would become
_______________________ an ion with a 1- charge or valence. Figure 2: Electron shells and ionic bonding.
_______________________ Thus, the combination of one atom of
sodium and one atom of chlorine forms
_______________________
the stable sodium chloride compound,

Basic Chemistry 4A.7 Revision No: A-0 / Revision Date: 03·31·98

 4A
CHAPTER

1a 2a 3b 4b 5b 6b 7b 8 1b 2b 3a 4a 5a 6a 7a 0
1 +1 2 0
H -1 He
1.008 4.00260

Basic Chemistry
Key
3 +1 4 +2 5 +3 6 +2 7 +1 8 -2 9 -1 10 0
Li Be Atomic number 50 +2 Oxidation states B C +4 N +2 O F Ne
Symbol Sn +4 -4 +3
+4
Atomic weight 118.69 +5
-1
Basic Chemistry

6.94 9.01218 10.81 12.011 14.0067 -2 15.9994 18.9984 20.17

-3
Transition elements
11 +1 12 +2 13 +3 14 +2 15 +3 16 +4 17 +1 18 0
Na Mg Al Si +4 P +5 S +6 Cl +5 Ar
Group 8
-4 -3 -2 +7
22.9898 24.305 26.9815 28.086 30.9738 32.06 35.453 -1 39.948

4A.8
19 +1 20 +2 21 +3 22 +2 23 +2 24 +2 25 +2 26 +2 27 +2 28 +2 29 +1 30 +2 31 +3 32 +2 33 +3 34 +4 35 +1 36 0
K Ca Sc Ti +3 V +3 Cr +3 Mn +3 Fe +3 Co +3 Ni +3 Cu +2 Zn Ga Ge +4 As +5 Se +6 Br +5 Kr
+4 +4 +6 +4 -3 -2 -1
39.102 40.08 44.9559 47.90 50.941 +5 51.996 54.9380 +7 55.847 58.9332 58.71 63.546 65.37 69.72 72.59 74.9216 78.96 79.904 83.80

37 +1 38 +2 39 +3 40 +4 41 +3 42 +6 43 +4 44 +3 45 +3 46 +2 47 +1 48 +2 49 +3 50 +2 51 +3 52 +4 53 +1 54 0
Rb Sr Y Zr Nb +5 Mo Tc +6 Ru Rh Pd +4 Ag Cd In Sn +4 Sb +5 Te +6 I +5 Xe
+7 -3 -2 +7
85.467 87.62 88.9059 91.22 92.9064 95.94 98.9062 101.07 102.9055 106.4 107.868 112.40 114.82 118.69 121.75 127.60 126.9045 -1 131.30

55 +1 56 +2 57* +3 72 +4 73 +5 74 +6 75 +4 76 +3 77 +3 78 +2 79 +1 80 +1 81 +1 82 +2 83 +3 84 +2 85 86 0
Cs Ba La Hf Ta W Re +6 Os +4 Ir +4 Pt +4 Au +3 Hg +2 Tl +3 Pb +4 Bi +5 Po +4 At Rn
+7
132.9055 137.34 138.9055 178.49 180.947 183.85 186.2 190.2 192.22 195.09 196.9665 200.59 204.37 207.2 208.9806 (209) (210) (222)

87 +1 88 +2 89** +3 104 105

Fr Ra Ac
(223) (226) (227)

*Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

**Actinides 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Table 5: Periodic table.

Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4A Basic Chemistry
NaCl. The one sodium valence electron
is transferred from the sodium atom to
the outer shell of the chlorine atom.
Why does sodium give up its elec-
tron and why does chlorine accept it?
The theory dealing with the behavior
of atoms assumes that every atom tries
to achieve a full outer electron shell
Atoms with with eight electrons. Atoms with one,
one, two and two and three valence electrons find it
easier to give away electrons, whereas
three valence those with four, five, six and seven
electrons find find it easier to accept them. In the
it easier to case of sodium and chlorine, sodium
gives one electron, resulting in a net
give away charge of +1, and chlorine takes on
electrons… one electron, resulting in a net charge
of 1. Neither atom is considered neu-
tral with these changes. The sodium
atom has become an ion with a positive
Covalent Bonding
The sharing of electron pairs to form
bonds between atoms is called cova-
lent bonding. Unlike sodium chloride,
where there is a transfer of electrons
…covalent (ionic bonding), covalent bonding is
bonding the simultaneous sharing of electrons.
Both water and hydrogen gas are good
is the examples of compounds with covalent
simultaneous bonds (see Figure 3). In a water mole-
sharing of cule, one electron from each of the two
hydrogen atoms is shared with the six
electrons. electrons in oxygens’ second electron
shell to fill it with eight electrons.
Likewise, each hydrogen atom in a
water molecule shares one of the six
electrons from the oxygen atom’s sec-
ond electron shell to fill its first electron
shell with two electrons. Compounds
with a high degree of electron sharing
have strong interatomic forces with
weak intermolecular forces. The weak
intermolecular forces usually are not
sufficient to maintain a rigid structure.
Because of this, covalently bound
compounds are often liquids and gases.
Basic Chemistry 4A.9
charge (written as Na+) and the chlo-
rine atom has become an ion with a
negative charge (written as Cl–).
The evidence to support electron
transfer and the formation of ions is
the phenomenon that melted NaCl
is a conductor of electricity, and if a
current is applied to the molten salt,
sodium metal collects at the negative
pole of the cell (cathode) and chlorine
gas collects at the positive pole (anode).
Thus, the sodium ion is called the
cation and the chloride ion is called
the anion. In writing the name of a
compound, the cation is usually writ-
ten first. Since sodium gives up an elec-
tron, it is said to be electropositive, and
since it readily gives up this electron, it
is said to be strongly electropositive.
Hydrogen bonding: Some covalent
compounds have incomplete sharing
of the electron in the bond. This results
in partial postive and negative charges
on the atoms arranged in a manner
which polarizes the molecule. In water
(H2O), for example, the two hydrogen
atoms remain partially positive and the
oxygen atom remains partially nega-
tive. The negative charges of oxygen
dominate one side of the molecule,
while the postive charges of the hydro-
gen atoms dominate the other side,
forming a polar molecule (see Figure 4).
The hydrogen atoms of water mole-
cules are attracted to the oxygen atoms
of other nearby water molecules. This
attraction of the positive hydrogen
pole of one molecule to the negative
oxygen pole of another molecule is
referred to as hydrogen bonding. The
forces of hydrogen bonding are esti-
mated to be only one-tenth to one-
thirtieth as strong as those of covalent
bonding. These weak bonds easily
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4A Basic Chemistry

Water:
2 Hydrogen atoms Oxygen atom Combine to form Water (H2O)

_______________________

_______________________ 1+ 1+
_______________________

_______________________

_______________________ Covalent bond

8+ 8+
_______________________ Shared electrons

_______________________

_______________________
1+ 1+
_______________________

_______________________
1 electron 6 electrons outer shell Each atom has full outer shell
_______________________ outer shell

_______________________ Hydrogen gas:

2 Hydrogen atoms Combine to form Hydrogen gas (H2)
_______________________

_______________________ Covalent bond

1+ 1+ 1+ 1+
_______________________ Shared electrons

Figure 3: Covalent bonding of water and hydrogen gas.

alternate between molecules and change Water molecule (H2O)
association, i.e., making and breaking
H+
bonds between nearby molecules.
Hydrogen side Oxygen side
Hydrogen sulfide (H2S) is a gas even positive charge O2– negative charge
though its a heavier molecule than
water (H2O), because the charge distri- H+
bution is not polar. The two hydrogen Polar charge orientation
atoms have only weak positive charge
and the sulfur is only weakly negative, H+
forming a balanced structure. The lack H+
of a strong polar structure allows the O2– H+ O2–
individual molecules to diffuse into
H+
a gas under standard conditions.
The polarity The polarity of water explains some
H+
of water of the phenomena seen in drilling
fluids. Clays and shales are strongly H+ O2–
explains charged, complex structures. The attrac- O2–
some of the tion of the water molecule’s charges to H+ H+
H+
phenomena the charge sites of clay platelets leads to
Attraction of positive hydrogen
clay hydration. Clays have a strong neg- O2–
seen in ative charge on their large planar surface
side to negative oxygen side
H+
drilling and positive charges along their thin
fluids. edges. The positive hydrogen side of the Figure 4: Polar molecule and
water molecule is attracted to and will hydrogen bonding in water.
hydrogen bond to the large negative

Basic Chemistry 4A.10 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER

4A Basic Chemistry

O O O O

H H H H H H H H H
Hydrogen
O O O O
bonded water
H H H H H H H H H
–
O O + O + O + O +
O O O O O O O
Si Si Si Si Si Si Si Si + Silica layer
O O O O O O O O
OH OH OH OH
Clay

Al Al Al Al Al Al Al Al Alumina layer
OH OH OH OH
O O O O O O O O

+ Si Si Si Si Si Si Si Si O Silica layer
O O O O O O O –
+ + + +
O O O O

H H H H H H H H H

O O O O Hydrogen
bonded water
H H H H H H H H H

O O O O

Figure 5: Hydration of clay by water through hydrogen bonding.

clay surface. This water adsorption can
be many water layers thick, spreading
and swelling adjacent clay layers (see
Figure 5). Cation exchange (exchange
of ionic bonded cations) within a clay
can displace the water of hydration and
flocculate the clay particles, because
their bonds are stronger than water’s
weak hydrogen bonds.
Many compounds contain both
Ionic bonding covalent and ionic bonds. Soda ash
is as strong (Na2CO3) is an example of a compound
that contains both covalent and ionic
as covalent
bonding and
both are much Compounds
stronger than
hydrogen A compound is a substance that is
composed of elements in definite
bonding. proportions. Common table salt is
an ionic compound; it can be broken
down into the elements sodium (Na)
and chlorine (Cl). The following
apply to all compounds:
bonds. The bonds between the carbon
and oxygen in the carbonate group
(CO32 –) are covalent (electron sharing),
while the bonds between the sodium
ion (Na+) and the carbonate group are
ionic (electron transfer). When soda ash
dissolves, the sodium dissociates from
the carbonate group, while the carbon
and oxygen of the carbonate group
continue to function as a single unit.
Ionic bonding is as strong as covalent
bonding and both are much stronger
than hydrogen bonding.
• The composition of a compound
is always the same; it is definite
and exact.
• Elements lose their identity (their
characteristic properties) when they
combine to form a compound.
• A compound is homogeneous.

Basic Chemistry 4A.11 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4A Basic Chemistry
Formulas
Since a specific compound always con-
tains the same elements combined in
exactly the same ratio, it is possible to
represent its composition by means of a
A compound’s formula. A compound’s formula repre-
formula sents one molecule of the compound.
Atoms and chemical compounds
represents do not react with or form just one
one molecule molecule at a time. Instead, millions of
of the molecules and atoms are reacting simul-
taneously. Due to their small size, it is
compound. impossible to count the number of
atoms involved in chemical reactions.
Weight is used to measure the quantity
of chemicals involved in chemical reac-
tions. Since one atom of sodium weighs
22.99 amu and one atom of chlorine
weighs 35.45 amu, then based on ratio,
the atoms in 22.99 g of sodium would
combine with the exact number of
atoms in 35.45 g of chlorine to form
salt. This principle of ratio works for
any unit of measure — grams, pounds,
kg, tons, etc. — but the gram is the unit
of measure most commonly used.
The sum of When expressed in grams, the atomic
the atomic weight corresponds to 6.023 x 1023
atoms. This amount is one “gram-atom”
weights of molecular weight or “mole.”
the atoms in A mole is a quantitative unit of
a chemical measure that contains the exact
number of atoms, molecules or for-
formula is mula units which have a mass in
called the grams equal to the atomic, molecular
formula or formula weight. A mole of an ele-
ment contains the same number of
weight. chemical units (atoms, molecules or
units) as exactly 12 g of carbon 12,
or Avogadro’s number; 6.023 x 1023
of chemical units. A common usage
of the mole is the formula weight
expressed in grams. For NaCl (salt),
the formula weight is 58.44, so one
mole of sodium chloride would be
58.44 g.
Basic Chemistry 4A.12
The number of atoms of an element
in a compound’s formula is equal to
the number of moles of that element
needed to make one mole of the com-
pound. In water, two moles of hydro-
gen react with one mole of oxygen to
form one mole of water. Expressed on a
weight basis, hydrogen (atomic weight
1.01) combines with oxygen (atomic
weight 16.00) in the ratio of 2.02 g
of hydrogen to 16.00 g of oxygen;
i.e., a ratio of two moles of hydrogen
to one mole of oxygen. The formula,
therefore, is H2O.
Carbon (atomic weight 12.01)
combines with oxygen in the ratio
of 12.01 g of carbon to 32.00 g of
oxygen to form carbon dioxide. The
formula, therefore, is CO2. The sub-
script 2 refers only to the oxygen,
and means that there are two oxygen
atoms per molecule. Atoms in a for-
mula which do not have a stated sub-
script, such as the carbon atom, are
understood to have a subscript of 1.
The sum of the atomic weights of the
atoms in a chemical formula is called
the formula weight. If the chemical for-
mula of a substance is the molecular
formula, the formula weight is also the
molecular weight. Thus, the formula
weight of NaCl is 58.44. This value is
obtained by adding the atomic weight
of sodium (22.99) to the atomic
weight of chlorine (35.45).
A specific compound always contains
the same elements combined in exactly
the same ratio by weight and the com-
position is represented by the simplest
formula that describes the compound.
CaCl2, Fe2O3 and BaSO4 are examples
of formulas of compounds.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4A Basic Chemistry
Stoichiometry - Stoichiometric Reactions
The reason compounds contain fixed
Stoichiometry ratios of elements is because atoms
deals with react with other atoms according to
their valence. As discussed previously,
the quantities atoms react according to these ratios
and exact based on the fixed weights of each
ratios of atom involved. Determination of the
substances
which react.
Equivalent Weight
In many cases, chemical testing and
reactions are done with unknown mate-
rials. Because we don’t know the exact
composition, it is often convenient to
express results in terms of “equivalents”
of a standard compound instead of
moles. For example, in mud engineer-
ing, we titrate water-base mud filtrate to
measure “total hardness” and express
the result as if it were all calcium. This
total hardness titration actually mea-
sures both magnesium and calcium, so
we are expressing the total hardness in
calcium “equivalents.”
The equivalent weight is defined as
the formula weight of an element, com-
_______________________ pound or ion divided by how many
times it takes part in a specific reaction.
_______________________
As an example, for acids the number of
_______________________ hydrogen atoms in the chemical for-
_______________________ mula determines the equivalent weight.
Acids react by donating protons (hydro-
_______________________
gen ions). Suppose sulfuric acid (H2SO4,
_______________________ formula weight 98) is used to reduce
_______________________ pH. The reaction can be written as:
H2SO4 + 2OH– → 2H2O + SO42–
_______________________
_______________________
_______________________
_______________________
_______________________
_______________________
_______________________
_______________________
Basic Chemistry 4A.13
weights is called “stoichiometry”.
Stoichiometry deals with the quantities
and exact ratios of substances which
react. Stoichiometric calculations allow
the exact weight and ratio of chemicals
which will react to be determined so
that a desired result can be achieved.
One mole of H2SO4 reacts with two
moles OH–. From this standpoint, 1⁄2
mole of sulfuric acid is equivalent to
one mole of hydroxyl. To remove only
one mole of OH–, then only 1⁄2 mole of
H2SO4 is needed. On a formula weight
basis this would be 98 ÷ 2 or 49 g.
Therefore, the equivalent weight of
H2SO4 is 49 g. To consume the same
amount of OH– using hydrochloric acid
(HCl, formula weight 36.5) which has
only one hydrogen atom, then the reac-
tion can be written as:
HCl + OH– → H2O + Cl–
Since one mole of HCl reacts with
just one mole of OH–, then the equiva-
lent weight of hydrochloric acid is its
formula weight, 36.5 g. By this equiv-
alent weight method, 49 g of H2SO4 is
equivalent to 36.5 g of HCl. Using this
principal if pilot testing in the labora-
tory shows that it takes 36.5 lb/bbl of
HCl to neutralize a high pH fluid, and
only H2SO4 was available to use at the
rig, then 49 lb/bbl of H2SO4 would also
neutralize the fluid.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4A Basic Chemistry
Balancing an Equation
One of the first steps involved in
determining stoichiometric reactions
is to balance the chemical equation.
Chemical Chemical equations must always have
equations an equal number of each atom on both
sides of the equation. If all of the reac-
must always tants and products are known, the best
have an equal approach is to single-out one element
number of of known valence and balance the
entire equation on the basis of that ele-
each atom… ment. Many elements can have more
than one valence, which complicates
the process. If present, oxygen should
be used to balance the equation. The
arrow or arrows indicate chemical reac-
tions or transformations and should be
considered to be like an equals sign (=)
in mathematics. Consider the following
unbalanced equation involving the
reaction between iron (Fe3+) and oxygen
(O2–) producing iron oxide:
Fe3+ + O22– → Fe23+O32–
This equation is not balanced with
respect to the number of atoms or
valence charges. Starting with oxygen,
the equation is not balanced since
there are two oxygen atoms on the
left side and three on the right. First,
_______________________ balance the number of oxygen atoms,
_______________________ then the iron atoms. The valence
charges are also not balanced, with
_______________________
four negative charges (2 x 2-) on the
_______________________
left and six negative charges (3 x 2-)
_______________________ on the right. If a 2 is used in front of
the iron oxide and a 3 in front of the
_______________________
oxygen, the equation then becomes:
_______________________
Fe3+ + 3O22– → 2Fe23+O32–
_______________________
The number of oxygen atoms and
_______________________ negative charges are now balanced.
_______________________
_______________________
_______________________
_______________________
_______________________
_______________________
Basic Chemistry 4A.14
Now, however, the iron must be bal-
anced. As a result of balancing the oxy-
gen atoms, there is now one iron atom
on the left and four iron atoms (2 x 2)
[with 12 positive charges, 2 x 2 x 3+]
on the right. In order to completely
balance the equation, there must be
four iron atoms on the left with 12
positive charges on the left. If a 4 is
placed before the iron, the equation
is balanced:
4Fe3+ + 3O22– → 2Fe23+O32–
Stoichiometrically, four moles of iron
combine with three moles of oxygen
to yield two moles of iron oxide.
Consider the following problem:
Using the reaction from above, how
many grams of oxygen would be
required to react with 140 g of iron
to produce iron oxide?
4Fe + 3O2 → 2Fe2O3
4 moles iron + 3 moles oxygen →
2 moles iron oxide
atomic weight Fe = 55.85,
so 4 moles Fe = 4 x 55.85 = 223.4 g
atomic weight O ≈ 16,
so 3 moles O2 = 3 x 2 x 16 = 96 g
Since only 140 g of iron is used (not
223.4), the ratio of 140 divided by 223.4
can be multiplied times the 96 g of oxy-
gen to determine the amount of oxygen
needed to react with 140 g of iron.
Oxygen required =
140 g Fe
x 96 g O2 =
223.4 g Fe
60.2 g O2
Therefore, it takes 60.2 g of oxygen
to react with 140 g of iron to produce
iron oxide.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4A Basic Chemistry

Solubility

SOLUTIONS
H+ H+
_______________________ If sugar is added to water, it will dis-
solve, forming a solution of sugar in H+
O 2–
_______________________ H+
water. The solution is homogeneous
_______________________ when no particles of sugar can be seen. O 2– O 2–
H+
_______________________ The sugar is referred to as the solute; it H+
is the substance that is dissolved. The
_______________________ Na+
water is referred to as the solvent; it is
_______________________ the substance that does the dissolving. H+ H+
_______________________ Small additions of sugar will dissolve O 2– O 2–
_______________________
until a point is reached at which the
solution is unable to dissolve additional H+ H+
_______________________ O 2–
sugar. This will be indicated when the
H+ H+
_______________________ crystals that are added drop to the bot-
_______________________
tom of the glass and will not dissolve, Sodium ion is compact with relatively strong bonds with water.

even if the contents of the glass are well

_______________________ H+
stirred. A solution which has dissolved
O 2–
_______________________ all the solute that it is capable of dis-
_______________________ solving at a given temperature is said to H+
be saturated and this quantity of solute O 2–
_______________________
is referred to as its solubility. H + H+
H+
EFFECTS OF BONDING
The solubility of compounds in polar Cl– O 2–
solvents, like water, can generally be H+
explained by their bonding. Polar H+
O 2–
covalent compounds, such as CO2,
usually are soluble in water. When H+
H+
their attraction to water’s hydrogen O 2–
bonds is greater than their attraction H+
to the charges of other molecules of Chlorine ion is larger with weaker bonds with water.
the compound, the molecules of the
compound will disperse into solution. Figure 6: Ionization of sodium chloride in water.
Nonpolar covalent compounds, such Salts (compounds) with either mono-
as methane (CH4), are usually insolu- valent cations (sodium (1+) in soda ash,
ble in water and other polar solvents, Na2CO3) or monovalent anions (chlo-
but are often dispersable in nonpolar rine (1-) in calcium chloride, CaCl2) are
solvents, such as diesel oil. When non- usually soluble in water. The salts of
ionic compounds dissolve, they become multivalent cations combined with mul-
molecularly dispersed not ionized. tivalent anions (calcium (2+) and sulfate
Many ionic Many ionic compounds are soluble in (2-) [in gypsum CaSO4, for example]) are
compounds water. If the forces of attraction between usually insoluble or only sparingly solu-
the water molecules and the ions are ble. The forces holding ions together in
are soluble greater than the forces holding the ions the salts of multivalent cations and mul-
in water. in their crystals, the ions will attract a tivalent anions are much greater than
“shell” of water molecules and be freed the forces holding the ions together in
from their crystalline lattice, as shown
for sodium chloride (see Figure 6).
Basic Chemistry 4A.15 Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4A Basic Chemistry

the salts of either monovalent cations or 1. Temperature. Solubility increases

monovalent anions. with increased temperature for most
Ionic bonded Ionic bonded compounds dissolve or solids and liquids. The solubility of
compounds solubilize into ions, whereas covalent gases usually decreases with increasing
bonded compounds are soluble as mole- temperature.
dissolve or cules. Brines are solutions of a high con- 2. pH. pH is a measure of the relative
solubilize centration of soluble salts and are more acid or base character of a solution
into ions… viscous than freshwater because the dis- (described in detail later). The solubility
solved salts reduce the free water by of many chemicals is a function of pH.
attracting large shells of water around Some chemicals, such as the multiva-
themselves, restricting the free move- lent salts of hydroxide and carbonate,
ment of the water. Ionic compounds are are more soluble in acidic conditions.
generally insoluble in nonpolar solvents Other chemicals are soluble only over
such as diesel oil. a neutral pH range, and still others
(organic acids such as lignite and lig-
QUANTIFYING SOLUBILITY
nosulfonate) are more soluble as pH
The quantity of solute that will dis- increases to >9.5. Calcium and magne-
solve in a quantity of solvent to give a sium ions are soluble at acid to neutral
saturated solution is referred to as the pH, but become less soluble at high pH,
solubility of the solute in the solvent. as shown for calcium in Figure 7. As
Solubility of a solid, liquid or gas in a the hydroxide ions increase with pH,
liquid is generally expressed in units they react with the calcium and magne-
of grams of solute per 100 g of water. sium to precipitate calcium hydroxide
Table 6 lists the degree of solubility of and magnesium hydroxide.
several common compounds used in Other compounds, such as carbonate
drilling fluids. and sulfide ions, change species with
Solubility
increasing pH. For instance, CO2, a gas,
(g per reacts with water to become carbonic
100 g acid at low pH. It will react with hydrox-
Compound Common Name water)
NaOH Caustic soda 119
ide to form bicarbonate ions in a neutral
CaCl2 Calcium chloride 47.5
pH range and finally carbonate ions at
NaCl Sodium chloride (table salt) 36 high pH (see Figure 8).
Water-base KCl Potassium chloride 34.7 The solubility of many mud chemi-
drilling fluids Na2CO3 Soda ash 21.5 cals is a function of the pH of the solu-
NaHCO3 Sodium bicarbonate 9.6 tion. For instance, not only are lignite
are generally CaSO4 Anhydrite 0.290 and lignosulfonate more soluble above
maintained Ca(OH)2 Lime 0.185 pH 9.5, but products like DUO-VIST (xan-
MgCO3 Magnesium carbonate 0.129 than gum) are more effective in the 7 to
in the 8 to CaCO3 Limestone 0.0014 11 pH range. Other additives are sensi-
12 pH range… Mg(OH)2 Milk of magnesia 0.0009
tive to high pH. Products like POLY-PLUST
BaSO4 Barite 0.0002
(PHPA) hydrolyze and become less effec-
ZnO Zinc oxide 0.00016
tive at high pH (>10.5). Most individ-
Table 6: Solubility of common chemicals. ual mud products have an optimum
pH range for maximum performance.
FACTORS AFFECTING SOLUBILITY
Water-base drilling fluids are generally
• Temperature maintained in the 8 to 12 pH range for
• pH (acid or base) improved chemical solubility and per-
• Ionic environment (salinity) formance, as well as for anti-corrosion
• Pressure and safety reasons. Mud engineers
should familiarize themselves with these

Basic Chemistry 4A.16 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4A Basic Chemistry
1,000
Filtrate calcium (mg/l)
900
800
700 NaOH solutions 68°F
600
500
400
300
200
100
0 0
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Figure 7: Decreasing solubility of calcium
with increasing pH.
ranges and maintain the drilling fluid
system within the optimum pH range.
3. Ionic environment (salinity). Of
particular importance to mud engi-
neering is the chlorides concentration,
or salinity. An increase in salinity gen-
erally increases the solubility of other
salts and additives and will affect such
…in solution, chemical reactions as precipitation. For
the compound example, calcium sulfate (gypsum and
with the anhydrite) has its greatest solubility in
a 15% salt solution, wherein it is four
lowest times as soluble as it is in freshwater.
solubility will This trend decreases as the salinity
precipitate approaches saturation. Lime (calcium
hydroxide) also is more soluble at mod-
first. erate salinity. Even polymers, which are
sensitive to precipitation by divalent
cations and other conditions, are more
_______________________
stable in saline environments. The
_______________________ ionic environment of the solvent has
_______________________ a great impact on the chemical reactions
that will take place and the stability of
_______________________
various products.
_______________________ 4. Pressure. An increase in pressure
_______________________ increases the solubility of a gas in a
_______________________
_______________________
_______________________
_______________________
_______________________
_______________________
_______________________
_______________________
_______________________
Basic Chemistry
100
CO32 -
CO2
Ca(OH)2 added to 80
HCO3-
Percent
60 Increasing salinity
40 shifts curves to
the left
20
HCO3- HCO3-
0
2 4 6 8 10 12 14
pH
Caustic soda (lb/bbl)
Figure 8: Carbonate-bicarbonate equilibrium.
liquid, but has practically no effect
on the solubility of liquids and solids.
This increased solubility of gas is par-
ticularly important when we consider
the downhole chemical environment,
where intruding or entrained gases
are subjected to high pressure and
may be solubilized.
The importance of the relative solubil-
ity of chemicals is that in solution, the
compound with the lowest solubility
will precipitate first. For example, if cal-
cium chloride (high solubility) were
mixed into water, it would ionize into
calcium and chloride ions. Then, if soda
ash (moderately soluble) were added, it
would ionize into sodium and carbon-
ate ions, and calcium carbonate (low
solubility) would precipitate immedi-
ately as the soluble calcium and soluble
carbonate ions react. Relative solubility
can be used to determine what chemical
to add to remove an undesirable chemi-
cal. The other ions which are present in
the solvent affect solubility.
4A.17 Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4A Basic Chemistry
pH and Alkalinity
pH
The pH The pH value is used to describe the
acidity or basicity of solutions. The pH
value is used
value is defined as the negative log of
to describe the hydrogen ion concentration. Low
the acidity or pH values correspond to increasing acid-
ity and high pH values correspond to
basicity of
high basicity. A change of one pH unit
solutions. corresponds to a ten-fold increase in
hydrogen ion concentration.
Water is a weak electrolyte which
exists in nature as molecules of H2O. It
can ionize to form hydronium (H3O+)
and hydroxyl (OH–) ions. The ioniza-
tion of water is statistically rare, with
only one molecule in 556 million
being ionized. Water is in equilibrium
with the above ions according to the
following equation:
2H2O H3O+ (aq) + OH– (aq)
The (aq) The (aq) indicates that the ions are
indicates dissolved in water, forming an aqueous
solution. Since water ionizes itself, the
that the ions process is called autoionization. This
are dissolved
equilibrium with the hydronium and
in water, hydroxide ions provides the basis for
the classification of acids and bases.
forming an Acids are substances that add hydrogen
aqueous ions, (H+), when dissolved in water,
solution. increasing the hydronium concentra-
tion [H3O+]. The concentration for dif-
ferent ions is indicated by the chemical
being shown in brackets, such as [H+]
for the concentration of hydrogen ion.
The equilibrium expression for the
autoionization process is:
Kw = [H+] [OH–]
This type of equilibrium expression is
used frequently to describe equilibrium
conditions of related chemical species.
The equilibrium constant is given the
symbol Kw, where the subscript (w)
refers to water. At 25°C, Kw = l.0 x 10–14,
Basic Chemistry 4A.18
Kw depends on temperature (increases
Kw) and ionic concentration of the
solution (salinity).
Kw, the product of [H+] and [OH–],
remains constant providing the tem-
perature is constant. In a neutral solu-
tion, the concentration of hydrogen
[H+] is equal to the concentration of
hydroxide [OH–]; therefore, each would
have a concentration of 1.0 x 10–7, and
the solution would have a pH of 7.0.
If [H+] increases, the [OH–] decreases
and the solution becomes more acidic.
Likewise, if the [OH–] increases, then the
[H+] must decrease and the solution
becomes more basic.
H+ (aq) and OH– (aq) ions are always
present in aqueous solutions in equilib-
rium with the solvent. H+ (aq), and OH–
(aq) can react with other ions, influenc-
ing the concentrations of other ions in
the solution. For this reason, reference
to the concentrations of H+ (aq) and
OH– (aq) are made. To assist in this ref-
erence, the terms pH and pOH are
defined as:
pH = - log [H+]
pOH = - log [OH–]
A convenient relationship between
pH and pOH is found by taking the
negative logarithm (indicated by a p)
of Kw, which gives:
pKw = -log Kw = -log [H+] -log [OH–]
Using the definitions of pH and pOH,
given above, we find that at 25°C:
pKw = pH + pOH
since Kw = l.0 x 10 –14, then
pKw = - log Kw = 14, which gives
pH + pOH = 14
This relationship of acids and bases
with values for pH and [H+] plus pOH
and [OH–] is shown in Figure 9.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4A Basic Chemistry

pH [H+] [OH–] pOH

removed from the solution, and the pH
0 1 Acids 10–14 14 remains neutral. Again, if the salt con-
_______________________
1 10–1 10–13 13 tains the cation of a strong base and
_______________________ the anion of a strong acid, the solution
2 10–2 10–12 12
_______________________ 3 10–3 10–11 11 will remain neutral. However, if the
_______________________
4 10–4 10–10 10 salt contains the cation of a strong base
5 10–5 10–9 9 and the anion of a weak acid, its solu-
_______________________ 6 10–6 10–8 8 tion will be basic (increasing pH), as
_______________________ 7 10–7 Neutral 10–7 7 is the case with Na2CO3 (soda ash).
8 10–8 10–6 6
_______________________
Conversely, if the salt contains the
9 10–9 10–5 5
cation of a weak base and the anion of
_______________________ 10 10–10 10–4 4
11 10–11 10–3 3
a strong acid, its solution will be acidic
_______________________
12 10–12 10–2 2
(decreasing pH). Naturally, if an acid is
_______________________ 13 10–13 10–1 1 added, the pH would decrease, whereas
14 10–14 Bases 1 0 the pH would increase if a base were
_______________________
added to a neutral solution.
_______________________
Figure 9: pH scale, acids and bases.
_______________________
ALKALINITY
_______________________ Note that low pH values correspond
Alkalinity titrations determine OH–,
to acids and low pOH values correspond
_______________________ HCO3– and CO32– concentrations by
to basic solutions. A change of one pH
measuring the amount of acid required
or pOH unit corresponds to a change in
to reduce pH. Borates, silicates, phos-
molar concentration by a factor of 10. A
phates, sulfates and organic acids (like
solution with a pH of 2 is not twice as
lignite) also can enter into the titration
acidic as a solution with a pH of 4; it is
and/or treatment calculations based on
100 times as acidic as a solution with a
alkalinity values. Alkalinity is the com-
pH of 4.
bining power of a base measured by the
Remember, the value of Kw changes
quantity of acid which can react to form
with temperature and ionic concentra-
a salt. In mud engineering, phenolph-
tion (salinity) so that pH values mea-
thalein alkalinity (P) is reported as the
sured with an electronic pH probe may
number of milliliters of 0.02 N H2SO4
not be valid unless the instrument
(water-base muds) required to titrate a
(meter or probe) and measurement
milliliter of filtrate (Pf) or mud (Pm),
are compensated for the temperature
reducing the pH to 8.3. The methyl
of the liquid and the salinity of the
orange filtrate alkalinity (Mf) measures
fluid. High-salinity pH measurements
the acid required to reduce pH to 4.3.
may require the use of a special “salt-
Alkalinity is compensated” pH probe.
Alkalinity is not the same as pH,
not the same although their values usually trend in
As discussed previously in regard to
the same direction. A strong base, such
as pH… salts, when NaCl (a neutral salt formed
as Caustic Soda, added to pure water
by the combination of a strong acid
would show this correlation between
and a strong base) is dissolved in water,
alkalinity titration values and pH, as
the Na+ ions do not combine with OH–
shown in Table 7; however, due to the
ions (to reduce pH), because NaOH is a
presence of HCO3–, CO32– — as well
strong base. Likewise, the Cl– ions do
as calcium and magnesium — in oil-
not combine with H+ ions (to increase
field waters and drilling fluids, no
pH) because HCl is a strong acid. As a
correlation should be made.
result, neither H+ ions nor OH– ions is

Basic Chemistry 4A.19 Revision No: A-1 / Revision Date: 02·28·01

 CHAPTER
4A Basic Chemistry
NaOH Pf
pH (lb/bbl) (cc 0.02N H2SO4) (ppm)
_______________________ 7 0.0000014 0.000005
_______________________ 8 0.000014 0.00005
9 0.00014 0.0005
_______________________
10 0.0014 0.005
_______________________ 11 0.014 0.05
12 0.14 0.5
_______________________
13 1.4 5 1,700
_______________________ 14 14 50
_______________________
Table 7: Relationship of pH and alkalinity for pure water.
_______________________
This table shows how small concentra-
_______________________ tions of caustic soda (NaOH) in pure
_______________________ water cause relatively high pH values
and filtrate alkalinity. To observe the
_______________________
effect of a more complex ionic envi-
_______________________ ronment, compare the higher amount
_______________________ of caustic required to increase pH in
seawater as shown later in Figure 10.
_______________________
Alkalinity measurements (Pf, Mf
_______________________ and other values) are used to calculate
Acids, Bases and Salts
Acids can be described as substances
which have a sour taste, cause efferves-
cence in contact with carbonates, turn
blue litmus red and react with bases,
alkalis, and certain metals to form salts.
All acids All acids contain hydrogen. Acids are
contain termed as “strong” or “weak,” accord-
ing to the concentration of hydrogen
hydrogen. ion (H+) that results from ionization.
Bases can be described as having a
bitter taste, a “slippery” feeling in solu-
tion, an ability to turn red litmus paper
blue, and an ability to react with acids
to form salts. Bases do not cause effer-
vescence in contact with carbonates.
Acids react with bases to form salts. A
base is termed strong or weak, depend-
ing on the quantity of the molecule
which disassociates into hydroxyl ions
(OH–) in solution.
Basic Chemistry
OH– hydroxyl, bicarbonate and carbonate
concentrations as described in API
0.0017 13B-1, Section 8, Table 8.1, and in the
0.017
Testing chapter. Because the Mf value
0.17
can be an unreliable indication of bicar-
1.7
17
bonate contamination if organic acids
170
or organic salts (like lignite or acetate)
are used, an alternative procedure uses
17,000 a pH measurement and the Pf value to
calculate the carbonate and bicarbon-
ate concentration. These calculations
help monitor and diagnose carbon
dioxide, bicarbonate and carbonate
contamination. In addition, these val-
ues give the mud engineer a more
thorough understanding of the ionic
and buffering environment of the
mud system, far beyond what can
be learned from a pH value alone.
Both acids and bases can be either
strong or weak, depending on the
elements in the compound and
their valence.
Salts are simply combinations of the
anion (negative ion) from an acid and
the cation (positive ion) from a base. A
salt may be neutral or have a tendency
toward the acid or base side, depending
on the relative strengths of the respec-
tive ions or groups. As discussed previ-
ously, the combination of a weak acid
and a strong base forms an alkaline
salt, while the combination of a strong
acid with a weak base forms an acidic
salt, and the combination of a strong
acid with a strong base forms a neutral
salt. Table 8 is a list of the most com-
mon acids, bases and salts that are
used in drilling fluids.
4A.20 Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4A Basic Chemistry

Chemical Name Common Name Formula Type

Hydrochloric acid Muriatic acid HCl Acid (strong)
Sulfuric acid — H2SO4 Acid (strong)
Nitric acid Aqua fortis HNO3 Acid (strong)
Phosphoric acid Orthophosphoric H3PO4 Acid (mod. weak)
Carbonic acid Soda (sparkling) H2CO3 Acid (weak)
Citric acid — H3C6H5O7 Acid (weak)
Sodium hydroxide Caustic soda NaOH Base (strong)
Potassium hydroxide Caustic potash KOH Base (strong)
Magnesium hydroxide Magnesium hydrate Mg(OH)2 Base
Sodium carbonate Soda ash Na2CO3 Base (weak)
Calcium hydroxide Slaked lime Ca(OH)2 Base (strong)
Calcium oxide Quicklime CaO Base (strong)
Sodium chloride Rock salt NaCl Salt
Potassium chloride Potash (muriate of) KCl Salt
Calcium chloride — CaCl2 Salt
Calcium sulfate Anhydrite (gyp) CaSO4 ( • 2H2O ) Salt

Table 8: Common acids, bases and salts.

BUFFER SOLUTIONS solution of a weak acid and the soluble

Certain solutions called buffer solu-
tions resist large pH changes when
a base or acid is added to a solution.
Many oilfield Many oilfield liquids and mud-treating
chemicals are buffered solutions.
liquids and
Buffer solutions generally consist of
mud-treating either a weak acid and a salt that con-
chemicals are tain the same anion or a weak base and
a salt that contain the same cation. The
buffered
buffering action of a solution consist-
solutions. ing of a weak acid plus a salt of the
acid comes about because: (1) added
base reacts with the weak acid to form
more of the common ion and (2)
added acid reacts with the common
ion to produce the weak acid. An
example of a weak acid is carbonic acid
(H2CO3). An example of a weak base is
ammonium hydroxide (NH4OH). If a
small amount of strong acid, such as
HCl, is added to pure water or to a
dilute solution of acid in water, the
hydrogen ion concentration (pH) of
the water or solution is noticeably
increased. If the same small amount
of acid is instead added to a buffered
salt of that acid, the increase in hydro-
gen ion concentration (pH) is so slight
that for all practical purposes it is negli-
gible. The anions of the salt of the weak
acid have taken the H+ ions as fast as
they were added and have reacted with
them to form more of the weak acid.
The net result is that the hydrogen ion
concentration has changed only very
slightly; and the pH is little changed.
This phenomenon can take place
very easily when the mud engineer is
titrating (with an acid) the alkalinity
endpoints. In fluids with high carbon-
ates, bicarbonates and hydroxides, as
soon as carbonates are converted to
bicarbonates, a buffer solution begins
to develop which resists changes in pH.
Triethanolamine, lime and mag-
nesium oxide are all chemicals used
to buffer pH-sensitive mud systems.
Buffering can be highly beneficial to
maintain stable fluid properties and
to resist the detrimental effects of
various contaminants.

Basic Chemistry 4A.21 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4A Basic Chemistry
ELECTROLYTE
Substances whose water solutions con-
duct electricity are called electrolytes
and contain both positive and negative
All solutions ions. All solutions of ionic compounds
are electrolytes. All acids, bases and salts
of ionic com-
are electrolytes. Electrovalent com-
pounds are pounds are formed by transfer of elec-
electrolytes. trons (ionic bonds); in the process,
positive and negative ions are produced.
The resulting solid compounds (salts
and hydroxides) all have an ionic crystal
lattice structure. This means that, in the
case of these electrovalent compounds,
the ions are formed when the com-
pound is formed. They exist before the
compound is dissolved in water. When
such a compound is dissolved, the ionic
crystal lattice is broken down and the
ions disassociate in solution; the water
merely acts as a solvent. Typical equa-
tions to illustrate the disassociation of
these already existing ions are:
Salt: NaCl = Na+ + Cl–
(as shown in Figure 6)
Lime: Ca(OH)2 = Ca2+ + 2OH–
Osmosis
_______________________
Osmosis is a phenomenon that takes
_______________________
place when two solutions of greatly dif-
_______________________ ferent solute concentration (salinity)
_______________________ are separated by a semi-permeable
membrane. During osmosis, there is
_______________________
a net movement of solvent (water)
_______________________ through the membrane from the solu-
_______________________ tion with a lower solute concentration
(lower salinity) to the solution with the
_______________________
higher solute concentration (higher
_______________________ salinity). Therefore, osmosis will tend
_______________________ to transfer solvent until the two solu-
tions have a similar solute concentra-
_______________________
tion (salinity). The driving forces in
_______________________ this process are the difference in solute
_______________________ concentration and the character of the
_______________________
semi-permeable membrane.
_______________________
Basic Chemistry 4A.22
Since the ability of a solution to con-
duct electricity is dependent upon the
presence of ions, it can be concluded
that solutions that are excellent con-
ductors contain high concentrations of
ions (completely ionized), while solu-
tions that are poor conductors contain
low concentrations of ions (not com-
pletely ionized). Electrolytes that are
completely ionized are called strong
electrolytes, whereas those that are not
completely ionized are called weak elec-
trolytes. With very few exceptions, salts
are strong electrolytes. Most hydroxides
(except Mg2+) are strong electrolytes and
accordingly classified as strong bases.
Acids such as HCl, H2SO4 and HNO3
are strong electrolytes and, therefore,
are classified as strong acids; most oth-
ers are moderately weak and are classi-
fied as weak acids. Pure water is a weak
electrolyte, and not as conductive as
salt solutions.
The “activity” of a solution is a mea-
sure of the vapor pressure or “relative
humidity” and is related to solute con-
centration (salinity). Water would have
an activity of 1.0; higher salinity reduces
activity. In drilling water-sensitive shales,
it is desirable for the drilling fluid and
formation to have a similar activity to
minimize the transfer of water from
the drilling fluid to the formation. Oil-
and synthetic-base fluids have the
potential to transfer water from their
emulsified water phase (usually calcium
chloride brine) if its activity is higher
than the activity of the formation
through osmosis.
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER

4A Basic Chemistry

Titrations

The chemical The chemical tests made in mud analy- important chemicals. Care should be
tests made ses are called titrations. Titrations are exercised to follow the exact procedure.
procedures which use standard solu- Formulas are also provided which will
in mud tions of a known concentration (N1) enable the engineer to make the neces-
analyses to determine the unknown concentra- sary calculations without having to
are called tion (N2) of a sample of known volume convert units.
(V2). The basic equation involving this
titrations. quantitative analysis is:
INDICATORS
V2 x N2 = V1 x N1 Chemicals used to determine the end-
point in titrating are called indicators.
Solving this equation for N2 gives
Indicators are compounds that change
the following:
color with either a change in pH or a
V
N2 = 1 x N1 change in chemical concentration. The
V2
color changes of acid-base indicators do
For a known sample volume (V2), so at a specific pH value. Different indi-
Chemicals using an indicator and titrating with a cators change color in acidic, neutral or
solution of known concentration (N1), basic pH conditions. Chemical indica-
used to
it is possible to determine the unknown tors are used which change color in the
determine the concentration (N2) of the sample by presence of calcium, magnesium chlo-
endpoint in measuring the volume (V1) required to rides and bromides. Table 9 lists the
titrating reach the endpoint. Proper procedures most common indicators used in mud
are outlined in the Testing chapter for analysis with the titrating chemical
are called quantitative measurements using stan- used and the color change the indicator
indicators. dard solutions for determining the undergoes at a specific condition.
Indicator Original Color Color Change Titration Titrating Chemical
Phenolphthalein Pink/red: pH >8.3 Colorless: pH <8.3 Pm Pf Pom Sulfuric acid
Methyl orange/ Green: pH >4.3 Yellow: pH <4.3 Mf Sulfuric acid
brom cresol green
Methyl orange Yellow/orange: pH >4.3 Pink/red: pH <4.3 Mf Sulfuric acid
Brom cresol green Blue: pH >3.8 Yellow: pH <3.8 — Sulfuric acid
Thymolphthalein Colorless: pH <9.5 Blue: pH >9.5 — Caustic solution
Methyl red Yellow: pH >5.4 Pink/Red: pH <5.4 PHPA Sulfuric acid
Calmagite or manver Wine red: Blue/purple: Total hardness Standard Versenate
or erio black T Presence Ca2+ and Mg2+ Absence Ca2+ and Mg2+ (0.01m EDTA)
CalVer II or Calcon Wine red: Blue/purple: Calcium Standard Versenate
Presence Ca2+ Absence Ca2+ (0.01m EDTA)
Potassium chromate Yellow Orange/red: Chlorides Silver nitrate solution
solution Excess AgNO3

Table 9: Common indicators.

Basic Chemistry 4A.23 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4A Basic Chemistry
Concentrations of Solutions
Molality (m). A molal solution is a
solution which contains one mole of
_______________________
solute per kilogram of solvent. Thus, a
_______________________ 1 m (molal) solution of NaOH would
_______________________ be 40 g of NaOH per 1,000 g of water.
_______________________
Molarity (M). A solution which con-
tains one mole of solute per liter of solu-
_______________________ tion is called a molar solution. Thus,
_______________________ 0.1 M (molar) HCl is a hydrochloric acid
_______________________
solution which contains 1/10 mole or
3.646 g of hydrogen chloride per liter
_______________________
of solution.
_______________________ If the normality (N) (see below) of a
_______________________ solution is known, then the molarity
(M) can be calculated by dividing the
_______________________
normality by its net positive valence.
_______________________ Molarity =
_______________________ Normality ÷ net positive valence
Normality (N). A 1.0 normal (N) solu-
_______________________
tion is defined as a solution with a con-
_______________________
centration that contains 1 g-equivalent
weight of a substance per liter of solu-
tion and is usually written as just 1.0 N.
For example, 1.0 N solution of HCl has
36.5 g solute per liter of solution.
Likewise, a 1.0 N solution of H2SO4
has 49 g solute per liter of solution.
If the Molarity (M) of a solution is
known, the Normality (N) can be cal-
culated by multiplying the molarity of
the solute by its net positive valence.
Normality =
Molarity x net positive valence
If the net If the net positive valence is 1, nor-
mality and molarity will have the
positive
same numerical value.
valence is 1,
normality
and molarity
will have
the same
numerical
value.
Basic Chemistry 4A.24
Milligrams per liter (mg/l).
Milligrams per liter is a weight-volume
relationship. A 100-mg/l solution con-
tains 100 mg of solute per liter of solu-
tion. Milligrams-per-liter concentrations
are often improperly reported as parts
per million, which is a weight-weight
relationship. Milligrams per liter can
be converted to parts per million if the
fluid density is known, by dividing
the mg/l value by the specific gravity
of the solution.
Parts per million (ppm). Parts per
million, abbreviated “ppm” is simply
the concentration by weight of one
chemical expressed in per million parts
of the total. It is normally used to
measure small concentrations. It is the
same as the weight fraction (decimal)
times one million (1,000,000) or the
weight percent times 10,000. Saturated
salt water, for example, is 26% salt by
weight; therefore, it would contain
260,000 ppm salt (26 x 10,000 =
260,000). Parts per million also can be
calculated directly from a titration
which yields a concentration in mil-
ligrams per liter by dividing the mg/l
value by the specific gravity of the
solution.
Equivalent Parts per Million (EPM).
EPM is the unit chemical weight of
solute per million unit weights of solu-
tion. The EPM of a solute in solution is
equal to the parts per million divided
by the equivalent weight.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4A Basic Chemistry

Concentration* Solute Weight Solvent Weight Solution Volume Solution Weight

1 m (molal) 1 g mole wt 1,000 g — 1 g mole wt + 1,000 g
1 M (Molar) 1 g mole wt — 1 liter —
1 N (Normal) 1 g equiv wt — 1 liter —
100,000 mg/l 100,000 mg — 1 liter —
100,000 ppm 100,000 mg 900,000 mg — 1,000 g

Table 10: Solution concentrations.

* There is no standard starting solvent Molecular weight sodium chloride:

volume for any of these solution con- 58.44
centrations. A specific weight of solute is Gram-moles NaCl =
either added to a specific weight of sol- (230 ÷ 58.44) = 3.94
vent or solvent volume is added until a Since there are only 918 g of water,
final volume of solution is obtained. not 1 kg (1,000 g), then the number
Example: For a simple 1.148 g/cm3 (SG) of gram-moles must be adjusted for
sodium chloride solution with a volume the 1 kg value.
of 1,000 cm3 which contains 230 g of Molality = 3.94 x (1,000 ÷ 918) =
dissolved salt, calculate the following 4.287 gram-moles NaCl per kg
compositions and concentrations: d) Molarity — moles of solute per
a) Composition in weight % 1 liter of solvent:
b) Composition in volume % From c) above, there are 3.94 gram-
c) Molality moles NaCl in the original 1,000-cm3
d) Molarity (1-l) solution.
e) Normality Molarity = 3.94 gram-moles-per-liter
f) mg/l sodium chloride
e) Normality — gram equivalent
g) ppm sodium chloride
weight per liter solution:
h) EPM
Since sodium chloride has a net pos-
i) Weight ratio of NaCl to H2O, (lb/lb)
itive valence of 1, normality is the
Total solution weight =
same number as molarity.
1,000 cm3 x 1.148 g/cm3 = 1,148 g
Normality = 3.94 gram-equivalent
Water weight = total wt - salt wt =
_______________________ weights per liter
1,148 - 230 = 918 g
_______________________ f) mg/l sodium chloride:
a) Composition in weight %:
Since 230 g (230,000 mg) sodium
_______________________ Weight % NaCl =
chloride are contained in the 1,000-cm3
(230 ÷ 1,148) x 100 = 20.0%
_______________________ (1-l) solution:
Weight % H2O =
_______________________ mg/l sodium chloride =
(918 ÷ 1,148) x 100 = 80.0%
230,000 mg ÷ 1 l = 230,000 mg/l
_______________________ b) Composition in volume %:
g) ppm sodium chloride — weight
_______________________ SG pure water (20°C) = 0.998 g/cm3
ratio x 1,000,000:
Volume of pure water =
_______________________ ppm sodium chloride = (230 ÷ 1,148)
(918 ÷ 0.998) = 920 cm3
_______________________ x 1,000,000 = 200,350 ppm
Volume % of water =
(920 ÷ 1,000) x 100 = 92% h) EPM — ppm divided by
_______________________
Volume of sodium chloride = equivalent weight:
_______________________ EPM sodium chloride =
1,000 - 920 = 80 cm3
_______________________ Volume % sodium chloride = (200,350 ÷ 58.44) = 3,428 EPM
_______________________ (80 ÷ 1,000) x 100 = 8% i) Weight ratio NaCl to H2O:
c) Molality — moles of solute per Grams NaCl ÷ grams H2O =
_______________________
kilogram of solvent: (230 ÷ 918) = 0.2505
_______________________

Basic Chemistry 4A.25 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4A Basic Chemistry
Mixtures, Solutions, Emulsions and Dispersions
All of these terms have significant
meanings to the mud engineer. The sub-
tleties in meaning often are overlooked
and not appreciated.
A mixture is a combination of two
or more substances with no consistent
composition throughout. Mixtures of
different kinds of nuts or candies are
common. Each substance in a mixture
retains its unique properties.
A solution is A solution is a homogenous mixture
a homoge- of two or more substances. A solution
has a consistent composition through-
nous mixture out. Solutions can be solids in solids
of two (metal alloys), solids in liquids (sugar
or more in water), liquids in liquids (alcohol in
water), gases in liquids (carbonated
substances.
Common Chemical Reactions in Mud Chemistry
This section concerns mud chemistry
problems commonly facing most mud
engineers. Reactions with various treat-
ment chemicals are illustrated with resul-
tant precipitants or results. For a more
detailed discussion of these reactions,
see the chapter on Contamination
_______________________ and Treatment.
_______________________
GYP OR ANHYDRITE CONTAMINATION
_______________________
The calcium ion, which can be derived
_______________________ from gyp or when drilling anhydrite,
_______________________ is a contaminant in most water-base
muds. One way to reduce calcium is to
_______________________
add soda ash. The following equation
_______________________ illustrates how calcium sulfate (or gyp)
_______________________ can be removed using treatments of
sodium carbonate (soda ash) to form
_______________________
calcium carbonate. The downward
_______________________ arrow implies precipitation of an insol-
_______________________ uble solid, whereas an upward arrow
would imply generation of a gas.
_______________________
CaSO4 + Na2CO3 →
_______________________ CaCO3 ↓ + 2Na+ + SO42 –
_______________________ Sodium Acid Pyrophosphate (SAPP)
_______________________ can also be used for treating anhy-
drite contamination. It should be
Basic Chemistry 4A.26
beverages) or gases in gases (air).
Whenever two substances that can
react with each other are in solution,
they will usually do so.
A dispersion is a two-phase system
in which one phase consists of finely
ground solid particles distributed in
the second phase. Drilling fluids with
clays and solids are dispersions.
An emulsion is a stable mixture of
immiscible liquids held together by
emulsifiers. Diesel oil and calcium
chloride brine are not soluble in each
other; however, they can be combined
to form an emulsion with the brine
being emulsified in the diesel oil to
form oil-base mud systems.
used with caution for this purpose,
because SAPP reduces pH and is not
stable at high temperatures as a mud
thinner. The reaction of SAPP with
gypsum is as follows:
Na2H2P207 + H2O → 2NaH2PO4;
2NaH2PO4 + 3CaSO4 →
Ca3(PO4)2↓ + 2Na+ + 3SO42 – + 4H+
CEMENT CONTAMINATION
Cement contains lime, Ca(OH)2, a
source of calcium and a flocculant
which can be removed by adding
sodium bicarbonate (NaHCO3). The
reaction is as follows:
Ca(OH)2 + NaHCO3 →
CaCO3↓ + NaOH + H2O
This reaction forms sodium hydrox-
ide and will result in elevated pH even
after the calcium from the cement is
removed. For severe cement contami-
nation, an acid should be used in com-
bination with sodium bicarbonate to
maintain an acceptable pH value.
Common acids used with sodium
bicarbonate are citric acid, acetic
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4A Basic Chemistry

acid, SAPP, and organic acids like
lignite or lignosulfonate.
SEAWATER
Magnesium ions and calcium ions are
present in seawater. Both of these ions
are detrimental to water-base muds.
Since magnesium hydroxide (Mg(OH)2)
and calcium hydroxide (Ca(OH)2) are
relatively insoluble at higher pH, caus-
tic should be used to remove magne-
sium and suppress the solubility of
calcium. The reactions are as follows:
Mg2+ + 2NaOH →
Mg(OH)2↓ + 2Na+ (pH >10)
Ca2+ + 2NaOH →
Ca(OH)2↓ + 2Na+ (pH >11)
Caustic soda Caustic soda is used to reduce the
magnesium and calcium in seawater
is used to
by first precipitating magnesium as
reduce the Mg(OH)2, and then increasing pH to
magnesium suppress the solubility of calcium and
precipitate lime. If lime is used in sea-
and calcium
water it, too, will remove magnesium,
in seawater… but the resulting calcium levels will be
very high and are undesirable. Gulf of
Mexico seawater requires 1.5 to 2 lb/bbl
caustic soda (4.3 to 5.7 kg/m3) to precip-
itate all magnesium, then convert the
14
calcium to lime, resulting in a pH >11.0
(see Figure 10). In seawater, the preferred
treatment for magnesium removal is
caustic, while the preferred treatment
for calcium removal is soda ash.
CARBON DIOXIDE GAS CONTAMINATION
Carbon dioxide (CO2) is an acidic gas
which exists in many formations and is
a common mud contaminant. CO2 in
an aqueous solution will form carbonic
acid (H2CO3), which will convert to
bicarbonate groups (HCO3–) at medium
pH values, then carbonate groups (CO32–)
at higher pH, as illustrated previously
in Figure 7. Small influxes may be
treated with caustic soda:
CO2 + H2O → H2CO3 (carbonic acid);
2NaOH + H2CO3
2Na+ + CO32+ + 2H2O (pH > 11)
Massive influxes should be treated
with lime. Be advised that the calcium
carbonate precipitate may cause scale
to form on the surface of the drill-
string and is difficult to remove from
the fluid with solids-control equipment
due to the ultra-small (submicron)
particle size.
H2O
Ca(OH)2 + CO2 → CaCO3 ↓ + H2O

13
Distilled water

12
Freshwater mud
Seawater
11
pH

10
Mg removed — Ca
begins to convert to
Ca(OH)2
9
Magnesium begins
to precipitate as
Mg (OH)2
8

7
0 0.5 1.0 1.5 2.0 2.5
Caustic soda (lb/bbl)
Seawater: pH 8.0, 390 mg/l Ca, 1,300 mg/l Mg, 19,000 mg/l Cl

Figure 10: pH vs. caustic soda for seawater.

Basic Chemistry 4A.27 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4A Basic Chemistry
CARBONATE AND BICARBONATE
CONTAMINATION
Bicarbonate (HCO3–) and carbonate
(CO32–) contamination can occur
through the conversion of CO2 gas,
mentioned above, or from the thermal
degradation of organic additives such as
lignite and lignosulfonate and from bio-
degradation of starch and other addi-
tives, among other sources. These ions
can be removed with calcium. However,
since calcium bicarbonate Ca(HCO3)2 is
soluble, all bicarbonates must be con-
verted into carbonates (above a pH of
about 11) before they can be completely
…H2S should precipitated as calcium carbonate. The
always be removal of bicarbonates and carbonates
can be achieved with any source of solu-
precipitated ble calcium under conditions of con-
with a source stant pH (if pH is high enough) or by
of zinc… increasing the pH with caustic soda in
the presence of calcium.
Lime (Ca(OH)2) is preferred for con-
verting HCO3– to CO32– and then pre-
cipitating the carbonates as CaCO3,
especially if the system pH will not be
elevated to >11.
2HCO3– + Ca(OH)2 →
CaCO3↓ + OH– + H2O
CO32– + Ca(OH)2 → CaCO3↓ + 2OH–
When a constant pH value must be
maintained, a combination of gyp and
lime treatments is required:
Ca(OH)2 + 2HCO3– →
CaCO3↓ + CO32– + 2H2O
CaSO4 • 2H2O + CO32– →
CaCO3↓ + SO42– + 2H2O
HYDROGEN SULFIDE
(H2S) CONTAMINATION
Hydrogen Hydrogen sulfide is a poisonous and
sulfide is a dangerous acidic gas encountered in
many formations and produced fluids.
poisonous It can quickly deaden senses and can be
and
fatal even at low concentrations. H2S is
dangerous characterized by its typical “rotten egg”
smell. For safety reasons, it should be
acidic gas… neutralized immediately with caustic
Basic Chemistry 4A.28
soda or lime to increase the pH to >11.5
to form sulfide (S2–), then precipitated
with a source of zinc.
Neutralization with caustic soda:
2NaOH + H2S
2Na+ + S2– + 2H2O (at pH >11.5)
Neutralization with maintaining
excess lime:
H2S + Ca(OH)2 →
Ca2+ + S2– + 2H2O (pH >11.5)
Converting hydrogen sulfide into just
sulfide by increasing pH is not a per-
manent reaction. If the pH were to
drop into the acid region, sulfide will
convert back into the poisonous hydro-
gen sulfide form. For this reason, H2S
should always be precipitated with a
source of zinc, such as zinc oxide.
Removal by precipitation with
treatments of zinc oxide (ZnO):
H2S + ZnO → ZnS↓ + H2O
REMOVAL OF OXYGEN WITH
OXYGEN SCAVENGER
Dissolved oxygen will cause increased
corrosion and can be removed with
treatments of a chemical containing
sulfite. Liquid ammonium bisulfite
solutions are the most common oxy-
gen scavengers and react with oxygen
as follows:
NH4HSO3 + 1⁄2 O2 + OH– →
NH4 + SO3 + H2O;
SO3 + 1⁄2 O2 → SO4
Soluble calcium may react to form
calcium sulfite, which has a maximum
solubility of about 43 mg/l in cold
water and less in hot water. The sulfite
residual at the flow line should not be
expected to exceed this level if the mud
contains high levels of calcium.
ACID TREATMENTS
The filter cakes containing acid-soluble
weight materials, such as calcium
carbonate used for non-damaging
reservoir drill-in fluids, are often
removed from the well with
hydrochloric acid treatments.
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER
4A Basic Chemistry
Calcium carbonate dissolution using
hydrochloric acid:
_______________________
CaCO3 + 2HCl →
_______________________ CaCl2 + CO2↑ + H2O
_______________________
PHOSPHATES
_______________________
Sodium Acid Pyrophosphate (SAPP)
_______________________ and other phosphates will react with
_______________________
and precipitate calcium according to
the following reaction:
_______________________
Na2H2P2O7 + H2O → 2NaH2PO4;
_______________________ 2NaH2PO4 + 3Ca(OH)2 →
_______________________ Ca3 (PO4)2↓ + 4H2O +2NaOH
_______________________
Although the reaction has caustic as
a byproduct, pH is still reduced, since
_______________________
SAPP is a weak acid and the reaction
_______________________ leaves only two hydroxyl groups for
_______________________ every six original hydroxyl groups.
_______________________ EFFECT OF LIGNITE ON CALCIUM
_______________________ Lignite contains calcium (from 1.5 to
5%) as part of its chemical makeup.
Organic acids like lignite also have the
ability to tie up calcium chemically.
This complexed calcium exists as a solid
particulate (flock) and may not be large
Basic Chemistry 4A.29
enough to be removed by mechanical
means. The filter cake will filter out
most of the calcium complexed with
the lignite. However, some lignite-
complexed calcium will pass through
the filter cake and paper so that it will
be collected with the filtrate. During
the titration of filtrate calcium, the
readily available calcium is titrated
first. As the titration continues, the
complexed calcium solubilizes and
this, too, will be titrated. This com-
plexed calcium is not available for
chemical reactions in mud systems.
One lb/bbl of solubilized lignite has
the potential to complex 200 mg/l cal-
cium. Keep in mind that although the
calcium titration may show a sufficient
excess of calcium, none may be avail-
able to react with carbonate and bicar-
bonate groups. So, it may be possible
to be experiencing a carbonate prob-
lem even though some calcium is
titrated in the filtrate when using
lignite as an additive.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4B Clay Chemistry
Introduction
A thorough understanding of clays can
be the mud engineer’s most valuable
tool. Clay may be added intentionally,
such as M-I GELT, or it may enter the
mud as a major contaminant through
dispersion of drill solids. In either case,
it becomes an active part of the system.
…it is For this reason, it is necessary to under-
necessary to stand basic clay chemistry in order
to properly control water-base muds.
understand Clay chemistry is also important with
basic clay regard to interactions between water-
chemistry base muds and shales which affect
wellbore stability.
in order Clay is a broad term commonly used
to properly to describe sediments, soils or rocks
control consisting of extremely fine-grained
mineral particles and organic matter.
water-base A good example is the clays (or some-
muds. times called gumbo clays) found in the
backyard or along riverbanks. These
clays are often soft and plastic when
wet, but become hard when dry. This
“soft when wet, hard when dry” physi-
cal property can be related to the pres-
ence of certain clay minerals. Clay is
also used as a group term for particles
with a size less than 2 microns in
diameter, which includes most of
the clay minerals.
…clay Clay minerals are fine-grained
minerals… aluminum silicate minerals having
well-defined microstructures. In min-
are used eralogical classification, clay minerals
to provide are classified as layered silicates because
viscosity, gel the dominant structure consists of lay-
ers formed by sheets of silica and alu-
structure and mina. Each sheet is a thin, plate-like
fluid-loss structure and is called a unit layer. A
control. typical layered silicate mineral, for
example, is mica or vermiculite, which
can be split into thin layers along the
cleavage planes. Most clay minerals are
platy in morphology. Depending on
the repeating units of the structure,
Clay Chemistry 4B.1
clay minerals can be further classified
as to the ratio of silica to alumina lay-
ers such as 1:1, 2:1 and 2:2, as well as
according to whether they are layered
or needle-shaped clay minerals.
In the drilling fluids industry, cer-
tain clay minerals such as smectite, a
major component of bentonite, are
used to provide viscosity, gel structure
and fluid-loss control. Formation clays
are unavoidably incorporated into the
drilling fluid system during drilling
operations and they may cause vari-
ous problems. Thus, clay minerals
can be beneficial or harmful to the
fluid system.
The term bentonite is used for
commercially-mined sodium montmo-
rillonite (which is a form of smectite)
that is used as an additive for drilling
mud (i.e. M-I GELT or M-I GEL SUPREMEE).
Geologically, bentonite is a bed of altered
volcanic ash. One of the biggest deposits
of this volcanic ash occurred over
60 million years ago in areas of North
America now known as the Blacks
Hills of Wyoming and South Dakota,
and the Big Horn Mountains of
Wyoming. Bentonite clay mined in
Wyoming actually comes from this
volcanically deposited bentonite bed.
Bentonite clay mined in other areas of
the world may be from other types of
geological deposits.
Because of their small particle sizes,
clays and clay minerals are analyzed
with special techniques such as x-ray
diffraction, infrared absorption and
electron microscopy. Cation Exchange
Capacity (CEC), water adsorption and
surface area are some of the properties
of clay minerals that are often deter-
mined in order to better characterize
clay minerals as well as to minimize
drilling problems.
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER
4B Clay Chemistry
Types of Clays
There are a large number of clay min-
erals, but those with which we are
concerned in drilling fluids can be
categorized into three types.
The first type are needle-shaped,
non-swelling clays like attapulgite or
sepiolite. It is believed that the shape
of the particles is responsible for the
clay’s ability to build viscosity. The nat-
ural fine crystal size and needle shape
causes it to build a “brush heap” struc-
ture in suspension and thereby exhibit
high colloidal stability even in the
presence of high electrolyte concen-
Clays exist tration. Owing to their shape and
in nature non-swelling characteristics, these clays
exhibit very poor filtration control. For
with a this reason, attapulgite is primarily used
stacked or as a viscosity builder in saltwater muds
layered and sepiolite is most often used as a
supplemental viscosifier for geothermal
structure… and high-temperature fluids. These
clays are rarely, if ever, present in for-
mation shales. M-I sells attapulgite
under the name SALT GELT and sepiolite
under the name DUROGELT.
The second type are the plate-like,
non-swelling (or slightly swelling)
clays: illite, chlorite and kaolinite,
discussed later.
Separating The third type are the plate-like,
these packs highly swelling montmorillonites.
The second and third types of clay
into multiple minerals are found in formation shales
layers is in the following order in decreasing
known as amounts: (1) illite, (2) chlorite, (3)
montmorillonite and (4) kaolinite.
dispersion. Because these clays are present in
drilled formations, they become dis-
persed in the drilling fluid system in
varying amounts. The montmorillonite
in shales is usually calcium montmo-
rillonite since it is in equilibrium with
the formation water, which is normally
rich in calcium.
Clay Chemistry 4B.2
Sodium montmorillonite (Wyoming
bentonite, M-I GELT and M-I GEL
SUPREMEE) is also normally added to a
mud to increase viscosity and reduce
fluid loss. The filtration and rheological
properties of the mud become a func-
tion of the amounts of various clays
contained in the mud. Since the mont-
morillonite is intentionally added to a
mud to control these properties, the
other clay types may be considered
contaminants, as they are not as
effective as a commercial clay.
Clays exist in nature with a stacked or
layered structure, with each unit layer
roughly 10 angstroms (Å) thick. This
means there are about a million layers
of clay per millimeter of thickness. Each
clay layer is highly flexible, very thin
and has a huge surface area. An indi-
vidual clay particle can be thought of
as being much like a sheet of paper or
a piece of cellophane. One gram of
sodium montmorillonite has a total
layer surface area of 8,073 ft2 (750 m2)!
In freshwater, the layers adsorb water
and swell to the point where the forces
holding them together become weak-
ened and individual layers can be sep-
arated from the packs. Separating these
packs into multiple layers is known as
dispersion. This increase in number of
particles, with the resulting increase in
surface area, causes the suspension to
thicken. Figure 1 is an actual photomi-
crograph of a bentonite particle. Note
that it resembles a fanned-out deck of
cards. Several of the plate-like particles
can be seen overlapping each other. It
is this characteristic shape of the parti-
cles that produces the so-called “shin-
gling” effect that is so important to
fluid-loss control.
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER

4B Clay Chemistry

2µ 2µ

ca One
Sili 10 Å unit
Tetrahedral a
min layer
Alu
Octahedral
ca
Sili
Tetrahedral

Figure 2: Idealized montmorillonite particle.

sheets. Three-layer clays are built of

unit layers composed of two tetrahe-
Figure 1: Photomicrograph of bentonite particles. dral sheets on either side of one octa-
hedral sheet, somewhat like a sandwich
Clays are usually either of the two-
(see Figure 2). Two-layer clays are built
layer type like kaolin or three-layer
of unit layers consisting of only one
type such as montmorillonite, chlorite
tetrahedral and one octrahedral sheet.
or illite. Each plate-like clay particle
Clays can consists of a stack of parallel unit lay-
Clays can either be electrically neu-
either be tral or negatively charged. For exam-
ers. Each unit layer is a combination
ple, pyrophyllite [Al2Si4O10 – (OH)2],
electrically of tetrahedrical (pyramid) arranged
a neutral clay, as shown in Figure 3,
silica sheets and octahedrical (eight-
neutral or faced) arranged alumina or magnesia
is similar to the negatively charged
negatively montmorillonite.
charged. All surface charges balance
– – – – –
O O + O + O + O +
O O O O O O O Silica
Si Si Si Si Si Si Si Si + layer
O O O O O O O O
OH OH OH OH
Al Al Al Al Al Al Al Al Alumina
OH OH OH OH layer
O O O O O O O O

+ Si Si Si Si Si Si Si Si O Silica
O O O O O O O –
+ + + + layer
O O O O

Figure 3: Electrically neutral pyrophyllite.

Clay Chemistry 4B.3 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER

4B Clay Chemistry

MONTMORILLONITE CLAYS In addition to the substitution of

(THREE-LAYER CLAYS) magnesium (Mg2+) for aluminum (Al3+)
_______________________ If just one atom of magnesium (Mg2+) is in the montmorillonite lattice, many
substituted for one atom of aluminum other substitutions are possible. Thus,
_______________________
(Al3+) in the lattice structure (arrange- the name montmorillonite often is used
_______________________ ment of atoms), it will then possess a as a group name including many spe-
_______________________ surplus electron or negative charge cific mineral structures. However, in
(see Figure 4). The net negative charge recent years, the name smectite has
_______________________
is compensated by the adsorption of become widely accepted as the group
_______________________ name, and the term montmorillonite
cations (positive ions) on the unit
_______________________ layer surfaces, both on the interior and has been reserved for predominantly
on the exterior surfaces of the stack. aluminous members of the group. This
_______________________
The cations that are adsorbed on the group of minerals includes montmoril-
_______________________ lonite, hectorite, saponite, nontronite
unit-layer surfaces may be exchanged
_______________________ for other cations and are called the and a number of other specific minerals.
_______________________ exchangeable cations of the clay. The ILLITES (THREE-LAYER CLAYS)
quantity of cations per unit weight of
_______________________ Illites have the same basic structure
the clay is measured and reported as
as montmorillonites, but they do not
_______________________ the CEC. The cation may be a single-
show interlayer swelling. Instead of
_______________________ charge ion such as sodium (Na+) or a
the substitution of Mg2+ for Al3+ as in
double-charge ion such as calcium
_______________________ montmorillonite, illite has a substitu-
(Ca2+) or magnesium (Mg2+). Thus, we
tion of Al3+ for Si4+, still giving a nega-
have sodium montmorillonite, calcium
tive charge. The compensating cations
montmorillonite and/or magnesium
are primarily the potassium ion (K+),
montmorillonite. Although Wyoming
as shown in Figure 6. The net negative
bentonite is generally described as
lattice charge that results from these
sodium montmorillonite, the exchange-
substitutions, by compensating potas-
able calcium and magnesium may con-
sium ions, is usually larger than that
stitute 35 to 67% of the total exchange
of montmorillonite by as much as one
capacity. The most typical property of
and a half times.
montmorillonites is that of interlayer
swelling (hydrating) with water (see
Figures 5 and 6).

Na+ Surface-bonded cations Na+

Surplus negative charges
– – – – –
O O + O + O + O +
O O O O O O O Silica
Si Si Si Si Si Si Si Si + layer
O O O O O O O O
OH OH OH OH
Al Alumina
Al Mg Al Al Al Mg Al
layer
OH OH OH OH
O O O O O O O O

+ Si Si Si Si Si Si Si Si O Silica
O O O O O O O – layer
+ O + O + O + O

Figure 4: Substitution of Mg 2+ for Al 3+ causing a negative-charged particle.

Clay Chemistry 4B.4 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER

4B Clay Chemistry

Tetrahedral
alumina

OH

Octahedral
silica
OH
Interlayer
distance OH

Tetrahedral
alumina

Exchangeable cations nH2O (adsorbed water) Swelling

Next unit
layer
tetrahedral
alumina

Oxygens OH Hydroxyls Aluminum, iron, magnesium

and Silicon, ocassionally aluminum

Figure 5: Structure of smectite.

The spacing between unit layers is
2.8 Å. The ionic diameter of the K+ is
Only the 2.66 Å. This allows the K+ to fit snugly
potassium between unit layers forming a bond
ions on the that prevents swelling in the presence
of water. Since the unit layers do not
external swell and separate when exposed to
surfaces water, the potassium ions (K+) between
can be the unit layers are not available for
exchanged exchange. Only the potassium ions on
the external surfaces can be exchanged
for other for other cations.
cations. Among the 2:1 clay minerals, smec-
tite, illite, and mixed layers of illite and
smectite are encountered during drilling
shale formations and often cause vari-
ous problems in borehole stability and
drilling fluid maintenance. The trouble-
some nature of these clay minerals can
be related to the weakly-bonded inter-
layer cations and weak layer charges
that lead to swelling and dispersion
upon contact with water. With increas-
ing burial depths, the smectite gradually
converts into illite/smectite mixed-layer
clays and finally to illite and mica. As
a result, shale formations generally
become less swelling but more disper-
sive in water with increasing depth.

Clay Chemistry 4B.5 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER

4B Clay Chemistry

CHLORITES (THREE-LAYER CLAYS) KAOLINITES (TWO-LAYER CLAYS)

Chlorites are structurally related to the Kaolinite is a non-swelling clay that
three-layer clays. In their pure form has its unit layers bound tightly
they will not swell, but they can be together by hydrogen bonding. This
made to swell slightly with alteration. prevents expansion of the particle
In these clays, the charge-compensat- because water is unable to penetrate
Kaolinite ing cations between montmorillonite- the layers. Kaolinite does not contain
does not type unit layers are replaced by a layer interlayer cations or surface charges
of octahedral magnesium hydroxide, because there is little or no substitu-
contain or brucite (see Figure 6). This layer has tion in either tetrahedral or octahedral
interlayer a net positive charge because of some sheets. However, some minor charges
cations or replacement of Mg2+ by Al3+ in the can come from broken bonds or impu-
brucite layer. rities. Therefore, kaolinite has a rela-
surface Chlorite is often found in old, deeply tively low cation exchange capacity
charges… buried marine sediments and normally (5 to 15 meq/100 g). Kaolinite is com-
does not cause significant problems monly found as a minor to moderate
unless present in large quantities. The constituent (5 to 20%) in sedimentary
cation exchange capacity of chlorite rocks such as shales and sandstones.
varies from 10 to 20 meq/100 g, primar- A summary of clay minerals is shown
ily due to broken bonds. The interlayer in Table 1 and a schematic comparison
distance of chlorite is usually about of the various clay structures shown in
14 Å. Chlorite also may form mixed- Figure 6.
layer clays with other clay minerals
such as smectite. The resultant mixed-
layer clay would have the properties of
both types of clay minerals.
Interatomic
Exchange Distance
Group Structure Charge Cation (Å) Swelling
Kaolinite 1:1 layer Nil None 7.2 None
Talc 2:1 layer Nil None 9.3 None
Smectite 2:1 layer 0.3 - 0.6 Na+, Ca2+, K+, Mg2+ 11 - 15 Variable
Vermiculite 2:1 layer 1.0 - 4.0 K+, Mg2+ 14 - 15 Variable
Illite 2:1 layer 1.3 - 2.0 K+ 10 Nil
Mica 2:1 layer 2.0 K+ 10 None
Chlorite 2:2 layer Variable Brucite layer 14 Nil
Sepiolite 2:1 chain Nil None 12 Nil
Palygorskite 2:1 chain Minor None 10.5 Nil

Table 1: Commonly encountered clays.

Clay Chemistry 4B.6 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER

4B Clay Chemistry

H2O H2O H2O

H2O Mg(OH)2 KK

H2O
KK
H2O H2O Mg(OH)2

1 crystal 1 crystal 1 crystal KK 1 crystal

H2O
H2O H2O Mg(OH)2
KK
H2O
Mg(OH)2 KK
H2O

Sepiolite
Needle-shaped clay H2O H2O H2O
H2O H2O Kaolinite Chlorite Illite
(Mg(OH)2 = brucite sheet) (K = potassium)
Plate-like, non-swelling clays
1 crystal Mg(OH)2 KK 1 crystal
H2O
1 crystal
H2O b H2O
H2O
1 crystal 1 crystal
a c
Mg(OH)2 KK
H2O

H2O H2O
H2O
Chlorite type Illite type
“a” Has the properties of chlorite
“b” Has the properties of montmorillonite H2O
“c” Has the properties of illite
Montmorillonite
Mixed-layer clays Plate-like, swelling clays

Figure 6: Clay structure comparison.

Cation Exchange Capacity (CEC)

The compensating cations that are When this test is run on a mud, the
adsorbed on the unit-layer surface may total methylene blue exchange capac-
be exchanged for other cations and are ity of all the clay minerals present in
called the exchangeable cations of the the mud is measured. It is normal
The quantity clay. The quantity of cations per unit procedure to report the Methylene
of cations weight of clay is measured and reported Blue Capacity (MBC) as the equiva-
as the CEC. The CEC is expressed in lent amount of Wyoming bentonite
per unit millequivalents per 100 g of dry clay required to obtain this same capacity.
weight of (meq/100 g). The CEC of montmoril- It is important to note that the test
clay is… lonites is within the range of 80 to does not directly indicate the amount
150 meq/100 g of dry clay. The CEC of bentonite present. However, an esti-
the CEC. of illites and chlorites is about 10 to mate of the amount of bentonite and
40 meq/100 g, and for kaolinites it is solids in the mud can be calculated if
about 3 to 10 meq/100 g of clay. one considers that the average drill
The Methylene Blue Test (MBT) is an solids have about 1/9 the CEC of ben-
indicator of the apparent CEC of a clay. tonite, and if the amount of drill solids

Clay Chemistry 4B.7 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4B Clay Chemistry
present in the mud is calculated from
a retort analysis. This estimation of
the quantity of added bentonite and
drill solids can be made more exact
by measuring the MBC of the drill cut-
tings. This procedure can be helpful
in estimating both the amount and
quality of the clays in the mud.
In order to have some idea of which
cations will replace other cations in
the exchange positions, the following
…any cation is generally accepted and is arranged
to the left in decreasing preference:
will replace H+ > Al3+ > Ca2+ > Mg2+ > K+ > NH4+ >
Na+ > Li+
any cation
to its right. In other words, any cation to the
left will replace any cation to its right.
Composition of Clay-Water Muds
In most In most areas, commercial clays, such
areas, as M-I GELT and M-I GEL SUPREMEE , are
added to water when preparing a water-
commercial base mud. The clays serve a dual pur-
clays…are pose: (1) to give viscosity to the drilling
added to fluid, and (2) to deposit a filter cake
that will seal permeable formations in
water when order to limit filtration losses and pre-
preparing a vent stuck pipe. In some areas, drilling
water-base can be performed starting with water
and allowing the drill solids to be
mud. incorporated, resulting in sufficient
properties to allow the well to be drilled.
In other situations, polymer-base sys-
tems are used where no clays are added
to the formulation.
Clay-water muds have water as the liq-
uid continuous phase in which certain
materials are held in suspension and
other materials dissolved. Numerous
mud additives are used to obtain special
properties but, basically, all components
can be divided into three categories.
1. The water phase is the continuous
phase of the mud. Depending on
location and/or available water,
Clay Chemistry 4B.8
The relative concentration of each
cation also affects this cation-exchange
preference. Even though calcium is
more difficult to replace than sodium,
if the ionic concentration of Na+ is
significantly higher than Ca2+, then
sodium will displace calcium. Cation
exchange may result from a change in
temperature since many compounds
have different solubility-to-temperature
relationships. Some of the common
calcium salts, such as CaSO4, decrease
in solubility at high temperatures while
most sodium compounds increase in
solubility. As the Na+/Ca2+ concentra-
tion increases, there is a tendency for
the Ca2+ on the clay to be replaced by
Na+ from solution.
this may be freshwater, seawater,
hard water, soft water, etc. It is
not uncommon to use a variety
of brine solutions from salty up
to saturation as the base liquid
to build a water-base system.
2. The reactive-solids phase is com-
posed of commercial clays, incorpo-
rated hydratable clays and shales
from drilled formations that are held
in suspension in the fluid phase.
These solids are treated chemically
to control the properties of the drill-
ing fluid. Various additives will be
used to obtain desirable properties.
3. Inert solids refer to those solids in
suspension that are chemically inac-
tive. These may be inert drill solids
such as limestone, dolomite or sand.
Barite is added to the drilling fluid
to increase the fluid density and is
also an inert solid.
The remainder of this chapter will
discuss the behavior of the reactive
solids in the water phase and how
this affects mud properties.
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER

4B Clay Chemistry

HYDRATION OF CLAYS phenomena allow clays to generate

The bentonite crystal consists of
three layers: an alumina layer with a
silica layer above and below it. The clay
platelet is negatively charged and has a
The thickness cloud of cations associated with it. If a
of the significant amount of these cations are
sodium, the clay is often called sodium
adsorbed-
montmorillonite. If they are primarily
water film calcium, then the clay is called calcium
is controlled montmorillonite.
Depending on the cations present,
by the type
the interlayer spacing of dry montmo-
and amount rillonite will be between 9.8 (sodium)
of cations… and 12.1 Å (calcium) and filled with
tightly bound water. When dry clay
contacts freshwater, the interlayer
spacing expands, and the clay adsorbs
a large “envelope” of water. These two
viscosity. As shown in Figure 7, cal-
cium-base bentonites only expand to
17 Å, while sodium bentonite expands
to 40 Å.
The thickness of the adsorbed-water
film is controlled by the type and
amount of cations associated with the
clay. Water adsorbed to the large, flat,
planar surfaces comprises the major
part of the total water retained by
hydratable clays. Divalent cations
such as Ca2+ and Mg2+ increase the
attractive force between platelets, thus
decreasing the amount of water that
can be adsorbed. Monovalent cations
such as Na+ give rise to a lesser attrac-
tive force and allow more water to
penetrate between the platelets.

Calcium montmorillonite

Ca2+ 17 Å

Ca2+
Silica
Alumina
Silica Ca2+

10 - 12 Å Ca2+

Hydration
water
1-2µ

Na+
Na+

+ water
Na+
Na+

Sodium or calcium Na+

montmorillonite
Na+
40 Å

Na+
Na+

Sodium montmorillonite

Figure 7: Comparison of swelling for calcium and sodium montmorillonite.

Clay Chemistry 4B.9 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4B Clay Chemistry
Because sodium bentonite swells four
times as much as calcium bentonite,
sodium bentonite will generate four
times the viscosity. A more compre-
hensive discussion of the role which
calcium-base exchange plays in calcium-
treated systems is covered in the Water-
Base Systems chapter.
A cation Smectite, in addition to adsorbing
water and cations on external surfaces,
may serve absorbs water and cations to surfaces
as a bond between layers in its crystalline struc-
ture. The ability of smectite to adsorb
to hold the
water is much greater than other clay
clay mineral minerals. The ability to adsorb water,
particles the quantity of exchangeable cations
together… (CEC) and the surface area are closely
related phenomena that are sometimes
termed colligative properties of clay.
These colligative properties are basi-
cally measurements of the reactivity
of the clay. Because CEC is easy to
…colligative measure, it is a practical method to
properties assess clay or shale reactivity. The CEC
of clay can be measured with a meth-
are basically ylene blue titration. When measuring
measurements the CEC, 0.01 N methylene blue solu-
of the tion is used so the number of milli-
liters of methylene blue solution
reactivity needed to reach the end point is
of the clay. equal to meq/100 g. The range of
CEC for pure clay mineral materials
is shown in the following table:
Clay CEC (meq/100 g)
Smectite 80 - 150
Illite 10 - 40
Chlorite 10 - 40
Kaolinite 3 - 10
Table 2: CEC range for pure clay mineral materials.
Smectite is clearly much more reactive
than other clay mineral materials. Shales
containing smectite are the most water-
sensitive and hydrate the most. Shales
containing other clay minerals have
less ability to hydrate but still may be
Clay Chemistry 4B.10
water-sensitive. Most shales contain sev-
eral types of clay in varying amounts.
The reactivity of a shale depends on the
types and amounts of clay minerals pre-
sent in the shale. Often the CEC is a
better measure of clay reactivity than
the mineralogical analysis inferred from
X-ray diffraction analysis.
CATIONIC INFLUENCE ON HYDRATION
As pointed out previously, the relative
replacing power of one cation by
another is shown in the following series:
H+ > Al3+ > Ca2+ > Mg2+ > K+ > NH4+ >
Na+ > Li+
A cation may serve as a bond
to hold the clay mineral particles
together, thereby decreasing hydra-
tion. Multivalent cations tie layers
together more firmly than monova-
lent cations, usually resulting in aggre-
gation of the clay particles. Potassium,
a monovalent cation, is the exception
to the rule. The adsorbed cations may
become hydrated and attract a water
envelope with a definite shape. The
size and shape of the hydrated cation
affects its ability to fit between inter-
layer clay surfaces and influences both
clay swelling and clay hydration. Spaces
within the crystalline montmorillonite
layers is 2.8 Å. Small ions, like potas-
sium, that can fit between clay layers
are more easily and permanently
exchanged. In addition, cations that
become large when hydrated expand
the interlayer distances to promote clay
hydration. Calcium is a good example,
having a hydrated diameter of 19.2 Å.
Lithium is another example, having
three water molecules and a hydrated
diameter of 14.6 Å. Monovalent cations
with large hydrated diameters cause the
most swelling and dispersion. Multivalent
cations with small hydrated diameters
are the most inhibitive.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4B Clay Chemistry

Table 3 lists the ionic diameter The ion exchange reaction is gov-
(crystalline) and hydrated diameter erned by the law of mass action; that
of cations common to drilling fluids. is the rate of exchange depends on
Once hydrated cations are adsorbed the concentration of the ions (i.e. the
in the interlayer region, they can be higher the ratio of K ion to Na ion,
dehydrated with time and exposure to the faster the rate of exchange
high temperatures so that the inter- of K+ for Na+).
layer distances actually shrink and In addition to ion exchange, ion fix-
become less reactive (see ion fixation ation will occur in clays with a high
discussed in the following section). layer charge. This increases the selec-
tivity of the clay for potassium by an
Ionic Diameter Hydrated Diameter order of magnitude. Montmorillonite
Cation (Å) (Å)
Li+ 1.56 14.6
clays, such as Wyoming bentonite and
Na+ 1.90 11.2 some gumbo-type shales which were
K+ 2.66 7.6 deposited in potassium-depleted envi-
Chemical NH4+ 2.86 5.0 ronments, are selective to potassium.
Mg2+ 1.30 21.6 Based on theoretical calculations, Eberl
reactions Ca2+ 1.98 19.2 finds that potassium fixation in smec-
between Al3+ 1.00 18.0 tite clays will occur if the layer charge
clay and Table 3: Ionic radii and hydration radii is high and will shift the equilibrium
of common cations. toward preferential cation exchange
potassium with potassium.
ions are CLAY REACTIONS WITH POTASSIUM IONS In the Gulf Coast, the smectite con-
unique… Chemical reactions between clay and tent of the shales and gumbos is derived
potassium ions are unique when com- from the weathering of igneous and
pared to other ions. The ion exchange metamorphic rock or recycled sedi-
model does not fully explain the inter- mentary smectite ultimately derived
action of potassium with clay. Special from igneous and metamorphic rock.
attention will be paid to this process Furthermore, the smectite clays in the
because of the widespread use of potas- Gulf of Mexico have undergone at least
sium in drilling and completion fluids some degree of alteration by the process
to stabilize reactive shales. Even in U.S. known as burial diagenesis.
…smectite offshore applications, where the potas- This diagenetic alteration can be sub-
sium level must be maintained below divided into a two-step reaction. The
clays in the 5% for environmental reasons, this first step is the creation of high-layer-
Gulf of small concentration of ions can help charged smectite by the substitution of
Mexico have stabilize active shale formations because aluminum for silicon in the tetrahedral
ion fixation can occur in some smec- layer of the smectite. The high-layer-
undergone at tite clays when they are exposed charged smectite is then converted to
least some to potassium. illite (actually mixed-layer illite/smectite)
degree of According to Eberl (1980), there are by fixation of potassium. This fixation
two ways that potassium can become of potassium occurs in nature even with
alteration… associated with clay minerals: a high sodium-to-potassium ratio in the
1. Ion exchange (discussed earlier). pore solution.
2. Ion fixation.

Clay Chemistry 4B.11 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4B Clay Chemistry
There is enough potassium available
…linking to allow smectite layers to transform
processes to illite layers in many geological set-
tings. In other geological settings, the
must be complete transformation cannot occur
understood because potassium is in short supply. In
in order to geological settings where transformation
of smectite layers to illite layers has been
understand limited by the unavailability of potas-
and control sium, high-layer-charged smectite can
rheological diagenetically develop. This is the case
with Gulf Coast smectite clays. They
changes in will generally have a high-layer charge,
drilling and a higher portion of the charge will
fluids. arise in the tetrahedral layer which
should be more selective toward potas-
sium at lower temperatures. Therefore,
when potassium becomes available from
drilling mud, even seawater muds with
a high sodium-to-potassium ratio,
the conversion of high-layer-charged
smectite layers to illite layers will
occur. The effect of this reaction is
to stabilize the shale.
In some gumbo shales, the high-
layer-charged smectite layers coexist
with lower-layer-charged smectite lay-
ers. The low-layer-charged smectite
layers will not fix potassium and, in
cases where the potassium concentra-
tion is greatly exceeded by sodium,
will behave according to classical ion
exchange theory. Thus, increasing the
potassium-to-sodium ratio in the mud
will help saturate the low-layer-charged
smectite layers with potassium and
provide additional shale stabilization.
CLAY-PARTICLE-LINKING PROCESSES
In addition to knowing the amount
and quality of the clays in a mud, it is
necessary to know the state of associa-
tion of the clay particles. The various
linking processes of clay particles are
Clay Chemistry 4B.12
important to the rheology of clay sus-
pensions. These linking processes must
be understood in order to understand
and control rheological changes in
drilling fluids.
The thin flat, plate-like particles of
clay have two different surfaces. The
large face or planar surface is negatively
charged and the thin, edge surface is
positively charged where the lattice
is disrupted and a broken bond sur-
face exposed. These electrical charges
and exchangeable cations make up an
electrical force field around the clay par-
ticles that determines how these parti-
cles interact with one another. If the
exchangeable ions are dissociated from
the clay surface, the repelling force
between the flat negatively-charged
plates is large, and the plates will be
dispersed from one another. Complete
dispersion is rare and probably can only
occur in dilute suspensions of purified
sodium montmorillonite. Usually, some
degree of linking between particles occurs.
Clay particles associate in one of
the following states: aggregation,
dispersion, flocculation or defloc-
culation (see Figure 8). They can be
in one or more states of association
at the same time with one state of
association predominating.
Aggregation Flocculation
(face to face) (edge to face) (edge to edge)
Dispersion Deflocculation
Figure 8: Association of clays.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4B Clay Chemistry
…defloccu- Aggregation (face-to-face linking)
lating chemi- leads to the formation of thicker plates
or packets. This decreases the number
cals are often of particles and causes a decrease in the
referred to plastic viscosity. Aggregation can be
as mud caused by the introduction of divalent
cations to the drilling fluid, such as
thinners. Ca2+. This could occur from additions
of lime or gypsum or by the drilling of
anhydrite or cement. After an initial
increase, the viscosity will decrease
with time and temperature to some
value lower than it was originally.
Dispersion, the reverse of aggrega-
tion, leads to a greater number of parti-
cles and to higher plastic viscosities.
…yield of Clay platelets are normally aggregated
before they are hydrated and some dis-
clays is
persion takes place as they hydrate. The
defined as degree of dispersion depends on the
the number electrolyte content of the water, time,
of barrels of temperature, the exchangeable cations
on the clay and the clay concentration.
15-cP mud
Lower salinity, longer times, higher
that can be temperatures and lower hardness lead
obtained from to more dispersion. Even Wyoming
bentonite will not completely disperse
one ton of
in water at room temperature.
dry material. Flocculation refers to edge-to-edge
and/or edge-to-face association of par-
ticles, leading to the formation of a
“house of cards” structure. This causes
an increase in viscosity, gelation and
fluid loss. The severity of this increase
is a function of the forces acting on
the linked particles and the number
of particles available to be linked.
Anything that increases the repelling
forces between particles or shrinks
the adsorbed water film, such as the
addition of divalent cations or high
temperature, promotes flocculation.
Deflocculation is the dissociation
of flocculated particles. The addition of
Clay Chemistry 4B.13
certain chemicals to the mud neutralizes
the electrochemical charges on the
clays. This removes the attraction that
results in edge-to-edge and/or edge-to-
face bonding between clay particles.
Since deflocculation results in a reduc-
tion in viscosity, deflocculating chemi-
cals are often referred to as mud thinners.
Deflocculation also aids in allowing the
clay particles to lay flat in the filter cake
to reduce fluid loss.
YIELD OF CLAYS
The yield of clays is defined as the
number of barrels of 15-cP (centipoise)
mud that can be obtained from one
ton of dry material. Figure 9 illustrates
why 15 cP was chosen as the defining
value for yield. The critical part of the
curve for all types of clay appears at
15 cP. Large additions of clay up to
15 cP promotes little viscosity increase,
whereas, small amounts of clay have a
pronounced effect on viscosity above
15 cP. This is not only true with com-
mercial clays but for hydratable drill
solids as well. It is also relevant that
a 15-cP clay suspension will support
barite in weighted-mud systems.
This graph can be very useful to the
mud engineer. For a given viscosity of
the various clays, data relative to slurry
density, percent solids by weight, yield
in barrels-per-ton, percent solids by
volume and pounds solids per barrel
of mud may be obtained.
For example, about 20 lb/bbl of ben-
tonite (M-I GELT ) is required to produce
a 15-cP viscosity mud. From the graph,
then, it would contain 51⁄2% solids by
weight, yield 100 bbl/ton, have 21⁄2%
solids by volume and weigh about
8.6 lb/gal.
Revision No: A-1 / Revision Date: 02·28·01
CHAPTER

4B Clay Chemistry

Slurry density (lb/gal)

8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0

60
Specific gravity of solids = 2.4

M-I GELT
SALT GELT
50

e
ntonit
Sub-be
40
Viscosity (cP)

30

lay
ec
tiv
Na
20

10

0
0 5 10 15 20 25 30 35 40 45 50
Solids (% wt)

200 100 75 50 40 30 25 20 18 16 14 12 10 9 8
Yield (bbl/ton of 15-cP mud)

2 4 6 8 10 12 14 16 18 20 25 30
Solids (% vol)

10 20 30 40 50 75 100 150 200 250

Solids (lb/bbl)

Figure 9: Viscosity curves resulting from different clay solids.

The yield would be less if a clay takes be improved by utilizing high-quality
up less water. By comparison, if sub- Wyoming bentonite.
bentonite was used to produce a 15-cP M-I GELT and M-I GEL SUPREMEE are
viscosity mud, it would contain 18% both Wyoming bentonites. They differ
solids by weight, yield only 28 bbl/ton, in that M-I GELT is treated with very
have 81⁄2% solids by volume and would small amounts of polymer (peptized) to
weigh almost 9.4 lb/gal. increase its yield, while M-I GEL SUPREMEE
Clays have many applications in is a non-treated bentonite. M-I GELT
drilling muds. Increasing the viscosity meets API Specification 13A, Section 4
of a drilling mud may best be accom- “Bentonite” specifications. M-I GEL
plished with the least amount of solids SUPREMEE meets API Specification 13A,
by adding a clay which has the high- Section 5 “Non-Treated Bentonite” speci-
est yield (M-I GELT ). Lower fluid-loss fications. M-I also sells OCMA bentonite
values can be obtained with bentonite which meets API Specification 13A,
since coarse and medium-sized parti- Section 6 “OCMA Bentonite” specifica-
cles are normally produced from the tions. NOTE: OCMA is the acronym for Oil
formation. The quality of the mud will Companies Materials Association.
Clay Chemistry 4B.14 Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER

4B Clay Chemistry

FACTORS AFFECTING THE 30

YIELD OF CLAYS 25

Viscosity (cP)
Hydration and Hydration and dispersion of dry clay 20
Salt solution
dispersion of are greatly affected if the makeup 15
water contains salt or various metallic 10 Calcium solution
dry clay are ions. For example, many drilling 5
greatly muds are prepared with seawater for 0
0 50 100 150 200 250 300
affected if the economy and convenience. A typical Salt (mg/l x 1,000)
analysis of seawater might contain the 0 1.5 3.0 4.5 6.0 7.5 9.0
makeup water following components: Calcium (mg/l x 1,000)
contains salt
Parts per Million Figure 10: Viscosity effect when adding
or various Components (mg/l) bentonite to water containing various
metallic ions. Sodium 10,550 concentrations of salt or calcium.
Chloride 18,970
Sulfate 2,650
Magnesium 1,270
Calcium 400
Potassium 380
Bromine 65
Other components 80
NOTE: Brackish water could contain the same components,
but at different concentrations.

Water containing any salt concen-

tration can be saturated with an addi-
tional salt. Saturated saltwater contains
about 315,000 mg/l sodium chloride. Initial 72 hr later
Approximately 120 lb/bbl of salt is
required to saturate freshwater. Figure 11: Hydration of bentonite in freshwater.
Figure 10 shows the effect of various
concentrations of these ions upon the
hydration of bentonite. In general, it
…hydration can be stated that the hydration of
of freshwater freshwater clays decreases rapidly with
increasing concentrations of these ions.
clays decreases This phenomenon is more apparent
rapidly with in Figures 11 and 12. Demonstrated in
increasing these examples is the hydration of two
identical cubes of bentonite, the first
concentrations in freshwater and the second in salty
of these ions. water. Figure 11 shows the bentonite Initial 72 hr later

cube initially in a beaker of freshwater

and then again 72 hr later. Hydration
and consequent swelling is readily
apparent. Figure 12 shows the ben-
tonite cube initially in the salty water
and again 72 hr later. It is obvious that
little or no hydration has occurred.
Water containing calcium or magne-
sium is referred to as “hard” water. To
obtain more viscosity from the clay, one
Clay Chemistry
Figure 12: Hydration of bentonite in salty water.
practice is to “soften” the water with
soda ash and caustic soda to precipi-
tate calcium and magnesium. When
high chloride concentrations exist, the
only method of reducing the concen-
tration is by dilution with freshwater.
When the makeup water is salty,
SALT GELT (attapulgite) may be used
4B.15 Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER
4B Clay Chemistry
Figure 13: Photomicrograph of attapulgite particles.
…attapulgite for achieving viscosity. Attapulgite is
clay will a unique mineral. Its crystalline struc-
ture is needle-like as shown in Figure
build similar 12. Its ability to build viscosity is inde-
viscosity in pendent of the makeup water. At the
any type of same concentration, SALT GELT in any
type water would give about the same
makeup viscosity as M-I GELT in freshwater. The
water… ability to build viscosity does not depend
on hydration, but rather upon the
extent to which the bundles of needles
are sheared. The resultant viscosity is
created by two elements:
1. The formation of brush-heap struc-
tures by the shearing forces. A sim-
ple analogy would be similar to
straw stirred into water.
2. Attractive forces between particles
created by broken-bond charges on
the edges of needles broken by the
shearing force.
Since the attapulgite clay will build
similar viscosity in any type of makeup
1 3
⁄4 bbl of 30-lb/bbl + ⁄4 bbl of 100,000-mg/l
prehydrated bentonite slurry
Figure 14: Addition of prehydrated bentonite to saltwater.
Clay Chemistry 4B.16
water, a question might be “Why not
always use attapulgite?” The answer
would be (1) greater cost, (2) lack of
filtration control due to particle shape
and (3) rheology characteristics are
more difficult to control.
Bentonite can be used as an effective
viscosifier in saltwater if it is first prehy-
drated in freshwater then added to the
salty water. It is beneficial to maintain
a 9 to 10 pH and treat the prehydrated
bentonite slurry with a deflocculant
before adding it to the salty water.
In this way, the initial flocculation
followed by a loss of viscosity from
dehydration in the saltwater environ-
ment is reduced.
This is shown in Figure 14. A slurry
consisting of 30 lb/bbl bentonite was
prepared and allowed to hydrate. It
was then added to a barrel equivalent
of water having a concentration of
100,000 mg/l sodium chloride.
From this figure, it is obvious that
the clay is dispersed in the saltwater
and the rheological properties show
that the clay is performing its func-
tion. Much of this viscosity will be
eventually lost through dehydration
over time, but a portion will always
remain. The resultant viscosity will
always be substantially higher than
making an addition of dry clay
directly to the saltwater.
= 1 bbl slurry with properties
NaCl water AV = 47, PV = 15 and YP = 63
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER

4B Clay Chemistry

70 60

60 50

50 40

Viscosity (cP)
Viscosity (cP)
40 30

30 20

20 10

10 0
0 1 2 3 4 5 6
Salt (mg/l x 1,000)
0
0 1 2 3 4 5 6 Figure 16: Effect of salt on prehydrated bentonite.
Calcium x 100 (mg/l)

Figure 15: Effect of calcium on prehydrated bentonite.

An entirely different reaction occurs
when salt or calcium is added directly
to a bentonite slurry prepared and
hydrated in freshwater. Figures 15
and 16 demonstrate this reaction.
To be noted is the initial increase
and subsequent decrease in viscosity
previously discussed under clay
particle associations.
Figure 15 represents initial viscosity
increase due to flocculation caused by
the addition of the divalent cation Ca2+.
considerations, since pH does affect vis-
cosity, is selection of the most desirable
pH range for optimizing the rheologi-
cal properties of the drilling fluid. From
the graph it can be observed that the
viscosity of a bentonite suspension is
lowest in the pH range of 7 to 9.5. This
is one reason why most water-base
drilling fluids are run in this range.
Increased dispersion of clay results
when pH is above 9.5, increasing the
viscosity of the drilling fluid.
70

This in turn causes aggregation of the

particles and a viscosity decrease due 60

to dehydration and decreased number

…all drilling of particles. 50

muds… Figure 16 shows essentially the same

Viscosity (cP)

thing except that flocculation and the 40

should aggregation are caused by mass action of
have a pH the Na+ due to its high concentration. 30

above 7. EFFECT OF PH 20
It is relevant at this time to also con-
sider the effect of pH on the yield of 10
bentonite. Figure 17 illustrates the vis-
cosity of a bentonite slurry as the pH 0
is varied. Most all drilling muds are 0 2 4 6 8 10 12
pH
treated to be alkaline, i.e., they should
have a pH above 7. One of the primary Figure 17: Effect of pH on Wyoming bentonite.

Clay Chemistry 4B.17 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4B Clay Chemistry
In previous discussions, the emphasis
has been toward getting the most vis-
cosity from the smallest addition of
material. The significance of pH is that
the viscosity created by values above
10 is sometimes out of proportion to
Principles of Chemical Treatment
Viscosity is Viscosity is the result of frictional as
the result of well as electrical forces existing in a
mud system. As drilling progresses,
frictional as solids are incorporated into the drill-
well as elec- ing mud. They will be ground and
trical forces broken into very fine particles, caus-
ing an increase in the viscosity of the
existing in a mud, unless these solids are removed
mud system. from the system. Drilling various con-
taminants will also cause flocculation
and an increase in viscosity.
Evaluating the rheological properties
of the mud will enable the mud engi-
neer to quickly determine the cause
of trouble and the proper treatment
to reduce viscosity. Water is effective
for reducing viscosity if solids are
high, but it is not the most economi-
cal treatment if abnormal viscosity is
caused by chemical flocculation (as
indicated by a high yield point and
gels). There are organic and inorganic
anionic additives that can be used to
effectively reduce flocculation.
The primary effect of anionic viscosity-
reducing chemicals is believed to be a
neutralization of residual broken-bond
cationic charges. The mechanism of
this action in water-clay suspensions
is to reduce that portion of viscosity
due to attractive forces between the
particles without substantially affecting
Clay Chemistry 4B.18
what is considered to be desirable mud
properties. For obvious reasons, such
as safety and corrosion, drilling muds
are rarely operated in the acidic range
with a pH below 7.
that portion of viscosity due to hydra-
tion of the clay minerals. Anionic mate-
rials are adsorbed on the edges of the
clay particles to satisfy the residual
broken-bond cationic charges. Anionic-
charged chemicals commonly used for
the treatment of drilling mud include
phosphates, tannins, humic-acid lignins
(lignite), lignosulfonates and low-
molecular-weight synthetic polymers.
This adsorption changes the balance of
forces acting on the clay particle from
an attractive force (flocculation) to a
repulsive force (deflocculation). Instead
of being drawn together, the particles
repel or tend to avoid contact with
one another.
Chemical treating agents reduce
flocculation in clay-water drilling flu-
ids by one or more of the following
mechanisms.
1. Removing the contaminant
by precipitation.
2. Reducing the effects of the con-
taminant by complexing the
contaminate (sequestering).
3. Neutralizing flocculation by
satisfying cationic charges on
the clay particles.
4. Encapsulating or forming a protec-
tive film around the clay particle.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4B Clay Chemistry
PHOSPHATES
The two principal phosphates used in
drilling mud are:
1. Sodium Acid Pyrophosphate (SAPP)
pH of 4.8.
2. Sodium Tetraphosphate (STP or
PHOS) pH of 8.0.
…phosphates These phosphates are powerful
are powerful anionic dispersants and only a small
treatment will produce maximum vis-
anionic cosity reduction. The amount of treat-
dispersants… ment for simple dispersion rarely
exceeds 0.2 lb/bbl. This means that for
a 1,000-bbl system, only 200 lb would
be required to thin the fluid. The phos-
phates can be added directly through
the hopper or from the chemical barrel.
If added from the chemical barrel,
approximately 50 lb of phosphate is
mixed with a barrel of water. The solu-
tion is then added directly to the mud
uniformly over one circulation.
Phosphates Phosphates are used principally in
are used low-pH muds and spud muds. They
lower viscosity in two ways: (1) they
principally neutralize attractive forces by being
in low-pH adsorbed on the surface of solids, and
muds and (2) they remove calcium and magne-
sium. The low pH of SAPP and its
spud muds. ability to remove calcium makes it an
excellent treating agent for cement
contamination. The phosphates are
seldom used by themselves in mud
treatment; rather, they are used to
supplement control along with caus-
tic soda and an organic thinner. If
SAPP (pH of 4.8) were used continu-
ously by itself, the mud would even-
tually become acidic. This could be
detrimental and lead to severe corro-
sion and excessive viscosity. PHOS
Clay Chemistry 4B.19
has a more neutral pH (8.0) that
makes it more applicable for routine
mud-thinning treatments.
The application of phosphates for
treatment is limited. The materials are
not effective mud thinners at moderate
temperatures. If the mud temperature
is much in excess of 175°F (79.4°C), the
phosphates revert to orthophosphates.
As orthophosphates, they may become
flocculants rather than deflocculants.
This does not rule out the application
of phosphates for sequestering calcium
at higher temperatures. As orthophos-
phates, they still have the ability to
decrease calcium, although their thin-
ning power is decreased. The phos-
phates also do not perform effectively
at higher salt concentrations.
LIGNITE
The basic lignite used for viscosity con-
trol is TANNATHINT (pH 3.2). Lignite is less
soluble at low pH, so to be effective the
pH of the mud must be in the alkaline
range or the lignite must be presolubi-
lized in a high-pH slurry before being
added to the mud system. Caustic soda
is usually added with low-pH lignite
additives. In field use, the ratio of caus-
tic soda to TANNATHINT will range from
1:6 to 1:2. The lignins are best added
through the mud hopper. TANNATHINT
performs best in mud systems with
pH values that range from 9 to 10.5.
CAUSTILIGT is a causticized lignite
that has a pH of about 9.5. K-17E is
a potassium hydroxide-neutralized
lignite with a pH of about 9.5.
XP-20KE (pH 10) is a prereacted chrome
lignite used primarily in conjunction
with SPERSENEE (chrome lignosulfonate).
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER
4B Clay Chemistry
It complements the performance
of SPERSENEE in M-I’s Chrome
Lignosulfonate System (CLS or
SPERSENEE/XP-20KE system). As an
integral part of the SPERSENEE/XP-20KE
mud system, XP-20KE is a drilling-
fluid stabilizer and emulsifier. It
decreases fluid loss and contributes to
the inhibitive properties of the mud.
It is the primary thermal stabilizer in
the high-temperature DURATHERME sys-
tem. The application of XP-20KE is
not limited to SPERSENEE/XP-20KE and
DURATHERME systems, and can be used
in a wide variety of deflocculated
water-base systems for fluid-loss con-
Lignite trol, thinning and increased thermal
stability.
additives
Lignite additives help form oil-in-
help form water emulsions and are generally not
oil-in-water effective at high calcium concentration.
They are only moderately effective at
emulsions…
higher salt concentrations.
LIGNINS
Lignins are a group of products similar
to lignite and lignosulfonate that come
from chemically-treated tree bark.
Quebracho is a lignin/lignite blend
designed to provide thinning and fluid-
loss control. In general, tannin products
are more soluble than alternative chem-
icals in lower-pH muds. They are more
effective at lower temperatures and
Clay Chemistry 4B.20
high-salinity environments as compared
to lignite-base additives. Tannins are
usually more expensive and provide a
shorter-term effect as compared to
both lignite and lignosulfonate. Desco,
from Drilling Specialties Co., a chrome
lignin, and Desco CF, a chrome-free
lignin, are widely used as thinners.
LIGNOSULFONATES
The lignosulfonates include SPERSENEE ,
a chrome lignosulfonate; SPERSENE CF,T
a chrome-free lignosulfonate; and
SPERSENEE I, a ferro-chrome lignosul-
fonate. These additives are versatile
materials that have wide applications
in many deflocculated water-base sys-
tems. They work well at all levels of
alkaline pH, can be used at elevated
salt levels and are effective in the
presence of higher calcium levels.
Lignosulfonate additives have a low
pH (about 3.0). For this reason, caustic
soda should be added along with all
SPERSENEE treatments. The amount of
caustic will vary according to the type
mud being run, but usually at one
part caustic for four parts SPERSENEE
. It
not only reduces viscosity and gel
strength, but when used in sufficient
quantities, it reduces water loss and
provides an inhibitive environment.
Additions of SPERSENEE are generally
made through the mixing hopper.
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER
4B Clay Chemistry
APPLICATION
Figure 18 demonstrates the changes of
viscosity that occur when plastic viscos-
ity and yield-point values are altered by
chemical contamination and treatment.
The data can be analyzed to determine
the effect on both the funnel viscosity
and apparent viscosity by varying mate-
rial additions to promote changes, then
interpreting the rheological values.
Whether measured in seconds/quart
with the funnel or in cP with the vis-
cometer, the apparent viscosity is com-
posed of two components: (1) solids
content and nature of these solids, and
(2) the electro-chemical attraction
between the solids.
As contaminants are introduced and/
or the solids content is increased, the
viscosity increases. If the Marsh-funnel
viscosity increases, then the apparent
viscosity will usually increase. It is also
true that if one decreases, the other
will usually decrease. However, if only
the apparent viscosity were measured,
this value is of little use for mud con-
Plastic trol. Plastic viscosity, yield point and gel
strengths are the important factors. Plastic
viscosity,
viscosity is more of a measure of the
yield point structural viscosity that is determined
and gel by the solids concentration. Yield point
and gels are more a measure of clay
strengths
hydration and flocculation. Yield points
are the and gels in clay free xanthan polymer
important muds are less affected by normal conta-
mination, flocculation/deflocculation
factors.
and anionic chemical thinning.
Clay Chemistry 4B.21
The principles of chemical treatment
in a clay-water fluid are shown in
Figure 18:
1. Introducing 1⁄2 lb/bbl of cement
caused flocculation to occur due
primarily to calcium contamina-
tion. Both the funnel viscosity
and the apparent viscosity increase.
Examination of the graph reveals
that this viscosity change was
brought about by increasing the
yield point (increased attractive
forces or flocculation). Little or no
change was experienced in plastic
viscosity because plastic viscosity is
due primarily to solids.
2. Ten % water was added to demon-
strate that water has little effect on
reducing yield point (flocculation).
Water does not remove calcium,
which is the cause of flocculation
or high attractive forces. Water can
only increase the separation of the
solids, but does not change the
association of the clays or alter
yield point.
3. The addition of 1 lb/bbl of PHOS
(for removing calcium) produces a
tremendous decrease in both the
funnel and apparent viscosity. This
was brought about by lowering the
yield point. The yield point was
reduced because PHOS reduces cal-
cium and deflocculates the clay par-
ticles. It is also shown that this
addition of chemical had little or
no effect upon plastic viscosity.
Revision No: A-0 / Revision Date: 03·31·98
CHAPTER

4B Clay Chemistry

120

Funnel viscosity (sec/qt)

100

scosity

80
Funnel vi

60

80
Apparent viscosity
Plastic viscosity
AV, PV and YP (cP or lb/100 ft2)

60

40

Yield point

20

A B C D E F G H I
0
Base 10% 200 10% 1/4
mud water lb/bbl water lb/bbl
M-I BART PHOS
1/2 1 1/4 1/4 10%
lb/bbl lb/bbl lb/bbl lb/bbl water
cement PHOS PHOS cement +
10 lb/bbl
clay

Figure 18: Principles of chemical treatment.

Clay Chemistry 4B.22 Revision No: A-1 / Revision Date: 02·28·01

 CHAPTER

4B Clay Chemistry

_______________________ 4. The second viscosity increase (Part
_______________________ D) was caused by the addition of
200 lb/bbl of barite (inert solids) to
_______________________
increase mud weight. The apparent
_______________________ viscosity change is almost the same as
_______________________ before, but for an entirely different
reason. This viscosity change resulted
_______________________
from raising plastic viscosity. The
_______________________ addition of more solids increased
_______________________ the friction between solids because
_______________________
the total surface area of the solids
increased. Yield point increased only
_______________________ slightly because the solids are closer
_______________________ together. Any attractive force will
_______________________
be more effective because the dis-
tance between particles is reduced.
_______________________
However, the funnel and apparent
_______________________ viscosity increased primarily because
_______________________ of increased plastic viscosity. The cor-
rect mud treatment here would be to
add water.
5. 1⁄4 lb/bbl of PHOS was added to
demonstrate that a slight reduction
in viscosity can be obtained by lower-
ing the yield point, and to also show
that chemical treatment alone will
not reduce high viscosity from solids.
Viscosity remained high even after
the treatment.
6. Adding water is the correct treatment
to reduce viscosity. Ten % by volume
water was added and the plastic vis-
cosity was reduced. Both the funnel
and apparent viscosities decreased
significantly because they are a func-
tion of plastic viscosity. The yield
point decreased only slightly.
7. Adding both a chemical contaminant
and reactive solids causes the third
viscosity increase, increasing both
yield point and plastic viscosity. The
1 both of the above.
⁄4 lb/bbl of cement increased the yield
point as in Part A. Plastic viscosity
was increased by adding 10 lb/bbl of
clay for the same reason as the viscos-
ity increased in Part D by the intro-
duction of solids. There is, however,
one great difference. The clay solids
hydrate and take up water. With less
free water available, the friction is
increased considerably with only a
small amount of solids. For a unit vol-
ume of solids, hydratable drill solids
will always increase viscosity more
than inert solids. The correct treat-
ment here is the addition of both
chemical thinners and water for dilu-
tion to lower both plastic viscosity
and yield point.
8. Addition of chemicals lowered
viscosity for the same reason as
in Part C.
9. Addition of water lowered viscosity
for the same reason as in Part F.
The following generalization can be
made for the most economic control
of flow properties to obtain optimum
conditions:
1. An increasing yield point, accompa-
nied by little or no changes in the
plastic viscosity, may be reduced or
controlled by the addition of chem-
ical thinners in a clay-water system.
2. An increasing plastic viscosity,
accompanied by little or no changes
in yield point, may be reduced or
controlled by water or the use of
mechanical solids-control equipment
to discard undesirable solids.
3. Simultaneous large increases in
both yield point and plastic viscos-
ity can be reduced or controlled by

Clay Chemistry 4B.23 Revision No: A-0 / Revision Date: 03·31·98

 CHAPTER
4C Contamination and Treatment
Introduction
A contami- A contaminant is any type material
nant is (solid, liquid or gas) that has a detrimen-
tal effect on the physical or chemical
any type characteristics of a drilling fluid. What
material… constitutes a contaminant in one type
that has a of drilling fluid may not necessarily be
a contaminant in another.
detrimental Low-gravity, reactive solids are conta-
effect on the minants all drilling fluids have in com-
physical or mon. These solids consist of drilled
solids incorporated into the system or
chemical through over-treatment with commer-
characteristics cial clays. Economically, drilled solids
of a drilling and the problems associated with their
fluid. control have greater impact on mud
costs than other type of contamina-
tion. However, the primary focus here
is on the following common chemical
contaminants of water-base muds:
1. Anhydrite (CaSO4) or gypsum
(CaSO4•2H2O).
2. Cement (complex silicate of
Ca(OH)2).
3. Salt (rock salt, makeup water, seawa-
ter, magnesium, calcium and sodium
chloride, and connate water).
4. Acid gases, including carbon dioxide
(CO2) and hydrogen sulfide (H2S).
With the exception of the acid
gases, these chemical contaminants
are directly related to ion exchange
reactions with clays. Therefore, the
concentration of the clay-type solids
in a water-base mud has a direct rela-
tionship on how severely the chemical
contaminant affects the mud properties.
The Methylene Blue Capacity (MBC) is a
good indication of the concentration of
clay-type solids. Muds with MBC levels
below 15 lb/bbl are less affected by
chemical contamination.
An ion exchange reaction can occur
when sodium bentonite is exposed to
chemical environments containing
high concentrations of other metallic
Contamination and Treatment 4C.1
ions, initially flocculating, then possibly
chemically converting the bentonite
to a lower-yielding clay. This affects
the amount of adsorbed water and the
size, shape and association of particles,
resulting in unstable rheology and
fluid-loss control.
The severity of these contaminants
made it necessary to develop mud sys-
tems that could tolerate them. These
systems include lignosulfonate muds,
low-colloid polymer muds, lime muds,
gyp muds and salt muds. Many of these
systems are deliberately pretreated with
lignosulfonate, salt (sodium chloride)
and calcium-containing materials such
as lime or gypsum. Therefore, when
additional concentrations of these cont-
aminants are encountered, they have
minimal effect on the systems.
The primary purposes of this
chapter are:
• To reveal the source(s) of each
chemical contaminant.
• To describe how each affects mud
properties.
• To describe how to use mud property
changes to identify the contaminant.
• To describe how to treat the mud to
restore the original properties.
Since changes in physical mud prop-
erties such as increased rheology and
fluid loss due to flocculation are similar
regardless of which chemical contami-
nant is present, the changes in physical
properties indicate only that a contami-
nant exists. An analysis of the changes
in chemical properties is necessary to
identify the contaminant. Therefore, the
sources, effects and treatment options
of each chemical contaminant are dis-
cussed in detail. A quick-reference guide
and tables, in metric and English units,
are included at the end of the chapter
(see Tables 2, 3 and 4).
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4C Contamination and Treatment
Anhydrite or Gypsum Contamination
There are few areas in the world where
anhydrite or gypsum is not drilled.
Anhydrite Anhydrite and gypsum are both calcium
and gypsum sulfate and nearly identical in chemical
composition. Gypsum (CaSO4•2H2O),
are both with its attached water, is more soluble
calcium than anhydrite (CaSO4). The severity of
sulfate this contaminant depends primarily on
the amount drilled. If only a small
and nearly amount of a contaminant is encoun-
identical in tered, it can be tolerated by precipitat-
chemical ing the calcium ion. If large amounts
are encountered, the mud system
composition. should be converted to a calcium-base
system. Both lime and gyp-base calcium
systems can tolerate anhydrite or gyp-
sum contamination without adversely
affecting the mud properties.
The initial effect of calcium conta-
mination on a bentonite-base mud
system is high viscosity, high gel
strengths and increased fluid loss.
The extent to which these properties
are affected is a function of concen-
tration of the contaminant, the con-
centration of reactive solids and the
concentration of chemical defloccu-
lants in the drilling fluid.
As shown below, when calcium sul-
fate solubilizes in water, it ionizes into
calcium and sulfate ions.
CaSO4 Ca2+ + SO42–
The solubility The solubility of CaSO4 is con-
of CaSO4 is trolled by pH, salinity and tempera-
ture. Increased pH and temperature
controlled decreases the solubility of gyp while
by pH,
increased mud chlorides increases
salinity and the solubility. The solubility of cal-
cium sulfate is reversible and will
temperature. reach some level of equilibrium
with the chemical environment.
Contamination and Treatment 4C.2
DETECTION FACTORS
The first indication of anhydrite or
gypsum contamination is an increase
in physical properties, including funnel
viscosity, yield point and gel strengths.
Chemical tests must be performed to
identify which chemical contaminant is
present since the increase in these phys-
ical properties is also the first indication
of other types of chemical contamina-
tion. The main indications of gyp or
anhydrite contamination include:
1. An increase in filtrate calcium. This
may not be apparent initially if there
is an excess of carbonate, bicarbon-
ate or phosphate ions present in the
mud, or if the pH of the mud system
is being increased. But when the solu-
bilized gyp depletes these chemicals,
a reduction in pH occurs because the
pH of gyp (6 to 6.5) is very low. This
reduction in pH will result in a large
increase in filtrate calcium, since the
solubility of calcium is inversely
proportional to pH.
2. Reduction of the pH and alkalinity,
and an increase in filtrate calcium,
are the most reliable indicators.
3. Due to the relatively limited solu-
bility of anhydrite and gypsum,
cuttings may contain traces of the
mineral. Many times, this is evi-
denced by the presence of small,
white, mushy balls of acid-soluble
material on the cuttings.
4. The qualitative test for the sulfate ion
should indicate an increase. However,
this test also detects the sulfonate ion.
The test is meaningless if lignosul-
fonate is used as the primary defloc-
culant unless a comparison is made
with uncontaminated mud.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4C Contamination and Treatment
TOLERATING THE CONTAMINANT
Treating the mud for
_______________________ gyp/anhydrite contamination:
1. Increase the concentration of defloc-
_______________________
culant in the system. Lignosulfonate
_______________________ and lignite are both effective defloc-
_______________________ culants in the presence of calcium.
This treatment may be sufficient,
_______________________
depending on the amount of anhy-
_______________________
drite or gypsum drilled. Lignite
_______________________ chelates the calcium ion, thereby
removing it. If there is too much
_______________________
calcium, soda ash (Na2CO3) may be
_______________________
required to precipitate it out.
_______________________ 2. The pH must be maintained in the
_______________________ range of 9.5 to 10.5 with caustic soda
(NaOH) or caustic potash (KOH). This
_______________________
pH range limits the solubility of gyp
_______________________ and enhances the performance of
_______________________ the lignosulfonate.
3. Any one of the following chemicals
_______________________
may precipitate an increase in fil-
trate calcium. Precipitating the cal-
cium with a source of carbonate
ions is extremely effective. Due to
the low pH of anhydrite/gyp (6 to
6.5), soda ash is the preferred car-
bonate because it has a higher pH
(11 to 11.4) than bicarbonate of
soda (8 to 8.5). When soda ash is
mixed in water, the pH increases
due to the formation of a hydroxyl
ion, as shown:
2Na2CO3 + H2O
HCO3 + CO3 + 4Na+ + OH– (pH <11.3)
If calcium ions are present, they are
precipitated as insoluble CaCO3 (lime-
stone). This is the reaction of soda ash
and gypsum:
Na2CO3 + CaSO4
Na2SO4 + CaCO3 (pH >11.3)
Contamination and Treatment 4C.3
A similar reaction occurs when
sodium bicarbonate is used as the pre-
cipitant. By-products of the reaction
are chemical compounds such as cal-
cium bicarbonate (Ca(HCO3)2), a highly
soluble material (depending on the pH).
With additional caustic soda to main-
tain the pH above 9.7, the bicarbonate
ion converts to carbonate. It then reacts
with the filtrate calcium to precipitate
CaCO3. However, the interim period
during which the bicarbonate ion is
present can create problems almost
as serious as the contamination itself.
Therefore, soda ash is preferred over
sodium bicarbonate. Do not over-treat
with soda ash or bicarbonate. Use
Table 2 to calculate the amount of
additive needed.
Phosphates also have the ability to
complex filtrate calcium. This reaction
produces an insoluble calcium phos-
phate. Common available materials
of this type are:
Sodium Acid Pyrophosphate (SAPP)
– Na2H2P2O7 (pH 4.8)
Sodium Tetraphosphate (STP or
PHOS) – Na6P4O13 (pH 8.0)
Phosphates are limited by their
relatively low temperature stability
(approximately 200°F). They convert
to orthophosphates above this temper-
ature. As such, they are not effective as
deflocculants but are still capable of
removing calcium. However, soda ash
is the preferred product for treating
out calcium from anhydrite or gyp at
temperatures above 200°F.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4C Contamination and Treatment
CONVERTING THE SYSTEM
TO A CALCIUM-BASE SYSTEM
When massive sections of anhydrite
or gypsum are drilled, the amount
of contamination makes it virtually
…add cal- impossible to maintain desirable
cium sulfate flow properties and fluid-loss control.
Therefore, it is necessary to add cal-
to convert cium sulfate to convert the system
the system to a calcium-base mud system.
to a calcium- The mud may be converted to a gyp
mud by treating with caustic soda, lig-
base mud
nosulfonate and additional gypsum. A
system. gyp mud is a low-pH system, but large
amounts of caustic soda are required to
maintain the pH in the desired range of
9.5 to 10.5. A viscosity hump (increase)
will occur as the additional gyp is
added, but with proper water, caustic
and lignosulfonate additions, the mud
will break over after one circulation,
and the viscosity will decrease. Gypsum
is added until it has no detrimental
effect on the mud properties and then
maintained in excess (5 to 8 lb/bbl) to
feed the chemical reactions occurring.
Typical calcium levels range from 600
Cement Contamination
The probability of drilling cement
exists on every well drilled. The only
circumstances under which cement is
not a contaminant is when clear water,
brines, calcium-base muds and oil-base
muds are used, or when the cement is
well cured. The most widely used mud
…cement can system is the low-pH bentonite system.
have very In this case, cement can have very
detrimental detrimental effects on the mud proper-
effects on ties. The severity of the contaminant
depends on factors such as previous
the mud chemical treatment, solids type and
properties. concentration, the amount of cement
Contamination and Treatment 4C.4
to 1,200 mg/l in a gyp mud, depending
on the pH.
The mud may also be converted to
a lime mud by applying the chemical
treatment just outlined. To convert to
a lime mud, additional lime is added
instead of gypsum and is maintained
in excess. To maintain lime in excess,
most of the lime must remain insolu-
ble. Therefore, the pH of the lime mud
must be controlled in excess of 11.5 by
additions of caustic soda and lime. The
caustic soda reacts with the calcium
sulfate to produce additional lime as
shown by the following equation:
2NaOH + CaSO4
Ca(OH)2 + Na2SO4
The resulting lime-treated mud
requires an abnormal amount of caus-
tic soda to maintain excess lime if large
amounts of anhydrite or gypsum are
drilled. Therefore, a gyp mud is usually
preferred. Both muds require the addi-
tion of a fluid-loss control agent that
is not too calcium sensitive such as
POLYPAC T R, POLY-SALE, RESINEX,T etc.
drilled, and the extent to which it has
cured in the hole. Keep in mind that
bulk barite is occasionally contami-
nated with cement during transporta-
tion or at the rig and can cause severe
cement contamination, even when it’s
not expected.
The initial effect of cement conta-
mination is high viscosity, high gel
strengths and loss of fluid-loss con-
trol. This is the result of an increase
in the pH and the adsorption of the
calcium ion onto the clay particles,
causing flocculation.
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER
4C Contamination and Treatment
Cement is a complex silicate of lime,
Ca(OH)2. When solubilized in water
or the water phase of a drilling fluid,
an abundance of hydroxyl ions (OH–)
is produced.
Ca(OH)2 Ca2+ + 20H– (pH <11.7)
The above reaction is reversible
and represents an equilibrium
between the concentration of cement
and the pH of the mud. The solubility
of lime decreases as the pH of the
mud increases. When the pH exceeds
11.7, lime is precipitated from solu-
tion. Therefore, the lime becomes
practically insoluble at a pH greater
than 11.7 and provides an excess or
reserve of unreacted lime due to the
undissolved cement.
The primary indication of cement
contamination is a substantial increase
in pH, Pm and in the calculated excess
lime content as measured by the Pm
and Pf.
If the amount of cement drilled is rela-
tively small, there is little problem. The
contaminated mud can be disposed of
at the shaker or it can be treated with
Cement con- deflocculants and precipitants. The stage
of the drilling operation is significant
tamination
when treating cement contamination.
at high… Minor contamination can be effectively
(BHT) must treated to leave a satisfactory fluid in the
hole as a packer fluid, but in many cases
be treated
insufficient time is taken to properly
quickly and condition the mud. Cement contamina-
totally… tion at high Bottom-Hole Temperatures
(BHT) must be treated quickly and
totally to avoid high-temperature
gelation or solidification.
The following options should be
considered when a large amount of
cement is drilled:
1. If the drilling operation is at an inter-
mediate or final stage, using water
rather than the drilling mud to drill
Contamination and Treatment 4C.5
the cement should be considered.
This can only be done when the
cement is in a hole that is fully cased
and there is no communication of
pressure through the cement.
2. If the drilling mud must be used, the
resulting contamination problems
can usually be resolved if the drill-
ing operation is at an intermediate
stage. There is usually adequate time
remaining at this stage of the opera-
tion for treatment and gradual dilu-
tion to properly condition the mud.
3. If the well is in the completion stage,
sufficient time should be allotted to
properly treat the cement contami-
nation, or a gelation problem could
develop. If a lime mud is used as the
packer fluid, the mud could simply
be treated with deflocculants and
dilution.
The effect of pH on the solubility of
the cement makes treatment with pre-
cipitants difficult unless there is time
for dilution and reduction of the pH.
The hydroxyl ions produced by the
cement increases the pH, rendering the
calcium (cement) insoluble. Therefore,
a severely contaminated mud may typi-
cally have low flow properties due to
the calcium ion exchange reaction,
high pH, high alkalinity, high Pm, low
filtrate calcium and generally high fluid
loss, depending on the chemical con-
centration of the mud. Caution should
always be exercised when treating
cement-contaminated mud. Low flow
properties derived from tests made at
low temperatures may not reflect the
condition of the mud at the bottom of
the hole, especially at bottom-hole tem-
peratures above 275°F. High-temperature
gelation can be a serious problem with
cement-contaminated muds.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4C Contamination and Treatment

TOLERATING THE CONTAMINANT 3. Available filtrate calcium may be pre-

Treating the drilling fluid
_______________________ for cement contamination:
_______________________ 1. Increase the concentration of defloc-
culants in the system. Lignosulfonate
_______________________
and lignite perform well in the pres-
_______________________
ence of calcium over a broad pH
_______________________ range. If additional fluid-loss control
is desired, TANNATHIN,T RESINEXT and
_______________________
XP-20KE are very effective in a high-
_______________________
calcium environment. Most cement
_______________________ contamination problems can be ade-
quately tolerated in this manner.
_______________________
However, if an excessive amount of
_______________________
cement is drilled, the mud can be
_______________________ converted to a low-lime system if
temperatures allow.
_______________________
2. Cement increases alkalinity when it
_______________________
becomes soluble. Therefore, it is not
_______________________ necessary to add caustic soda with
_______________________ the deflocculants. The low pH of
deflocculants such as lignite and
SAPP offset some of the hydroxyl
ions generated by the cement. This
aids in reducing the pH and Pm,
which increases the solubility of
the cement (and calcium), allowing
precipitation.
cipitated with bicarbonate of soda or
SAPP. There are different opinions as
to which of these is the most effec-
tive, but sodium bicarbonate reduces
pH and Pm just as SAPP does.
4. If cement is drilled with a poly-
mer system, the polymers will be
hydrolyzed by the high pH and
precipitated by the calcium (Ca)
(see Figures 1 and 2). Therefore, it
is necessary to reduce the pH and
precipitate the calcium (Ca2+) out
as soon as possible.
5. In this case citric acid (H3C6H5O7)
is the additive to use. It precipitates
cement as calcium citrate and reduces
the pH. Treating with citric acid:
2(H3C6H5O7 •H2O) + 3Ca(OH)2 →
Ca3(C6H5O7)2 ↓ + 8H2O
6. Using solids-removal equipment to
discard the fine particles of cement
is another method to reduce the
contamination. This removes the
cement before it can be dissolved
at a lower pH.

CH2 CH2 CH2 CH2 CH2 CH2

CH CH CH CH CH CH
+2NH3
+2OH–
C C C C C C

O NH2 O NH2 O O– O O– O O– O O–

Figure 1: Hydrolysis of polyacrylamide into polyacrylate at high pH, liberating ammonia gas.

CH2 CH2 CH2 CH2 CH2 CH2

CH CH CH CH CH CH

+Ca2+
C C C C C C

O O– O O– O O– O O– O O Ca OO

Figure 2: Precipitation of polyacrylate by calcium.

Contamination and Treatment 4C.6 Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER
4C Contamination and Treatment
Sodium bicarbonate is an excellent
treating agent for cement contamina-
Phosphates tion as it precipitates calcium and
effectively reduces pH. Depending on the pH of
the fluid, sodium bicarbonate forms
remove carbonate (CO32–) and bicarbonate
calcium (HCO3–) ions which will precipitate
and aid in calcium to form calcium carbonate
(limestone) as shown below:
deflocculating
NaHCO3 + Ca(OH)2 →
the contami- NaOH + H2O + CaCO3 ↓
nated fluid. The use of bicarbonate reduces the
pH. This is the result of the reaction
of HCO3 with the NaOH required to
convert the HCO3 to CO3.
When using bicarbonate of soda,
the objective is to provide a source
If a massive of carbonate and bicarbonate ions to
combine with the excess lime and cal-
amount of cium ions. A frequent problem associ-
cement must ated with this method of treatment is
be drilled, over-treatment with carbonate mater-
ial. If carbonates are present in excess
then some of that required to precipitate the cal-
form of cium, mud problems associated with
acid will be the carbonates is possible. It is often
better to undertreat cement contami-
required… nation initially, then observe the
results before additional treatments.
Carbonate Contamination
Chemical contamination from soluble
carbonates is one of the most misun-
derstood and complicated concepts in
drilling-fluid chemistry. Carbonate/
bicarbonate contamination usually
results in high flow line viscosity,
Contamination and Treatment 4C.7
Another approach to treating
cement is the use of SAPP (phos-
phate). Phosphates effectively remove
calcium and aid in deflocculating the
contaminated fluid. The commonly
used phosphates convert to ortho-
phosphates above temperatures of
±200°F. They are no longer effective
as deflocculants in this form, but still
remove calcium effectively.
An additional benefit in using phos-
phates is pH, Pf and Pm reduction. SAPP
has a pH of 4.8 and PHOS has a pH of
8.0. Another benefit is that there are no
harmful by-products resulting from this
reaction that can create other mud
problems. SAPP is preferred if the Pm
needs considerable reduction.
If a massive amount of cement must
be drilled, then some form of acid will
be required. Even if bicarbonate is used
to remove all calcium and excess lime,
a undesirably high pH often results.
In these cases, citric acid, SAPP, acetic
acid or a low-pH lignite or lignosul-
fonate must be used in combination
with bicarb.
NOTE: Soda ash should not be used
to treat cement contamination due to
its high pH.
high yield point and progressive gel
strengths, and could result in solidi-
fication of the mud. These increases
in viscosity occur as the carbonates
and/or bicarbonates flocculate the
clay-type solids in the mud.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4C Contamination and Treatment
_______________________ The source of carbonates and
_______________________ bicarbonates are:
1. Carbon dioxide (CO2) from the air
_______________________
is incorporated into the mud through
_______________________ mud mixers in the pits and through
_______________________ mud mixing and solids-removal
equipment discharges. As the CO2
_______________________
dissolves, it becomes carbonic acid
_______________________ (H2CO3) and is converted to bicarbon-
_______________________ ates (HCO3) and/or carbonates (CO3)
_______________________
depending on the pH of the mud.
2. Over-treatment with soda ash or
_______________________ bicarbonate of soda when treating
_______________________ cement or gyp contamination.
_______________________
3. CO2 gas intruding from the
formation and formation water.
_______________________
4. Bicarbonates and/or carbonates
_______________________ from by-products of the thermal
_______________________ degradation of lignosulfonate and
lignite at temperatures above 325°F.
5. Some impure barite contains
carbonate/bicarbonate ions.
The following chemical equations
illustrate how CO2 dissolves to form
carbonic acid (H2CO3) and is con-
verted to bicarbonates (HCO3) and/or
carbonates (CO3) depending on the
pH of the mud. These equations
show that the chemical reactions
are reversible as a function of pH.
Therefore, CO3 can revert back to
HCO3 or even CO2 if the pH is
allowed to decrease.
CO2 + H2O H2CO3
– if carbonate ions exist, not only must
H2CO3 + OH HCO3– + H2O and
HCO3– OH– CO32– + H2O
This is also illustrated graphically in
Figure 3 which shows the distribution
of carbonic acid (H2CO3), bicarbonate
(HCO3) and carbonates (CO3) vs. pH.
Contamination and Treatment 4C.8
100
H2CO3 CO32 -
80
HCO3-
Percent
60 Increasing salinity
40 shifts curves to
the left.
20
HCO3- HCO3-
0
0 2 4 6 8 10 12 14
pH
Figure 3: Carbonate-bicarbonate equilibrium.
USING CHEMICAL ANALYSIS TO IDENTIFY
CARBONATE/BICARBONATE CONTAMINANT
The pH/Pf method of carbonate/bicar-
bonate analysis is based on the amount
(ml) of 0.02 N sulfuric acid (H2SO4)
required to reduce the pH of a mud fil-
trate sample from an existing pH to an
8.3 pH. This covers the pH range in
which hydroxyls and carbonates exist.
Table 1 shows that if no carbonates
exist, very little caustic soda is required
to achieve typical pH ranges of drill-
ing fluids, and that the corresponding
Pf is also low. As examples, 10 pH,
0.0014 lb/bbl caustic soda and 0.005 Pf
or 11 pH, 0.014 lb/bbl caustic soda and
0.05 Pf. The Pf is low because the con-
centration of OH ions (caustic soda)
is low. A very small concentration of
hydrogen (H) ions from the sulfuric
acid (H2SO4) is required to convert the
OH ions to water (HOH) and reduce the
pH to 8.3, (the Pf end point). However,
the OH– ions be neutralized as above,
but each carbonate ion must be con-
verted to a bicarbonate ion by the addi-
tion of 0.02 N sulfuric acid to reach the
Pf end point of 8.3 pH. This makes the
Pf higher (for an equivalent pH) in a
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4C Contamination and Treatment
filtrate that contains carbonates com-
pared to a filtrate that does not. This
difference in the Pf where carbonates
exist compared to the Pf where no car-
bonates exist, and a pH measurement
of the concentration of hydroxyls
makes it possible to calculate the con-
centration of carbonates and bicar-
Once the bonates. Once the concentration of
concentration carbonates is known, the concentra-
tion of calcium required to precipitate
of carbonates it out can be calculated.
is known, the
NaOH Pf
concentration pH (lb/bbl) (cc 0.02N H2SO4) (ppm)
of calcium 7 0.0000014 0.000005
8 0.000014 0.00005
required to 9 0.00014 0.0005
precipitate it 10 0.0014 0.005
11 0.014 0.05
out can be 12 0.14 0.5
calculated. 13 1.4 5 1,700
14 14 50
Table 1: Relationship of pH and alkalinity for pure water.
The Pf/Mf method of carbonate/bicar-
bonate analysis is based on the amount
(ml) of 0.02 N sulfuric acid required to
reduce the pH of a mud filtrate sample
from an existing pH to an 8.3 pH and
a 4.3 pH, respectively. This range also
covers the pH range in which carbon-
ates, bicarbonates and carbonic acid,
exist. As discussed above, if no carbon-
ates exist, very little caustic soda is
required to achieve typical pH ranges
of drilling fluids and that the corre-
sponding Pf and Mf values are low.
However, if carbonate/bicarbonate ions
exist, not only must the hydroxyl ions
be neutralized, but each carbonate ion
must be converted to a bicarbonate
ion by the sulfuric acid to reach the Pf
end point of 8.3 pH. This makes the Pf
higher for an equivalent pH where car-
bonate/bicarbonate ions exist compared
to a mud with no carbonate/bicarbon-
ate ions. When all the carbonates have
Contamination and Treatment
been converted to bicarbonates and the
8.3 Pf end point has been reached, more
0.02 N sulfuric acid must be added to
convert all the bicarbonates to car-
bonic acid before the 4.3 Mf end
point is reached.
If no carbonate/bicarbonate ions
exist, no reaction with bicarbonates
occur in the pH range of 8.3 to 4.3.
Therefore, the Mf will be only slightly
higher than the Pf. But if the carbon-
ate/bicarbonate concentration is high,
the Mf will also be much higher than
OH– the Pf. Since this is not a qualitative
analysis like the pH/Pf method, some
0.0017
guidelines must be established.
0.017
0.17 1. If the Mf is less than 5 ml of 0.02 N
1.7 sulfuric acid, there is usually no
17 carbonate problem.
170 2. If the Mf is greater than 5 ml of
0.02 N sulfuric acid, and the Mf/Pf
17,000 ratio is increasing, carbonate con-
tamination is a strong possibility
and a more quantitative method of
determination (such as the pH/Pf
or Garrett Gas Train (GGT)) should
be used.
NOTES:
1. High concentrations of lignite (or
organic salts such as acetates or for-
mates) in muds can cause a high
Mf. These organic chemicals buffer
the pH between 4.3 and 8.3.
2. API 13B-1 describes a Pf/Mf calcula-
tion for hydroxyl (OH), carbonate
(CO3) and bicarbonate (HCO3) con-
centrations, as well as an alternative
P1/P2 method.
The GGT may also be used to deter-
mine the quantity of carbonates. This
device estimates the total carbonates in
mg/l as CO3. Total carbonates include
HCO3 and CO3. To convert mg/l to
millimoles/liter, divide mg/l by 60.
4C.9 Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4C Contamination and Treatment
TREATING A CARBONATE/BICARBONATE
CONTAMINANT
Treating this contaminant is compli-
cated since HCO3 and CO3 ions can
exist together at various pH levels.
Only the CO3 ion can be treated with
free calcium to form the precipitate
CaCO3. The coexistence of CO3 and
HCO3 form a buffer compound that
remains at the same pH level but at
increasing Pf or Mf levels. As the car-
bonate/bicarbonate buffer zone is
formed, the Pf increases while the pH
remains relatively constant. It is not
until a pH of 11.7 is attained that all
of the bicarbonate ions are changed to
carbonate ions. Therefore, bicarbon-
ate/carbonate ions coexist in the pH
range of 8.3 to 11.7 (see Figure 3). The
concentration of HCO3 is insignificant
at a pH greater than 11.7.
Since calcium bicarbonate [Ca(HCO3)2]
is too soluble to form a precipitate,
HCO3 ions should be converted to
CO3 ions with hydroxyl (ions). To
convert HCO3 to CO3, the pH should
be increased to at least 10.3 but not
above 11.3. When free calcium is added
It may to CO3, the two react to form CaCO3.
Calcium carbonate (CaCO3) is a rela-
take several tively insoluble precipitate. Therefore,
applications
150 to 200 mg/l free calcium should
of lime or be maintained in the system. If the pH
is less than 10.3, lime (Ca(OH)2) should
gyp over be used to increase the pH because it
several
is both a source of hydroxyl ions and
circulations a source of calcium to precipitate the
carbonates. If the pH is between 10.3
to completely and 11.3, both lime and gyp should be
treat out the
used together to provide a source of
carbonates.
Contamination and Treatment 4C.10
calcium without changing the pH. If
the pH of the mud is above 11.3 where
calcium is not very soluble, gyp should
be used as both a source of calcium
and to reduce pH. The concentration
of lime and gyp required is provided
in Graphs 1 and 2 and in M-I com-
puter programs such as PCMODE 3 and
M-I QUIK CALC-II.E These graphs are
based on the Pf/pH method of treat-
ment. Therefore, the pH and Pf values
must be measured accurately. An accu-
rate pH meter is absolutely necessary
to use these graphs.
The reaction of lime and gyp to form
calcium carbonate is illustrated below:
Treating with lime:
(CO32–) + Ca(OH)2
CaCO3 ↓ + 2(OH–)
Treating with gyp:
(CO32–) + CaSO4
CaCO3 ↓ + (SO42–)
It may take several applications of lime
or gyp over several circulations to com-
pletely treat out the carbonates (CO3).
Serious mud problems can occur if
carbonate/bicarbonate contamination
is not properly identified and treated.
If the pH of the mud is allowed to drop
to 10 or less, carbonates, which are
beneficial in small concentrations, are
converted to bicarbonates. Very high
viscosities and gel strengths can develop
if this occurs. Adding a large concentra-
tion of deflocculants and caustic appears
to deflocculate the mud but what really
occurs is that the addition of caustic
soda converts the bicarbonates to car-
bonates. This results in a large reduction
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER

4C Contamination and Treatment

_______________________
60 CO3 fraction (FW) of the fluid must be
_______________________ known to use the graphs. Graph I has

Yield point (lb/100ft2)

50 HCO3 been modified to allow 20 millimoles/
_______________________ 40 liter of carbonates to remain in the
_______________________ 30 mud after treatment.
_______________________ 20 METHOD A (USING LIME ONLY)
_______________________ 10 On Graph I, enter the vertical axis at
_______________________ 0 the Pf value and proceed horizontally
0 20 40 60 80 100 120 140 160 180 200
_______________________
to the intersection of the pH line. From
Millimoles/liter
this point, proceed downward to the
_______________________ intersection of the horizontal axis and
Figure 4: Effect of bicarbonate and
_______________________ carbonate concentration on yield point. read the carbonate concentration in
_______________________
millimoles per liter. Then go upward
in viscosity (see Figure 4). This phenom- to the top of the graph, and read the
_______________________ enon will recur until the problem is pounds per barrel of lime required to
_______________________ properly identified and treated. precipitate the carbonates. Graph II
The addition of deflocculants may indicates the concentration and treat-
_______________________
be required to improve flow proper- ment of bicarbonates and is used in the
_______________________ ties once the carbonate ions have identical manner. Enter the vertical
been neutralized. axis at the Pf value, go across to the
Treatments determined by the follow- pH line and upward to the top of the
ing methods are designed to remove all graph to determine the pounds per bar-
bicarbonates and all but 20 millimoles/ rel of lime required to precipitate the
liter carbonates. In Graphs I and II, bicarbonates. Add the amount of lime
a quantitative analysis of carbonate from both graphs, and then multiply
and bicarbonate ions is shown with by the water fraction (FW) to determine
corresponding additives necessary for the treatment necessary.
precipitation. The pH, Pf and the water

Contamination and Treatment 4C.11 Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4C Contamination and Treatment

_______________________
Lime required (lb/bbl)
_______________________ .1 .5 1 2 3 4 6 8 10
_______________________ 100.0
80.0
_______________________ 60.0 14.0
_______________________ 40.0 13.9
13.8
_______________________ 13.7
20.0 13.6
_______________________ 13.5
13.4
_______________________ 10.0 13.3
8.0 13.2
6.0 13.1
_______________________ 13.0
Pf (cm3)

4.0 12.9
_______________________ 12.8
12.7
_______________________ 2.0 12.6
12.5
_______________________ 12.4
1.0 12.3
_______________________ 0.8 12.2
12.1
0.6 12.0 Example:
_______________________ 11.9 11.8
0.4 pH = 10.7; Pf = 1.7;
_______________________ 11.7 11.6 Wf = 0.80
0.2 11.5

11.0
<10
0.0
1 3 6 10 30 60 100 200 300 600 1,000
Millimoles/liter
60 ppm 600 6,000 60,000
CO3 (millimoles/liter)

For constant pH .1 .5 1 2 3 4 6 8 10 20 30 50
Gyp required (lb/bbl)

Graph I: Concentration and treatments for carbonates.

Example: this point, proceed downward to the

pH = 10.7; Pf = 1.7; FW = 0.80 intersection of the horizontal axis and
From Graph I: read carbonate concentration in mil-
CO3 = 33.5 millimoles/liter limoles per liter. Continue downward
Lime required = 0.34 lb/bbl and read pounds per barrel of gyp
required for precipitation of the car-
From Graph II: bonates. Graph II indicates the concen-
HCO3 = 3.3 millimoles/liter tration and treatments of bicarbonates
Lime required = 0 lb/bbl and is used in the identical manner.
Total treatment = The bottom scale reflects the quantity
(0.34 lb/bbl + 0 lb/bbl)(.80) of lime and gyp necessary for precipita-
= 0.27 lb/bbl lime tion at a constant pH. Requirements of
METHOD B (USING LIME AND GYP FOR additives necessary for treatment of
CONSTANT pH) carbonates and bicarbonates are then
added together and adjusted for the
On Graph I, enter the vertical axis at
water fraction of the mud.
the Pf value and proceed horizontally
to the intersection of the pH line. From

Contamination and Treatment 4C.12 Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4C Contamination and Treatment

_______________________
Lime using lime only (lb/bbl)
_______________________ .1 .2 .3 .4 .5 .6 .8 1.0 2.0 3.0 4.0 6.0 8.0 10.0
_______________________ 100.0
80.0
_______________________ 60.0

_______________________ 40.0

_______________________
20.0
.5
_______________________ 11
_______________________ 10.0 .0
8.0 11
_______________________ 6.0
.5
_______________________ 4.0 10
Pf (cm3)

_______________________
.0
_______________________ 2.0 10

_______________________ 5
1.0 9.
_______________________ 0.8 Example:
0.6 0 pH = 10.7
9.
_______________________ Pf = 1.7
0.4 Wf = 0.80

0.2

0.0
1 3 6 10 30 60 100 200 300 600 1,000
HCO3 (millimoles/liter)

Gyp required (lb/bbl)

.1 .2 .3 .4 .5 .6 .8 1.0 2.0 3.0 4.0 5.0 6.0 8.0 10.0

For constant pH
and lime required (lb/bbl)

.1 .2 .3 .4 .5 .6 .8 1.0 2.0 3.0 4.0 5.0 6.0 8.0 10.0

Graph II: Concentration and treatments for bicarbonates.

Example: multiplied by the water fraction (FW)

pH = 10.7; Pf = 1.7; FW = 0.80 to determine the required treatment.
From Graph I: When using the old API P1/P2
CO3 = 33.5 millimoles/liter method of determining carbonates,
Gyp required = 0.8 lb/bbl Equivalent Parts per Million (EPM) is
used. To convert EPM to millimoles/liter,
From Graph II: EPM is divided by the valence. For
HCO3 = 3.3 millimoles/liter example: 80 EPM of carbonate is the
Gyp required = 0.1 lb/bbl same as 40 millimoles/liter carbonate
Lime required = 0 lb/bbl because CO3 has a valence of 2, and
Total treatment = (0 lb/bbl)(0.80) = 20 EPM of bicarbonate is the same as
0 lb/bbl lime and 20 millimoles/liter bicarbonate because
(0.8 lb/bbl + 0.1 lb/bbl)(0.80) = HCO3 has a valence of one. The cur-
0.72 lb/bbl gyp rent API 13B-1 P1/P2 method reports
Quantities of lime or lime and gyp mg/l. Divide mg/l carbonate by 60
determined from the graphs must be to obtain millimoles per liter (61
for bicarbonates).

Contamination and Treatment 4C.13 Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4C Contamination and Treatment
Salt Contamination
The three naturally occurring types of
rock salt encountered in drilling opera-
tions are halite (NaCl), sylvite (KCl)
and carnallite (KMgCl3•6H2O); also,
see the chapter, “Drilling Salt.” These
salts are listed in the order of increas-
ing solubility. Two other common salts
are magnesium chloride (MgCl2) and
calcium chloride (CaCl2). These two
Halite…is salts do not occur naturally in the crys-
the most talline form due to their extreme solu-
bility. However, both can occur singly,
frequently
together or with other dissolved salts
drilled salt in connate water.
and is the A saltwater flow can be far more
detrimental to flow properties than
major
drilling into rock salt since the salts
constituent are already solubilized and react with
of most the clays more rapidly. When a salt-
saltwater water flow occurs, the mud density
must be increased to control the flow
flows. before time can be taken to condition
mud properties.
The mechanism of contamination
in the case of salts is based on cation
exchange reactions with the clays, mass
action by the predominant cation and
sometimes pH. The only systems on
The presence which dissolved salts have little or no
effect are clear water, brines, oil-base
of halite
muds and some low-colloid polymer
can be systems. Whether the source of salt is
confirmed by from makeup water, seawater, rock salt
an increase or from saltwater flows makes little dif-
ference on bentonite-base mud systems.
in chlorides. The initial effect is high viscosity, high
gel strengths, high fluid loss and a large
increase in the chloride content with
smaller increases of hardness in the mud
filtrate. Salt base-exchanges with the
clays to flush the calcium ion from the
clay particles, resulting in an increase in
hardness. Detecting a chloride increase
does not define the problem well
enough to know how best to treat
the mud since the chloride test does
Contamination and Treatment 4C.14
not indicate what metallic ion(s) are
associated with the chlorides.
For a better understanding of
these salts and how to treat the con-
tamination in each case, the salts
and/or their associated cations are
described separately.
HALITE (NaCl)
Halite (common table salt) is the most
frequently drilled salt and is the major
constituent of most saltwater flows. The
initial effect on drilling mud is floccula-
tion of the clays caused by mass action
of the sodium ion. The funnel viscosity,
yield point, gel strengths and fluid loss
will all increase when halite is encoun-
tered. The presence of halite can be con-
firmed by an increase in chlorides. The
clays dehydrate with sufficient sodium
and time. In doing so, the particle size
is decreased due to the reduction in
adsorbed water. The released water
rejoins the continuous phase of the
mud, which may result in a slight
reduction in plastic viscosity. But the
dehydrated clay particles flocculate,
causing a high yield point, high gel
strengths and a high fluid loss. The fluid
loss will increase in direct proportion
to the amount of salt incorporated
into the mud.
Treating the mud involves adding
enough deflocculant to maintain desir-
able flow properties and dilution with
freshwater to obtain suitable rheology.
Chemical treatment must be continued
until the clays have been deflocculated.
Additional caustic is required to raise
the pH. This depends on how much
salt is drilled and whether there is a suf-
ficient amount to dehydrate all the
clays in the system. If the pH is reduced
to less than 9.5, the pH may need to be
increased with caustic soda for the acid-
base deflocculants to become soluble in
order to be effective.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4C Contamination and Treatment
Pure halite has a pH of 7. Therefore,
the more halite drilled, the more caustic
is required to maintain the pH above
9.5. Halite also has an effect on the
instruments used to measure pH. If pH
paper is used, the accuracy of this paper
is affected by the chloride concentration
and will indicate a lower pH as the chlo-
rides increase. If the halite is pure, a pH
reduction greater than one unit is not
expected up to complete saturation of
the mud. However, pure halite is rarely
encountered. Associated minerals such
as anhydrite are usually present to some
extent, which will increase the filtrate
calcium. Therefore, some caustic soda
will usually have to be added along with
the deflocculants to maintain the pH in
the proper range.
A greater degree of accuracy can be
attained if a pH meter is available. The
normal probe used in this instrument
contains a potassium chloride (KCl)
solution and is inaccurate when mea-
suring pH in high-sodium-content
solutions. Therefore, a special salt-
compensated probe should be used
to measure pH in high-salt muds.
The chloride titration is used to indi-
cate the degree of saturation of NaCl
solutions, since a quantitative measure-
ment for sodium does not exist for field
use. Since neither sodium nor chlorine
can be economically precipitated from
the mud, there is no alternative but to
tolerate the concentration of halite that
enters the mud system. Dilution with
freshwater is the only economical way
to reduce the chloride concentration.
If massive salt or frequent salt
The stringers must be drilled, the mud
should be saturated with salt to avoid
complex salt washout and hole collapse. Whether
“carnallite” saturated or not, a fluid-loss-control
is relatively agent is usually necessary at concentra-
tions greater than 10,000 mg/l. This
rare. could be one of several materials such
as RESINEXT, POLY-SALE, SP-101,T MY-LO-JELE ,
Contamination and Treatment 4C.15
POLYPACT R and prehydrated bentonite.
The addition of bentonite is usually
recommended regardless of the specific
type of salt contamination. Under these
circumstances, dry bentonite should
not be added directly to the system.
The bentonite should be prehydrated
and protected with additional chemical
before adding it to the active system.
SYLVITE (KCl)
The response of the mud properties to
sylvite contamination and the treat-
ment of the mud for sylvite are identical
to that for halite. If the mud contains
no chlorides other than those obtained
from drilling the sylvite salt, the chlo-
ride titration value would be an accurate
measurement of the potassium ion con-
centration. However, this is rarely the
case. It is not uncommon to find these
salts interbedded. The quantitative titra-
tion for the potassium ion can be used
to identify the salt as either pure sylvite
or partially sylvite for geologic purposes.
It is important to know the type of
salt to be drilled. Since the solubility
of sylvite is slightly greater than halite,
a massive sylvite salt section drilled
with a saturated halite fluid would still
wash out to some extent, although not
as severely as if freshwater is used. It is
difficult to prepare a saturated KCl
fluid with desirable flow properties,
fluid-loss control and good suspension
characteristics. However, if required
(and assuming that hole conditions
would permit), a clear, saturated KCl
fluid could be used.
CARNALLITE (KMgCl3•6H2O)
The complex salt “carnallite” is rela-
tively rare. However, it does occur to
some extent in parts of the United
States, South America, Europe and the
Middle East. The most notable occur-
rence is in Northern Europe underly-
ing the North Sea drilling area. This
is the Zechstein salt that consists of
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER
4C Contamination and Treatment
interbedded halite, sylvite and carnal-
Mud lite. Mud problems associated with
problems carnallite are severe and two-fold:
1. When solubilized, there are two
associated strong cations (calcium and magne-
with sium) acting on the clays to cause
carnallite flocculation and dehydration. Mud
treatment would not be too difficult
are severe… if this were the only problem.
2. In the presence of hydroxyl ions
(OH–), the magnesium from the dis-
solved carnallite precipitates as mag-
nesium hydroxide (Mg(OH)2). This
precipitate (Mg(OH)2) is a thick jelly-
like substance that acts as a viscosifier.
At the relatively low pH of 9.9, there
are sufficient hydroxyl ions present
for the precipitate to have a profound
effect on mud viscosity. Magnesium
can only be precipitated by caustic.
This reaction starts occurring with as
little as 0.03 lb/bbl of caustic soda.
Therefore, caustic soda should not be
used if it can be avoided. A viscosity
Saltwater Flows
Connate waters can contain a broad
spectrum of salts. The origin of these
salts is directly related to the origin of
the sediments themselves. Since marine
sediments are deposited in seawater,
they usually contain salts similar to
those found in seawater. However, with
most of the water driven off in the com-
paction process, the salt concentration
can be considerably higher.
The solubility The solubility of most common salts
of most com- is directly proportional to temperature.
As the temperature of a salt solution
mon salts is increases, the solubility of the salt in
directly pro- that solution increases. A solution satu-
portional to rated with a certain salt at surface tem-
perature is capable of holding more salt
temperature. in solution at elevated temperatures. In
addition, other chemical reactions such
as leaching of minerals from sediments
by groundwater can enrich connate
Contamination and Treatment 4C.16
increase will occur if magnesium is
precipitated by caustic soda.
Most drilling muds are run in an alka-
line state to maximize the performance
of the clays and other chemicals used to
treat drilling fluids. They are also run in
the alkaline state to minimize corro-
sion. Calcium should be removed by
raising the pH and treating with soda
ash to neutralize the calcium as CaCO3.
Sodium sulfate (Na2SO4) is one chemi-
cal available to control filtrate calcium
in high magnesium content fluids. The
chemical reaction is as follows:
Na2SO4 + Ca2+ → 2 Na+ + CaSO4↓
This reaction does not affect the
potassium or magnesium content.
However, it will control filtrate calcium
to a maximum of 400 mg/l. This is the
equilibrium solubility of CaSO4, or gyp-
sum, and is indicated by the reversible
segment of the above equation.
waters with additional anions and
cations. Many of these can be detrimen-
tal to drilling fluids. Those waters highly
enriched in calcium and magnesium are
the most detrimental.
In the case of high-magnesium-
content water, the relationships
previously discussed under carnallite
apply. The indicators for magnesium
are as follows:
1. A rapid pH reduction occurs.
2. Mud thickens with additions of
caustic soda or soda ash.
3. Titrate for magnesium ion
concentration.
The total hardness titration is
reported as soluble calcium in mg/l.
However, this titration also detects mag-
nesium. To verify the presence and con-
centration of magnesium, calcium and
magnesium must be titrated separately.
Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER

4C Contamination and Treatment

Indicators for a high-calcium-content NaCl - Halite

water flow, assuming little or no
magnesium present would be:
1. A lesser effect on pH.
2. A positive mud response to caustic
soda or soda ash additions.
3. Titrate for the true calcium ion
concentration.
The terms high-calcium- or high-
magnesium-content connate water is
used because sodium salt is nearly
always present. This illustrates the
point that the chloride determination
can be misleading. For instance,
observe the variance in the ratio of
chloride to the associated metallic
ions in the salts previously discussed.
KCl - Sylvite
MgCl2 - Magnesium chloride
CaCl2 - Calcium chloride
KMgCl3 - Carnallite
In a pure solution of one salt, that salt
can be identified by the chloride con-
tent and titrating for the cations (except
sodium). However, in mixed-salt solu-
tions the problem becomes complex to
the point of becoming an academic
exercise. This is especially true since
only calcium, potassium and magne-
sium can be easily identified in the
field. The chlorides not associated with
the identifiable cations are assumed to
be associated with the sodium ions.

Hydrogen Sulfide (H2S) Contamination

The most The most serious and corrosive conta- neutralization of OH–. In order to off-
serious and minant discussed in this chapter is set the harmful aspects of the H2S gas,
hydrogen sulfide (H2S) gas. This gas is the pH must be increased to at least
corrosive destructive to tubular goods and toxic 11, or a safer level of 12, by adding
contaminant to human life. The appropriate personal caustic soda or lime. The following
discussed in protective equipment and worker chemical reaction describes the alka-
safety measures should be taken imme- line application to H2S. This can also
this chapter diately if H2S is identified. Hydrogen be seen in Figure 5.
is…(H2 S). sulfide gas originates from: H2S + OH– HS + H2O
1. Thermal deposits. H2S + OH –
HS– + H2O
2. As a formation gas.
HS– + OH– S2– + H2O
3. Biologic degradation.
4. Breakdown of sulfur containing 100
H2S HS-
materials.
Hydrogen sulfide gas can be identified
10
by the:
% of total sulfides

1. Reduction of pH of the mud.

2. Discoloration of mud (to dark
1
color) due to the formation of FeS
from barite.
3. Rotten egg odor.
0.1
4. Viscosity and fluid loss increase due
to pH reduction. S2-
5. Formation of a black (FeS) scale on 0.01
steel drill pipe. 0 2 4 6 8 10 12 14
pH
Since H2S is an acid gas, the pH
of the mud is quickly reduced by Figure 5: Distribution of sulfides with pH.

Contamination and Treatment 4C.17 Revision No: A-0 / Revision Date: 03·31·98
 CHAPTER
4C Contamination and Treatment
The bisulfide (S2–) ion may be removed
by a reaction with zinc oxide to form
zinc sulfide, which is insoluble.
S2– + Zn2+ → Zn S–
A 1-lb/bbl treatment of zinc oxide
removes approximately 1,100 mg/l
sulfides. NOTE: Check local environmental
regulations and aquatic toxicity require-
ments prior to using any zinc compound.
No more than 2 lb/bbl of zinc oxide
should be used to pretreat for H2S. The
addition of 1 to 2 lb/bbl of SPERSENEE
is recommended when pretreating.
To protect tubular goods from the
…oil-base corrosiveness of H2S, an oil-base mud
mud…acts may be recommended. The oil acts
as a filming agent in the presence of
as a filming
H2S. Hydrogen embrittlement is the
agent in the cause of tubular destruction due to
presence the H0 (atomic hydrogen) entering the
of H2S. small, highly stressed metal pores and
re-forming as H2 (molecular hydrogen)
gas, causing an expansion in the vol-
ume of the hydrogen molecule, which
ruptures the metal.
H2S is no less toxic in oil-base muds
than in water-base base muds. Actually,
more safeguards should be used with
oil-base muds than with water muds
Quick Reference for Recognizing
and Treating Contaminants
CEMENT CONTAMINATION
Symptoms
1. Increased viscosity and gel strengths.
2. Increased pH, Pm and Pf
(particularly Pm).
3. Increased fluid loss.
4. Increased excess lime and soluble
calcium (later).
Treatment
1. Depending on the type of system in
use, SAPP or TANNATHINT and sodium
Contamination and Treatment 4C.18
due to the solubility of H2S in oil. The
detection of hydrogen sulfide in mud
is tested by two methods:
1. Garrett Gas Train (GGT).
2. Hach test.
Both tests are fast, simple and have
easy-to-define results, but the Garrett
gas train is more accurate and gives a
quantitative result. The procedure is
described in RP 13 B.
If H2S is detected in mud when
using the soluble filtrate test on the
garrett gas train, action should be
taken to:
1. Immediately raise the pH to at least
11.5 to 12 with caustic soda.
2. Buffer the pH with lime.
3. Begin treatments with zinc oxide
to remove soluble sulfides from
the system.
If it appears that H2S is bleeding in
(flowing) from the formation, the mud
density should be increased to shut off
the flow of gas into the wellbore.
The chemistry of hydrogen sulfide
gas is quite complex. The actions
described above are recommended
to minimize the toxic aspects of this
corrosive contaminant.
bicarbonate may be used to lower
the pH and precipitate the soluble
calcium (see Tables 2 and 3). The
clay particles are then free to react
with the thinner or deflocculant
in use.
2. Large treatments of water and
SPERSENEE to control flow properties.
Additions of bentonite are made to
obtain desired fluid loss after flow
properties are under control.
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER
4C Contamination and Treatment
_______________________ MAGNESIUM CONTAMINATION
_______________________ Symptoms
1. Unstable yield point and fluid loss.
_______________________
2. High levels of hardness after treating
_______________________ calcium with soda ash.
_______________________ Treatment
NOTE: The following treatment is for minor
_______________________
levels of contamination, such as from sea-
_______________________
water. DO NOT use caustic when treating
_______________________ massive magnesium contamination (such
as from carnalite).
_______________________
1. Raise pH of mud to 11 with caustic
_______________________
soda or caustic potash (KOH) to
_______________________ remove magnesium (see Tables 2
_______________________ and 3).
2. Maintain pH at this level to prevent
_______________________
magnesium from resolubilizing
_______________________
from Mg(OH)2.
_______________________
GYPSUM OR
ANHYDRITE CONTAMINATION
Symptoms
1. Increased viscosity and gel strengths.
2. Increased fluid loss.
3. Increased soluble calcium.
4. Possible decrease in Pf and pH.
Treatment
1. Precipitate or sequester soluble cal-
cium with phosphates or soda ash
(see Tables 2 and 3). Reduce viscosity
with treatments of lignosulfonates
and caustic soda. Lower fluid loss
with treatments of bentonite,
POLYPACT R or RESINEX.T
2. Allow gypsum or anhydrite to remain
in the system to give a soluble cal-
cium level above 600 mg/l. Control
viscosity with lignosulfonate treat-
ment, pH with caustic soda, and fluid
loss with bentonite and POLYPACT R.
SALT CONTAMINATION
Symptoms
1. Increased viscosity.
2. Increased fluid loss.
3. Increased soluble chloride
and calcium.
4. Decrease in pH and Pf.
Contamination and Treatment 4C.19
Treatment
1. Dilute NaCl concentration with
water if the salt formation is to be
cased off shortly after drilling. Treat
the fluid with lignosulfonates for
viscosity control; caustic soda and
lime on a 1:2 ratio for pH and Pf
control; POLYPACT UL and bentonite
for fluid-loss control.
2. If the salt is not to be cased off, and
the formation is to be left exposed
for a long period of time, saturate
the system with sodium chloride
(salt) to prevent further hole enlarge-
ment. Control the viscosity with
treatments of lignosulfonates plus
caustic soda and lime. Small treat-
ments of POLYPACT R are effective for
viscosity control if solids are con-
trolled in the proper range. Control
fluid loss by additions of starch
and/or POLYPACT R and prehydrated
bentonite additions. If starch is used
for fluid-loss control, maintain NaCl
at 190,000 mg/l to prevent fermenta-
tion of the starch, or use a biocide.
SALTWATER-FLOW AND
GAS-KICK CONTAMINATION
Symptoms
1. Increase in mud pit level.
2. Increase in rate of returns
from wellbore.
Treatment
1. Shut pump down.
2. Pick up off bottom to clear
the kelly bushing.
3. Close in the well with BOP.
4. Measure the drill pipe pressure and
calculate the additional mud density
required to balance the kick.
5. Increase the mud weight to the
required density while circulating
the kick out at a reduced pump rate.
6. If it is a gas kick, remove the
gas from the system by the use
of surface circulating equipment
and de-gassers.
Revision No: A-1 / Revision Date: 02·28·01
 CHAPTER

4C Contamination and Treatment

_______________________ 7. If it is a saltwater flow, dump salt- Treatment

_______________________
water at the surface (if possible), 1. Raise the pH to 10.3 to 11.3.
then condition the fluid with addi- 2. Add lime and/or gyp, two soluble
_______________________
tional deflocculants and caustic sources of Ca to remove carbonates
_______________________ soda. Dilution of the NaCl ion con- as CaCO3 (see Tables 2 and 3).
_______________________ centration with freshwater may be
HYDROGEN SULFIDE CONTAMINATION
required. Small treatments of lime
_______________________
and caustic soda may also be Symptoms
_______________________ required for pH and Pf control. 1. Decreasing alkalinities.
2. Slight foul odor (rotten egg)
_______________________
at the flow line.
_______________________ CARBONATE CONTAMINATION 3. Mud or pipe turns black.
_______________________ Symptoms Treatment
_______________________
1. High gel strengths. 1. Increase pH to 11 to 11.5 with
2. Increasing Pf with constant pH. caustic soda.
_______________________ 3. Increased difference between Pf 2. Buffer with lime.
_______________________ and Mf. 3. Add zinc oxide* (see Tables 2 and 3).
_______________________
4. Increasing carbonate or
bicarbonate levels.
_______________________
Treating Concentration
Contaminant Contaminating Ion Treatment (lb/bbl)
Carbon dioxide Carbonate Gyp to reduce pH mg/l x Fw x 0.00100
Lime to raise pH mg/l x Fw x 0.000432
Bicarbonate Lime to raise pH mg/l x Fw x 0.00424
Gypsum and anhydrite Calcium Soda ash mg/l x Fw x 0.000928
SAPP mg/l x Fw x 0.000971
Sodium bicarbonate mg/l x Fw x 0.00735
Lime or cement Calcium and hydroxyl Sodium bicarbonate lb/bbl excess lime x 1.135
SAPP lb/bbl excess lime x 1.150
Citric acid lb/bbl excess lime x 1.893
Hard or seawater Calcium and magnesium Caustic soda mg/l x Fw x 0.00116
Hydrogen sulfide Sulfide (H2S, HS–, S2–) Zinc oxide* plus mg/l x Fw x 0.00091
sufficient caustic soda
to maintain the pH
above 10.5
*Other zinc compounds such as chelated zinc or zinc carbonate may also be used. An excess should always be maintained in the system.
NOTES:
1. Fw is the fractional % of water from retort.
2. Excess lime = 0.26 (PM – (Pf x Fw)).

Table 2: Chemical treatment in U.S. units.

Contamination and Treatment 4C.20 Revision No: A-1 / Revision Date: 02·28·01
CHAPTER

4C Contamination and Treatment

Treating Concentration
Contaminant Contaminating Ion Treatment (kg/m3)
Carbon dioxide Carbonate Gyp to maintain pH mg/l x Fw x 0.00285
Bicarbonate Lime to raise pH mg/l x Fw x 0.00121
Gypsum and anhydrite Calcium Soda ash mg/l x Fw x 0.00265
SAPP mg/l x Fw x 0.00277
Sodium bicarbonate mg/l x Fw x 0.002097
Lime or cement Calcium and hydroxyl Sodium bicarbonate kg/m3 excess lime x 3.23
SAPP kg/m3 excess lime x 3.281
Citric acid kg/m3 excess lime x 5.4
Hard or seawater Calcium and magnesium Caustic soda mg/l x Fw x 0.00285
Hydrogen sulfide Sulfide (H2S, HS–, S2–) Zinc oxide* plus mg/l x Fw x 0.002596
sufficient caustic soda
to maintain the pH
above 10.5
*Other zinc compounds such as chelated zinc or zinc carbonate may also be used. An excess should always be maintained in the system.
NOTES:
1. Fw is the fractional % of water from retort.
2. Excess lime (kg/m3) = 0.074178 (PM – (Pf x Fw)).

Table 3: Chemical treatment in metric units.

Contaminant WT FV PV YP Gels FL pH Pm Pf Mf Cl– Ca2+ Solids Treatment

Cement Bicarb, or SAPP,
— ↑ — ↑ ↑ ↑ ↑ ↑ ↑ ↑ — ↑pH↓ — or thinner, bicarb
11.5 and citric acid
Gypsum or Caustic, dilution
anhydrite water and
— ↑ — ↑ ↑ ↑ ↓ ↓ ↓ ↓ — ↑ — thinner, or soda
ash (plus fluid-
loss polymer)
Salt Caustic, dilution
water, thinner
— ↑ — ↑ ↑ ↑ ↓ ↓ ↓ ↓ ↑ ↑ —
and fluid-loss

↑
polymer
Carbonate or pH <10.3: lime
bicarbonate pH 10.3 to 11.3:
— ↑ — ↑ ↑ ↓ ↓ → ↑ — ↓ —
↑
↑

lime and gyp

pH >11.3: gyp
H2S Caustic, lime and
— ↑ — ↑ ↑ ↑ ↓ ↓ ↓ ↓ — — zinc source
↑

(zinc oxide)
Old Dilution
water and
— — — — — — — — ↑
↑

solids-removal
equipment
Solids
New Dilution water,
solids-removal
↑
↑

↑
↑

equipment and
thinner

↑ Increase ↓ Decrease — No change Slight increase Slight decrease

↑
↑

Table 4: Quick reference for recognizing and treating contaminants.

Contamination and Treatment 4C.21 Revision No: A-1 / Revision Date: 02·28·01