,Mud

Chemistry-

~: "Zit-;::::: it iiiOQ

~~

MA.GCOBAR TECHNICAL MEMORANDUM

Mud Engineers deal with chemistry daily. Chernistry is the study of matter, including its composition, its properties, and its transformation. into or reaction with othe substances {chemical reactions .

• MatteI" 15 sdmetliing t at as mass and,c..o~c-c-u-p-ie""'s

space. Mass,is a measure of a body's inertia, and it is a measure of the amoun oCmateriaLa body contains. ass causes the Dody to have weig t in a gravitational field, and along with the length of time,

constitutes one of the fundamental quantities on whichall physical measurements.are based. TFie space occupie-d by amaterial is the ¥olume of

that material. Common urri'fs [-af volume a:(;~ .gallons, barrels or milliliters. Density is defined as ihe mass of a material e

unit volume, ounds per gallen, peunds per square .. inch. or pounds per square foot are common units for density in the oilfield. Specific gra¥ity 1S the ratio of the mass 0 a 00 ' . or liquid to the mass of an equal vol me of (lure Wiater at 40 centigrade or some ath¢T previou 1 deteonined temperature. :rhe weighrof a materiai is die quantity ef mass which is dependent on gravitational

attraction. _

_~ __ -='C.:::;LA;..:;SSIFICATIONI Materials en or in the earth fall 'n one 0

states: solid, liquid. or gas.

AU of the material on or in tne eartli can e separated into rwo categories, hQmogeneoul (pure. substances) and heteroeenQous (mixtures of pUl"e sub<stances). typical mixture found in nai ure is gravel,

it 1:5 distinctly heterogeneous in. appearance. Nearly everything in nature is a mixture. Pure substances, on the other hand, may be found in laboratories. Each is identified as a pure substance because it is homogeneous and its composition is exactly rlre same wherever you find it andexa:rnine it.

These pure substanzes c«n be furdie s 15div·ae '7 into. two classes~element5 and compound;, ~. Th elements-are thos pure su stances which cannot be broken down into two or more simpler substances by the methods ordinarily available in the laboratory. A compound, in contrast, can be resolved into two or more simpler substances. A substance is a compound if it can be resolved into two or more elements; if it cannot be broken down into two or more dements, it must, itself. be an element. -It is convenient to. ref~r to an e ernenr by Use 0 ':l ~ abbreviation ca led :a sy b I ~atlte than the ull name. able I is a list of elements ana symbols (or ormlas) which are commonly used in drilling muds.

'TAB~lIE II

NIAM.E Aluminum Barium Calcium Carbon Chloride Hydrogen Magnesium Nitrogen xygen IRhosphorous ;Potassium Silico

S.YMBOL

ATOMS

H'"d ."'" IH 2H d·3Hh .so Y rogen Isotopes: 1 , I ,an I." ave masses ill'

1:0078, 2.0140, .and 3.0~605respectively. The fra:_i.) nons of each Isotope m nature are 9.9985 )( 10 "p

-4 d' -II ".. .,.

15)( 10 ,an 1.0· atomic mass unit respectively.

The atomic weight of hydrogen is therefore: (9.9985 )( 10-1) 1.0078 + (1.5 x 10-4) 2.0140 + (.3..01605) 10-11"

; 1.00 8 _ ..

e Atomic Mass Scale is '3 re ativ mas based on Ilc isotope hioh has.~n»mu (a'tom' unit) value of 12,00 .

'-----~-

A substance that is compese of ce:~tain e ements

in definite proportions or amounts is a compound. '_ Compounds can e I5roken own into two or more dements. Common table salt is a compound; it can

be broken down into the elements sodium and chlor-

ine. If we examine hundreds of compounds, either

by synthesizing (forming them from elements in the laboratory), or by analyzing them (breaking them down into their component elements), we can make

the following conclusions:

1. The composition of a compound is always the same; it is definite and exact ..

2. When elements combine to farm compounds, energy is either liberated or absorbed ..

3. Elements lose their identity (their characteristic properties), when they combine to form a. com'pound.

4. The compound substance is homogeneous. In

MAGCO~BA!R TECHNICAL M'EMORANDU'M

contrast, mixtures are not of defirnte composition; they are generally not homogeneous.

FORMULAS m ~o 1(;; crunpoun.fl alwi\i S sarne elements combined.i exact] she arne tit' ~y.

eight, It is possibe to reE esens-irs GO ll]prlsitiot1(,b means of a formula l!;arD n combInes witG" oxygen in th ratio of -2:00 gms of carbon to 31.9988 gms of oxygen. That means that carbon dioxide is made up of carbon and oxygen combined in the ratio of 1 gram-atom carbon to 2 gram-atoms of oxygen .. The formula is therefore C02; the subscript 2 refers only to the oxygen and means that there are 2 oxygen a toms per molecule.

Hydrogen combines with oxygen in the ratio of 2.,0158 gms of hydrogen to 15.9994 gms of oxygen; that is, a ratio of 2 gram-atoms of hydrogen to 1 gram-atom of oxygen. The formula for water is therefore H20.

Suppose we analyze an unknown compound and find that it contains 31.9% potassium, 28.9% chlorine, and 39.2% oxygen. How shall we calculate the formula of the compound? Per cent means "parts per 100". Therefore, to say that a compound contains 31.9% potassium. 28.9% chlorine. and 39.2% oxygen is equivalent to saying that 100 gms of the compound contains 31.9 gms of potassium, 28.9 gms of chlorine and 39.2gms of oxygen. To fmd the fonnula we must. find the relative number of gram-atoms of each element present. This is done on a ratio basis between the element in question as compared to oxygen .. Therefore, 31.9 gms of potassium";" 39.] gros per gram-atcm > 10.815 gram-atoms of potassium; 28.9 gms of chlorine ..;- 35..46 gms per gram-atom » ,0.815 gram-atoms of chlorine, and 39.2 gms of oxygen+ 16 gms per gram-atom =' 2..45 gram-atoms of oxygen. The ratio of gram-atoms of potassium to gramatoms of chlorine to gram-atoms of oxygen is ,0.815 to 0.815 to 2.45 .. To reduce this to a small wholenumber ratio we win divide each number by the smallest, which is 0.815. That gives a ratio ofl gramatom of potassium to 1 gram-atom of chlorine to 3 gram-atoms of oxygen. The formula is therefore KCl03.

We can summarize the method illustrated in the above examples as foHows:

] .. Determine the exact composition of the compound, that is, the weights ofeach dement that combines, or the per cent of each element in the compound, either by analysis or synthesis.

2. Divide the weight of each element or the per cent of each element by its gram atomic weight. The simplest ratio between the quotients gives the simple chemical formula. Table 2 lists common compounds the mud engineer uses in his work.

NAME

Silvcf"Nittafe :Alummum OXide Barium Sulfate Barium Car onate Bariurn Hy'drQxide Calcium Hydroxide Calcium Sulfate CalCIUm Carbonate Calcium Chloride ydrochloric Acid ydrogen Oxide ~ulfu[jc ACid

drogen Sulfide Nitric Acid \Potassium Chloride Sodrurn Hydroxide SodIUm Bicarbonate So3ium Chlor ide

'TABLE 2

FORMULA COMMON NAME

, gOO l\bO] BaSO.

Baco~-

Ba(OH "

Ca(OH 1 Bime

CaSO. Gypsum Anhyd~t

CaCOl Limestone "

CaCh HCI H20 HlSO. EhS HNO, KCI NaOH NaHCOJ NaCI

If. Sped IC group-af.aroms tnat acts as a single unit because they a~ held together by forces caned. chemical bonds re caned mol.cul.s. We ave learned t t rh a 0 ' i . he'S allesr'unii into which an element can be divided and stil] retain the properties of the element. There is, obviously, a smallest unit in which a compound can exist and still retain the properties of the compound; however, thenamre of this unit varies from one group of compounds to another so it can't be described as simply as in. the case of the atom .. For a great many compounds the Urn! is a. neutral particle whose composition, in terms of atoms, is represented correctly by the simple chemical formula of the compound. This particle is called a molecule. Thus the smallest particle of carbon dioxide is a molecule of CD2, consisting of 1 atom of carbon in combination with 2 atoms of oxygen.

llh'-,,""u'''"m-of die r mi - eigHts 6f'tlie atoms represented by the formula of uhstanGe is the formula weIght of that substance I e- 'ann a-is the true chemical orrnula; the" formula weight is also the molecular weight of the substance .. Thus the formula weight of NaCI is. 58.443. This value is obtained by adding the atomic weight of sodium (22.989) to the atomic weight of chlorine (35.453). One gram-mole of sodium chloride would he 58.443 gms, or we can drop the gram and just say 1 mole ofNaCl would be 58.443 gms.

A specific compound always contains the same dements combined in exactly the same ratio by weight and thecomrposition is represented by a formula. of that specific compound .. CaCla, FC203,

MAGCOBAR TECHNICAL MEMORANDUM

and Ba504are examples of formulas of compounds.

1lhe valence 0 ato may: oe regarded as the

tendeney to combine with other atoms and is measured by the number of hyatogen or Ilalogen ato s

hich one atom of rhe given element can comhin with or replace. Examination of Table may raise c~rtain questions. In compounds H20, HCI and H2S04, why does one atom of chlorine combine with one atom of hydrogen while one oxygen atom combines with two hydrogen atoms? Why do sodium and chlorine combine in the ratio of one atom of sodium to one atom of chlorine (NaCI), while with calcium the ratio is 1 to 2 (CaCh)? These questions can be answered by assuming that in any compound the atoms are attached to or attracted to each other by bonds of some sort and that each element is provided with a definite number of bonds wi th which it can attach i tsel f to other elements. The number of bonds determine the combining capacity or valence of the element. The hydrogen atom is selected as a standard of reference and is assumed to have one bond or a valence of one. Because one atom of hydrogen combines with one atom of chlorine, the valence of sodium in NaCl must also he one .. Likewise, the valence of Kin. KCI is also 1 for the same reason. The valence of Ca in eaCh must he 2 since there is one Ca for every two Cl's, If we consider the compound H2S04 we see that the valence of So.. must he 2 since there are two hydrogen atoms. The sulfate radical (504) is taken as a complete unit. In the case of caustic or NaOH. since Na has a valence of 1 then the hydroxyl radical (OH) must have a valence of 1. In the case of lime or Ca( OHh, since calcium has a valence of 2 then there must be two hydroxyl radicals of the OH atom. On the basis of what has been stared one can say that the valence of an element represents the number of atoms of hydrogen, or their equivalent, with which one atom o the element will combine. Table 3 is a list of commOD elements and radicals with their respective valences.

(ELEMENT Hydrogen Oxygen Potassium Sodium Calcium Magnesium Aluminum

TABLE 3

SYMBOL VALENCE '1'1 o K

RADICAL SYMBOL VALENCE

,

ATOMIC STRUCTURE

; .

The mass number of 12 is illustrated as the presuperscript and the atomic number of 6 is shown as the presubscript of this isotope of carbon.

Protons, neutrons, and electrons are called the elementary particles of an atom and have masses (m) as follows:

al -23

Mass of protons equ s 0.16724 xl0 grams.

Mass of neutrons equals 0.16757 x lO;-23_:§rams. Mass of electrons equals '0.10000910 x]o grams.

MAGCOBAR TECHNICAL MEMORANDUM

The mass of an atom is approximately equal to the sum of the masses of the p+, n and e - the a tom contains. TVsmg die atomIC mass scale am ... ~ ass of the elemental artIcle'!; illustrates the fo lowj~g~

Mass of proton equals 1.00728 amu, Mass of neutron equals 1.00867 amu. Mass of electrons equals 0.000549 amu ..

The weight depends on gravitational attraction, whereas, mass is independent of all forces.

Mass is the true measure of the quantity of matter.

Having obtained a picture" of what is believed. to be the structure of the atom, the question now arises: just what happens when atoms of different elements combine to form compounds? Atoms of one dement combine with atoms of another element to form a compound either by transfer of electrons or by sharing pairs of electrons.

Na

THE NEUTRAILATOMS

REACTIO;N BY TRANSF:ER OF AN ELECTRON

N'a + 'IONI

(I·· ION THE PRO:DUCTS OF THE RiEACTI·ON

The sodium nucleus has 12 neutrons and eleven protons .. The electrons are shown in the orbitals surrounding the nucleus. The first orbital or shell must not contain more than two electrons and each SIIC~ ceeding shell cannot contain more than eight e1 ec-

trons .. The outermost orbit is designated as the valence electron orbit.

!1 The chlorine atom is also shown with its electron

configuration. Note that the chlorine atom has seven electrons in its outermost orbit. Thus in the combination ofl atom of sodium and 1 atom of chlorine to form the compound, N act the 1 sodium valence electron is transferred from the sodium atom to the outer shell of the chlorine atom.

Why does sodium give up its electron and why does chlorineaccept it? The theory deal!ing with the behavior of elements assumes that every atom tries to achieve an 8~electron shell. Atoms with 1, 2, and 3 valence electrons find it easier to give awaydectrons whereas those with 4, .5, 6 and 7 find it easier to accept them. In the case of sodium and chlorine, sodium gives one electron resulting in a net charge of +1 and chlorine takes on one electron resulting in a net charge of-L Neither atom is considered neutral with these changes .. The sodium atom has become an ion with a positive charge written as Na+ and the chlorine atom has become an ion written as cr.

The evidence to support the belief that electrons are transferred and ions are formed is the fact that melted NaCl is a conductor of electricity; during the conductivity process sodium metal collectsat the negative pole of the eel] (the cathode) and the chlorine collects at the positive pole (the anode). Thus the sodium ion iscalled the cation and the chlorine ion the anion. In writing the name of a compound the cation is always written first. Since sodium gives up an electron it is said to be electropositive, and since it readily gives up this electron. it is said to be strongly electropositive.

N elltral~a-r-o-m-s-c-o-n_'t-ain an equal numBer of pro ORS ana electrons. An ion is an atom or group of atoms with a positive or negative charge. A net positive r negative charge on an atom or group of atoms is a result of the removal or addition of eleG_trcns in the :extranuclear zone of the atom or gr p of atoms. Positive ions are called cations and negative ions anions. Placed in an electric field cations move (cOward the negative electrode (cathode) ana anions move toward the positive electrode (anode

""-----S·OUJl'IQNS·------

If a small quantity of sugar is dropped into a glass of water it will soon disappear. We say that it has dissolved and that a solution of sugar in water has been formed. ['he so ution will be Observed to ~ e hom genecus; no particles of sugar can be seen. Th sugar is referred to as the solute; It IS the substance that is dissolved. The water is referred to as [he solventi It is the substance that does the dissolvin . If more sugar is ai:lclea, a sm quantIty at a tune, to the solution just prepared. it will continue to dissolve. Finally, however, the solution will be unable to dissolve any more sugar. This win be indicated by the

MAGCOBAR. TECHNICAL MEMORANDUM

fact that crystals that are added will drop to the bottom. of the glass and will not dissolveeven though the contents of the glass are well stirred .. .A solution which has dissolved all the solute that it is capable of dissolving at a given temperature is said to be saturated. In most cases, if the temperature is increased, more solute win go into solution.

I ••

• . SOLUB!IILITY

The quantity of solute that will dissolve in a quantity of solvent to give a saturated solution is referred toas the solubility of the solute in the solvent. Solubili.ty ofa solid, liquid or gas in a liquid or gas in a liquid is generally expressed in units of grams o: solute per 100 grams of solvent. Table 4 lists the degree of solubility of common compounds used in drilling fluids.

;"'·N ... :.O .... · u:H'-- __ .... T.mor:aL Solubility

eaCb 41...5

NaCi 35

KCi ~_.Y.7

1lS'alC03 21 5

An increase in temperature generaUy increases the solubility ora solid in a liquid and also a liquid in a liquid. An increase in pressure increases the solubility of a gas in a liquid, but has practically no effect on the solubility of liquids and solids in liquids. Calcium chloride, magnesium chloride ana magnesium sulfate increase in solubility with temperature in neutral solutions, but in alkaline (base) solutions tend to react and precipitate as calcium carbonate and magnesium hydroxide .. Magnesium becomes less soluble as water alkaliniry increases.

An acid is escribed as a substance which has a sour taste, causes effervescenoe in. contact with carbonates and turns blue litmus red. Bases have opposite properties, in solution tney (10 not have a sour taste, do not cause effervescence in contact with carbonates and turn red litmus blue. A salt is simply a combination of acid and base" radicals, A salt may be neutral or have a tendency toward the acid or base side depending upon the relative strengths of the respective radicals The strengdi of an aCI IS sunply a measure of ItS capacity to liberate hydrogen ions. whereas the strength of a base depends upon its generation of hydroxide ions. Tab]e 5 is a list of common acids. bases and sahs that are used in drilBng fluids.

TAlLIE 5

COMMON, ACIDS, BASES, AND SALTS

N!AME FORMULA TYPE

y rochlonc ACl HCI Acid

Sulfuric Acid H2S04 Acid

Nitric Acid HN03 Acid

Sodium Hydroxide NaOH Base

Calcium Hydroxide Ca(OH)2 Base

Sodium Chloride N aCI Salt

Ealcium Chloride CaCh Salt

ose suostances w ose water solutions conduct electricity and hence are concluded to contain positive and negative solute ions are called electro Iytes. AI] soluble electrovalent compounds Jre electrolytes. All acids, bases and salts are electrolytes .. Electrovalent compounds are formed by transfer of electrons; in. the process positive and negative ions are produced. The resulting solid compounds, (salts and hydroxides),. all have an ionic crystal lattice .. 'This means that, in the case of these electrovalent compounds. the ions are formed when the compound 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 are thereby set free in solution; the water merely acts asa solvent. Typical equations to illustrate the setting free of these already-existing

lOIlS are:

NaCl ~ Na+ + cr

Ca(OH)2 : Ca ..... '" 20H-

Since the ability of a solution to conduct electricity is dependent upon the presence of ions, we can conclude that the solutions that are excellent conductors contain a high concen tration of ions (completely ionized) while the poor conductors contain low concentrations of ions (not completely ionized). Electrolytes that are completely ionized are called strong-electrolytes whereas those not completely ionized ate called weak electrolytes. With very few exceptions all salts are strong electrolytes. Most bydroxides except Mg are strong electrolytes and accordingly classified as strong bases, Acids such as HGI,. H2S04 and HN03 are strong electrolytes and, .therefore, classified as strong acids- most others

·,.are moderately weak and classified .3S weak acids ..

Pure water is a weak electrolyte.

li INDICATORS

aterials used to . etermine the end-point in titrating are called indicators. ndicators are compounds t3cJds or fbases) tbat change color with a change in pH. The color change of each acid-base indicator changes over a specific range of pH values. Sbme indicators change color in the acidic, neutral,

MAGCOBAR TE.CHNICALMEMORANDUM

or basic range of hydrogen ion concentra tion. Table 6 represents some of the indica tors and color changes the indicators undergo at specified pH values used in

mud analyses. -

T.ABU6

COLcOR OF BASE FORM YELLOW

INDICATOR '(OlOR

OF ACID FORM RED

Metliyl orang,e + L-=----.."..,..r;-;-----::"'4

Brom Cresol F:recn Green Yellow

ethyl or;onge Red Yellow

Phenolphrhalem Colorless Red

Thyrnolphrhalem Colorle,s Blue

Brorn Cresol green Yellow Blue

Tl,T:RATIONS

The chemicalchecks made in mud analyses are called titrations.· ifrations are processes using a "standar solution of known concentration to deterrnrne the concentration of an unknown sample 0 \known volume ~he asi equation "nvolv-ing t"hi

quantitativ an~lysis is: "

Milliliters, x NI = Milliliterss x N2 Solving this equation for N gives the foHowing; Milliliters, x NI

Milliliterss

For one milliliter sample, using an indicator, and titrating with a pipette using a solution of known concentration (N2), it is possible to determine the concentration (NI) of the unknown sample. Proper procedures are outlined in the Drilling Fluids Engineering Book for each quantitative check using stan-

dard solutions for determining unknown cations and anions. Care should be exercised to follow the exact procedure. Formulas are also provided which will enable the engineer to make the necessary calculations without 'employing a great deal of mathematics in converting units.

INORMALITY AN!O PPM

here are several ways to express the concentration of a chemical. Two common methods are by IDoSOJmaUty and parts per million. A ~ normal

olution is defined as a solution of such a concentr - tion that it contains one gram-equivalent of a suHstance per liter of solution. For example, 1.0 normal HCl is 36.5 gms per liter of solution. 1.0 normal FhSO~ 1549 gms per liter of solution. Parts per mil« han, abbreviated ppm is simply the product of die weight per cent times 10,000, or the milligrams pe liter divided by the solution density in gms per liter. Saturated salt water, for example, is 26% salt b eight; therefore, it would contain 260,000 ppm s t.

Water exists in nature as molecules of H20; hydronium (H30;l') and hydroxide (OH-) ions, Water is in equilibrium with the above ions according to the foHowingequation:

2H20 ~ H30+(aq) ... OH-(aq)

The subscript (aq) indicates the ion is dissolved in water, forming an aqueous solution. Since water ionizes itself, the process is called autoloni,lation. This equilibrium with the hyaromum and1iy roxioe ions provide the basis for the claSSIfication of aciCls and 6ases. Acid" are substances hat when ilissolveel in water Increase the concentration of{H30+) in solution ..

The equilibrium expression for the autoionization

process IS:

K", = (H+) (OH-)

This equilibrium expression is used frequently; the equilibrium constant is given the specific symbol Kw,

where the subscript (w) refers to water. At 24°C, K w = 1.0 X ]0~14. Kw depends on temperamre and increases with increasing temperature.

The product of (H+) and (OH-) must remain the same at all times providing the temperamre is constant. En a neutral solution:

(ll+) == (OH-); (tr)2 == Kw; (H') = (OH-) = 10-1 If (H+) increases, the (OH-) must decrease or the solution becomes more acidic. As a solution becomes more basic, the (H+) decreases and the (Of-r) increases.

H+ (aq) and OH\ aq) ions are always present in aqueous solution in equilibrium with the solvent. H'{aq) and OH-(aq) can react with other ions, and the (I·n and (OH-) can influence the concentrations of these other ions in the solution. For this reason reference to the concentrations of H+( aq) and OH-( aq) are made .. To assist in this reference the terms pH and pOH are here defined ..

pH '" - log (H+)

pOH "log (OH-)

A convenient relationship between pH and pOH is found by taking the negative logarithm of:

K", - (H+) (OH-)

which gives,

- log Kw = - log (H+) - log (OH-)

Using the definitions of pH and pOH given above we find that at 25° C:

pK", '" pH + ~H

Kw == 1.0)( 1.0-14 and

pKw '" - log Kw = 14 " pH + pOH

Figure I illustrates the scale of pH and pOH values in relationship to the (If) and (Ofr) ..

MAGCOBAR TECHNICAL MEMORANDUM

(H+)

FIGURE I (OH-)

pOH

pH

1 '0 10-14 14

to-I I A 10"1] 13 A

.10-2 2 C l'O~12 12 C

10-3 3 11 10-11 111 t

10-4 4 D 10-10 10 D

1O-~ 5 10-9 9

l'O-fI 6 10-8 8

to-7 7 NEUTRAL 10"7 7 NEUTRAL

1~& B 1~6 6

10-9 9 B io" 5 B

10-10 1'0 A 10-4 4 A

10"" 11 S J lO-l 3 S J

1'0-12 12 E 10-2 2 E

1'0-13 13 to-I 1

to-14• 14 1 '0

Note that low pH values correspond to high acidity and low pOH values correspond to high basicity. A change of one pH or pOH unit corresponds to a change in molar concentra tion by a factor of 10. A solution with a pH of 4 is not twice as acidic as a solution with a pH of2, but a solution with a pH of 4 is 100 times. as ~asic as a. solution with a l'~ of2.

When NaClls dissolved 1D water the Na Ions do not tie up OH- ions because NaOH is a strong base. The cr ions do not tie up H+ ions because HCI is a strong acid. As a result neither ~ ions nor OH- ions are removed from the solution, and it remains neutral. In other words, if the salt contains the cation of a strong base and the anion ofa strong acid, the solution will remain neutral. If the salt contains the cation of a strong base and the anion of a weak acid and can therefore be formed by the neutralization of a strong base by a weaker acid, its solution reacts alkaline; such is the case with Na2C03 (Soda Ash). Naturally, if an acid is added, the pH would decrease, whereas the pH would increase if a base were added to a neutral solution.

SOl.UBILITY AS A FUNCTION OF pH

The solubility of mud chemicals are generally a function of the pH of the solution. Water based drilling fluids are generally run with a pH in the range of 7-11 for safety and corrosion reasons. Muds have been run with pH values other than within the range above; however, this is the exception rather than the rule.

Lignosulfonate and/or lignite muds' optimum pH ranges are 9.5 and above. Duovis' effectiveness is optimized within the pH range of7-l!. Most of the products in our product line have optunumpH ranges and, therefore, each mud engineer should familiarize himself with these and run the drilling fluids within these pH ranges.

Al.KALlNITY

Alkalinity ritrations illustrates; OH-, HCO)", and CO)" concentrations. Berates, silicates, phosphates. sulfides and solubilized lignites also can enter into the titration and or treatment calculations based

on alkalinity values. Alkalinity is the combining power of a base measured by the maximum number of equivalents of an acid which can react to form a salt. Alkalinity is reported as the number of milliliters of 0.02 N H2S04 required to titrate a milliliter of filtrate or mud.

alinity is not tne sam as pH. strong base

added to pure water would illustrate a correlation between alkalinity titration values and pH; however, due to the presence of HeOl. COl. etc. in drilling fluids, no correlations should be made.

Treatments based on alkalinity will be further expanded in the section of this handout entitled.:

Common Chemical Reactions in M.ud ChemIstry.

BUFFER SOLUTIONS

When an acid or a base is added to pure water, the concentrations of rt and OH" change markedly. Certain sohrtlOns callea buHer solutions prevent a large change in the concentrations of H+ and Old~

w en a base or acid is added to a solution S . ~t.zc ?.H)

'Bltffel' solutions general] consist of a weak acid plus a salt containing the anion of the weak acid, or a weak base plus a salt containing the cation of the base. The buffer cation of a solution consisting 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 (H2C03) and of a weak base is ammonium hydroxide (NH.tOH). 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 of the water or solution is noticeably increased. If the same small amount of acid is added to the same amount of solution containing a weak acid and the soluble salt of that acid, the increase in hydrogen ion concentration is so slight that for all practical purposes it is negligible. The anions of the salt of the weak acid have taken the H+ ions as fast as they were added and have tied them up in the form of molecules of the weak acid. The net result is that the hydrogen ion concentration has changed only very slightly; thus the pH has for all practical purposes remained constant,

This phenomenon can very easily take place when the engineer is titrating his mud filtrate for carbonates and bicarbonates. In. the case where carbonates and hydroxides are present, as soon as carbonates are converted to bicarbonates, a buffer solution begins to develop which resists changes in pH with small additions of acid.

COMMON CHEMICAL R,EACTIONS IN MUD CHEMISTRY

This section deals with mud chemistry problems common to most mud engineers. Reactions with

MAGCOBAR TECHNICAL MEMORANDUM

various treatment chemicals are illustrated with resultant precipitants or results documented.

'GYP' OR ANHYiDRITE: CONITAMINATI:ON The calcium ion, which can be derived from gyp or anhydrite. is a contaminant in some of our water base muds. One way to reduce the availability of these free ions is to add soda ash. The following equation illustra res how calcium sulfate (or gyp) is reacted widl sodium carbonate (soda ash) to form calcium carbonate. The downward arrow implies precipitation. whereas an upward arrow implies a

ga.s: .. ~

CaS04 -I- Na2C03 - CaCO} j + 2Na + SO;;:

Another reaction £orgyp contamination is barium carbonate (BaC03) .. The reaction is as follows:

CaS04 + BaCO) - CaC03 I + BaS041 Another product which can be used for treating out thecakium is sodium acid pyrophosphate ·(SAPP). The reaction following a SAPP addition is as follows:

N a2H2P207 + H20 - 2NaHzP04 2NaH.2P04+CaS04- Ca3(P04pl +N3.2S04 +2It

CEMENT CONTAMINATION

Cement or Ga(OHh can be treated by adding sodium bicarb (NillC03). The reaction is as foUows:

Ca(OH)1;.NaHC03-CaC03l+Na++Off + H20 Soda ash can also be used for treating c," from cement contamination when the pH of the mud is

less than. 11 .5. The reaction is as foUows: ..

Ca(OH)2 + Na2C03 - CaC03 l 2Na+ ;. 20ti SEA WATER

Magnesium ions as calcium ions are both present in sea water. Both of these ions are detrimental to water base muds. Since Mg(OH)2 is relatively insoluble, either caustic or lime may be used for treatment. The reactions are as follows:

Mg++ + 2NaOH- Mg(OHh l+ 2Na+ Mg * + Ca(OH)2 ...... Mg{OH)2 j + Ca~

In actual practice the caustic is used to precipitate the magnesium and the lime is used to suppress the solubility of the calcium.

WHEN C02 GAS COMIES IINTO'

THE WELLBOR.:!

Treatment with caustic soda: 2NaOH + CO2 - 2N:t + C03 + H20

Treatment with lime may be used in clear water drilling, although the calcium carbonate precipitate formed may have a bad scaling effect on the drill string:

Ca(OH}2 + C02 ...... GaC03 + H20

WHENI H2S GAS COMES INTO TIHE WELL BORE

Treatment with caustic soda:

2NaOH "'" H2S ...... NaT S= + H20

Treatment with lime:

excess Ca(OH)2

HzS + Ca(OH)2 ...... Ca""" + S= + H20

Treatment with basic zinc carbonate:

H2S +ZnC03 + 2NaOH- ZnSI + NazC03 + 2H20 Treatment with bonite Sponge:

Fe)04 -I- 6H2S - 3FeS2~ + 4H20 + 2H2 r pH less than 7 .. .0

TRIEATM'ENT OF OXYG'EN liN ~DRILUNG FLUIDS WITH O'S~ 1 (SODIUM SULFI,TIE CATAILYZED WITH' CO,BALT CHLORIDE),:

Na2S03 + 11202- Na2S04

ACIDIFICATIIONI

Siderite upon acidification with muriatic acid::

FeCO) + 2HCI- feCh + C02." + H20

LoWate upon acidification with muriatic acid:

CaC03 + 2HCI - CaCh + CO2 t + H20

COj AND IHC'O; CONITAM.IINATI,ON

Bicarbonates and carbonates may be reacted with calcium; however. since calcium bicarbonate Ca(HC01)Z is soluble. all bicarbonates must be converted to. carbonates before the insoluble precipitate calcium carbonate can be formed. These reactions may be carried out under conditions of constant pH (if pH is, higb enough) or by increasing the pH in the presence of calcium.

Lime Ca(OH)2 is preferred for converting HGOl to CO; and then precipitating of the carbonates as CaC03 if the pH will not be elevated to a point that severe flocculation of clays becomes a problem.

HCO; + Ca(OHh ~ CaC03 1 + OH- + H20 CO;' + Ca(OH)2 "#- CaC031 + 20H-

When a constant pH value must be maintained, a combination of gyp and lime treatments are required ..

Ca(OH)2 + 2HCO- - CaC03 + CO~ + 2H20 CaS04.2H20 + CO) '" CaCO) l + SO~ + 2H20 PHOSPHATES

SAPP. when solubilized, precipitates calcium according to the following reaction:

NazH2P207 + H20 - 2NaH2PO,*

2NaH2P04 + 3Ca(OHp- Ca3 (P04pl +4A20+2NaOH SOLIDS

Solids •. the root of most mud problems, wiU be considered in another handout entitled: Soll;ids.

LIGNITES' EFFECT ON CALCIUM,

Lignites aU contain calcium as part of their inherent chemical makeup. Lignites also have the capability to tie up calcium. These floes of calcium can be removed from solution by mechanical means; therefore, the filter paper in an .API filterpress wiD contain some calcium after a fluid loss has been run.

Calcium both inherent and complexed by lignites

MAGCOBAR TECHNICAL MEMORANDUM

is. therefore, not available for reductions in mud systems. Although you may show calcium presence in your titrations, you may simultaneously be experiencing a CO)' or HeOl problem when drilling with a lignite mud.

BENTONITE

At temperatures greater than 2500 F, flocculation of bentonite clays occurs, causing rheology problems, For this reason bentonitic day concentrations (added or drilled), must he maintained at the absolute minimum concentration in areas where the downhole temperature is greater than 2500 F. This may be illustrated by the addition of several sacks of gel to raise the viscosity prior to logging or running casing. The gel additions will give the desired viscosity increase to the mud on the surface, but downbole the temperature has increased the yield of the bentonite to a level where the mud becomes a viscous, unpumpable medium. Polymeric materials should be utilized to elevate viscosity values in the above instance because they demonstrate a reduction in viscosifying effect at elevated temperatures.

STOICtffQ IIU ~ REJU!TIONI

A molar solution IS a solution whic contains(lfne mole of solute per kilogram of 50 vent. The term mole is simply an abbreviation for gram- olecula weight. Thus a 1 molal solution ofNaOH woul b 'W grams of NaOH per 1000 grams of water.

MOLAR

If. solution which contains one rfi'Ole of solute per It-fer of solution is called a molar solution. Thus 0.1 molar Hel is a hydrochlori acid solurion which contains 1/10 mole or .646 grams of hydrogen chl r= lide per liter.

EQUIVALENIT PARTS PER MILLION (EMP)

he Equlvalen Weight is defined as die atomic or formula weign of an element. compound. or 10n divided by its positive valence. For example, the molecular weight of CI is 36.5 and since the valence of hydrogen is 1, then the equivalent weight IS 36.5.

The molecular weight of H2S04 is 98 and since [he valence of hydrogen which is taken twice is Q, t e e equivalent weight is 98/2, or 49.

BALANCING AN EQUATION

One of the first steps involved in stoichiometric reactions is to balance the equation involving the reactants and products .. Assuming the reactants and products are known, the best approach in balancing an equation is to single out one element of known valence and balance the entire equation on the basis of that element. Many elements assume more than one valence which often times presents problems to the beginner in balancing equations. More often than not, oxygen is the element that is used to balance the equation. Consider the followin~ equation involving the reaction between iron (Fe+ ) and oxygen (02) producing iron oxide:

fe ++++ 02 - Ft2+++ 0) iron oxygen iron oxide

One can easily see that the above reaction is not in balance with the charges. There is more oxygen on the right than on the left. To balance this equation we will concentrate first upon balancing the oxygen atom, then the iron (ferric) atom. We see that we have 4 negative charges on the left and 6 negative charges on the right. If we place a 2 in front of the iron oxide and a 3 in front ofrhe oxygen, we see that the equation then becomes:

Fe+-++ + 302 - 2FerO~

The oxygen atoms are now balanced. As a result of balancing the oxygen atoms there are now two Ft2++-;; atoms on the right or a total of twelve positive charges. In order to complete the balance there must be twelve on the left so the equation finally becomes:

4fe +++ + 30~ - 2FC!2+++ 03

4 moles + 3 moles = 2 moles

This is a. t,rial and error procedure and sometimes becomes quite involved. Consider the following additional problem:

How many grams of oxygen would be required to react with 140 grams of iron to produce iron oxide? The solution to this type of problem employs the use of ratio and' proportion.

AtomicWt. Fe = 55.85 Atomic Wt. 0 '" 16 140 gms x gms

4Fe + 303 ..... 2Ft203

4 moles + 3 moles = 2 moles 4 x 55.85 - 6 x 16

223.2 gms 96 gms

Setting up the ratio and proportion gives: 223.2 gm Fe _ 96 gm 02

140gmFe X

X = (140 gmFe)(96 gm02) =60.3 gm Os 223gmFe

Therefore, it takes 60.3 gms of oxygen to react with 140 gms of iron to produce iron oxide.

Consider the problem of involving the treatment of lime for bicarbonate. The unbalanced reaction is

MAGCOBAR TECHNICAL MEMORANDUM

as fellows:

HC01+ Ca(OH)2 _.. CAC03 ! + CO) + H20 Treating this example the same as the previous one and concentrating on the ,oxygen atom, we have the following balance equation:

HCO; + 112 Ca(OHp -1I2CaCOJ! +H20+0K Thi:s equation tells us that 2 equivalents of carbonates are formed from one equivalent of bicarbonate. Therefore, it would take a 2 to 1 eqeivalenr ratio of lime and bicarbonate in the precipitation reaction.

An example involving com;positiions and 'can-

c·entr·a,tlons would be as follows:

a) Composition in weight per cent

b) Volumetric per cent of water

c) Molality

d) Pounds NaCI per pound H2

Basis of calculation: 1000 cc of solution Total Weight= 1(00)( 1.148 = 1148 gms.

NaCl =230 gros

H20 = U48 - 230 = 918gms

a) Composition in weight %

Weight % NaCl = (230/U48) x 100= 20.0% Weight % H20 = (918/1148) x 100 '" 80.0% b) Volumetric per cent water

Density of pure

water at'200C= 0.998 gms/cc Volume of

pure water = 918/ .998 '" 920 cc Volumetric %

of water =(920/10C(0)x 100=9.20%

c) Molality

The gram-moles of NaCl ;;;;

Wt. NaCI 230

;;----

Mol. wt. N aCl 55.8

;; 3.93 gm-moles

Since by definition molality is moles of solute per kilogram of solvent and since there are 91B gms of solvent and not 1000 gms, then the correct number of gram-moles of NaCl is:

1000 _ -

3.93;;-- 4.28 gm-moles NaCl per 1000 gms water

918 - -

d) Pounds NaCl per pound H20

230

lh. NaC1 per lb. H20 '" 918 ;; 0.251

R,EPO:RTI'NG UNITS AND CO:NVERSIIONS The foHowing is a reproduction of an entry in API Bulletin 0 11, "Glossary of DrilHng Fluid and Associated Terms."

PPM or Part Per Million-s- Unit weight of solute per million unit weights of solu-

don (solute plus solvent), corresponding to weight-percent except that the basis is a million instead of a hundred. The results of standard AP~ titrations of chloride. hardness" etc. are correctly expressed in milligrams (mg) of unknown per liter but not in ppm. At low concentrations, mg/t is about numerically equal to ppm,. A correction for the solution specific gravity or density in g/ml must be made as follows:

mg/I

ppm .. -__:::;.--. sola den. glmI

mg/l

%bywt.- _ - _ ,

(10,000}(soln den •. glrol)

ppm

B::-_=_ --::

W,OOO

Thus, 316,000 rng/l salt is commonly called 316,(H)0 ppm or 31.6 percent, which correctly should be 264,000 ppm and 26.4 percent, respectively.

, Equivalents per liter= Eq/l=

gil

Eq. W.

•. Equivalents per minion" epm= ppm Eq. w.

Equivalent Weight = Eq. W.= M,W./Valence .Gram-Mo]e" gM.oI '" Molecular weight in grams MiUiequivalents per liter

.. meq/I = (mOO)(.eq.ll) '" (10(H)).{gll ) Eq. W.

Milligrams per liter = mg/l ;; (ppm)(s.g.) MiUim.oles pel!' liter .. m mol/I

.. (1000)(mo]/l) = (1000) (g/l. ) M.W.

Molecular Weight= M .. W ... Sum of atomic weights .. -'of an element or compound.

• gil

Moles per liter .. mol/I .. -_ --.

M.W ...

mg/I arts per million '" ppm - s.g.

Specific gravity = s.g,

density sample .' .

"',. (at same conditions)

density water

Si.. Weight percent=wt%= ppm _ mgt]

,.. 10,000 (s.g.)(W,OOO)

EPM to pounds per barre]

Molecular weight 350.

x - pounds per barrel

1,000,000

." valence