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Drilling Fluids

---The Lifeblood of the Well

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Drilling fluids should:


Remove cuttings from the bottom of the hole and carries them to the surface Hold cuttings and weight material in suspension when circulation is interrupted Release sand and cuttings at the surface Wall the hole with an impermeable cake Minimizes adverse effects upon the formation Cool and lubricates the bit and drill string

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Drilling fluids should:


Support part of the weight of the drill stem and casing Control subsurface pressure Transmit hydraulic horsepower Maximize down hole information obtained Transmit electronic data from down hole tools. Help preserver and protect the drill string and casing
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Drilling fluids should not:


Be harmful to personnel nor the environment Interfere with formation evaluation Damage the production rate from the formation Cause corrosion of the drilling equipment and subsurface tubulars

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Why concern?
All drilling problems are related to drilling fluids Many wells are abandoned because of poor drilling fluids Costly

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Drilling fluids are selected on the basis of:


The types of formations (shaleyness) to be drilled The range of temperature and pressure encountered The type of formation evaluation needed The water quality available Ecological and environmental considerations And, $$$$$$

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LIQUIDS

GAS

GAS-LIQUID MIXTURES

AERATED WATER

FOAM

WATER_BASE MUD

OIL_BASE MUD

AIR

NATURAL GAS

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Water Base Mud Compositions

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Water Base Mud


Water phase can contain many different dissolved chemicals Oil is seldom used today, because of ecological considerations Active solids (clays) are affected by the water present Inactive solids(both low and high gravity) increased the viscosity of the mud
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Oil Base Mud Compositions

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Oil Base Mud


Diesel or Mineral Oils are used The emulsified water phase contains salts for osmotic control All solids affect the viscosity of the mud

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Gas Base Mud


Used when the low hydrostatic pressure are possible Under-Balanced Drilling

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Drilling Fluids Chemistry


Reading Assignment
Chap 2.1.4, 2.1.6, 2.1.7, 2.1.8, 2.1.9 Chap 2.3.5, 2.3.6

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Ionization & pH
Ionization:
Breaking up of a molecule into negatively charged anion and positively charged cation Example:
NaCl => ionizes into Na+ and Cl CaCl2 => Ca2+ + 2Cl-

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I dissolve 1 mole of CaCl2 in water, CaCl2=Ca2+ + 2Cl So, I get 1 mole of Ca2+ and 2 moles of Cl If the total volume of solution is 1 liter, then the concentration of Ca2+ is 1M The concentration of Cl- is 2 M.

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Ion Product of Water


For water Kw=[H+] x [OH-]=1x10-14 remains constant in any aqueous solution (room temperature and pressure). For pure water, [H+]=[OH-] [H+]2=10-14=>[H+]=[OH-]=10-7 M

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pH
H2O is slightly ionized H2O H+ + OH pH is the negative log of [H+]
pH= - log[H+]

For pure water


pH=-log[H+]=-log(10-7)=7

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pH
pH<7 pH=7 PH>7 [H+]> [OH-] [H+]= [OH-] [H+]< [OH-] Acidic Neutral Basic

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pH Measurement
pH paper
Dyes color compare to the standard color

pH meter
Measure the electropotential generated between a special glass electrode and a reference electrode. Must be calibrated using buffered solutions of known pH
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Example 2.2
Compute the amount of caustic (NaOH) required to raise the pH of water from 7 to 10.5 (the molecular weight of caustic is 40) Solution: Kw=[H+] x [OH-]=1x10-14 pH=-log[H+][H+]=10-pH [OH-]= Kw/[H+] = Kw/10-pH= 1x10-14 / 10-pH = 10pH-14 [OH-]2-[OH-]1= 1010.5-14- 107-14=3.161x10-4M Molecular Weight of caustic (NaOH) is 40 40x3.161x10-4=0.0126g/L is required.
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Concentration
Molality---the number of gram-moles of solute per kilogram of solvent Molarity---the number of gram-moles of solute per liter of solution Normalitythe number of gram equivalents of the solute per liter of solution [one gram equivalent weight(gew) is the weight of the substance that would react with one gram-mole of hydrogen]

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Concentration
Parts per million(ppm)---the number of grams of solute per million grams of solution Milligrams per liter---the number of milligrams of solute per liter of solution Percent by weight---the number of grams of solute per 100 grams of solution

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Example 2.4
A CaCl2 solution is prepared at 68F by adding 11.11g of CaCl2 to 100 cm3 of water. At this temperature, water has a density of 0.9982g/cm3 and the resulting solution has a density of 1.0835g/cm3. Express the concentration of the solution using:
Molality Molarity Nomality Parts per million Milligrams per liter Percent by weight
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Solution The molecular weight of CaCl2 is:


40.08+2x(35.457)=111 (Table 2.2) CaCl2 : 11.11/111=0.10009 moles Water: mass=density x Volume=0.9982x 100=99.82 grams molality=0.10009/(99.82/1000)=1.003 g-mol/kg The volume of solution is: (11.11+100)/1.0835=102.38cm3=0.10238Liter molarity=0.10009/0.10238=0.9776 g-mol/L

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Since 0.5 mol of CaCl2 would tend to react with 1 mol of hydrogen, the gram-equivalent weight of CaCl2 is half of the molecular weight. Thus, normality=11.11/(111/2) /0.10238=1.9553gew/L parts per million=11.11/(11.11+99.82)x 106 =100153ppm milligrams per liter=11.11x 1000/0.10238 =108517mg/L percent by weight=11.11/(11.11+99.82)=0.1002 =10.02%
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Alkalinity
The ability of a solution or mixture to react with an acid. Filtrate Alkalinity Pf=Phenolphthalein end point of the Filtrate, pH=8.3 Mf=Methyl orange end point of the Filtrate, pH=4.3 Quantifies amount of alkaline materials in the liquid phase Whole Mud Alkalinity Pm= Phenolphthalein end point of the Mud, pH=8.3 Mm =Methyl orange end point of the mud, pH=4.3 Quantifies amount of alkaline materials in the solid plus liquid phase
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Why do we measure Alkalinity?


To determine the amount of alkaline ions. Is the OH- ion the only alkaline ion in water muds?
CO32- and HCO3- can react with H+ CO32-+ H+ = HCO3 HCO3-+ H+ =CO2+HOH

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Why do we measure Alkalinity?


To estimate amount of : carbonate (CO32- ), bicarbonate (HCO3-), and hydroxyls (OH- )
If Pf=0, the alkalinity is due to bicarbonate alone If Pf=Mf, the alkalinity is due to hydroxide alone If 2Pf>Mf, the alkalinity is due to a mixture of carbonate and hydroxides. If 2Pf<Mf, the alkalinity is due to a mixture of carbonate and bicarbonates. Mud alkalinity allows estimate of lime (Ca(OH)2) content of a mud.

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Converting Ca(OH)2 Concentration from 0.02N to Field Units of lbm/bbl


Molecular weight=40.08+2x(1.008+16)=74.10 0.5mol Ca(OH)2 can react with 1 mol of hydrogen=>the gram-equivalent weight of Ca(OH)2 is half the molecular weight (37.05g/gew)
0.02 gew 37 .05 g 0.35lbm / bbl 0.26 lbm / bbl 1L gew g/L

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Free Lime
All values (Pm, Pf, Mm, and Mf) are reported in cm3 of 0.02N (normality=0.02) sulfuric acid per cm3 of sample Pm and Pf indicate the reserve alkalinity of the suspended solids Free lime is given by: 0.26(Pm-fwPf) fw is the volume fraction of water in the mud

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Example 2.5
A drilling mud is known to contain Ca(OH)2. The alkalinity tests are conducted to determine the amount of undissolved lime in suspension in the mud. When 1cm3 of mud filtrate is titrated using 0.02N H2SO4, 1.0 cm3 of H2SO4 is required to reach phenolphthalein endpoint and 1.1 cm3 of H2SO4 is required to reach the methyl orange endpoint. When 1cm3 of mud is diluted with 50cm3 of water before titration so that any suspended lime can go into solution, 7.0cm3 of H2SO4 is required to reach the phenolphthalein endpoint. Compute the amount of free lime in suspension in the mud if the mud has a total solids fraction of 10%

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Solution Pf=1.0cm3 and Mf=1.1cm3 Because both Pf and Mf have approximately the same value (Pf=Mf), the alkalinity is due to hydroxide alone. Pm=7.0cm3 Volume fraction of water=1-0.1=0.9 Free lime=0.26(Pm-fwPf) =0.26(7.0-0.9*1.0)=1.59lbm/bbl

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Acids, Bases, Salts and Buffered Solutions


Acids--- Compounds that yield hydrogen ions (H+) when dissolved in water; they react with bases (example: HCl) Bases--- Compounds that yield hydroxyl ions(OH-) when dissolved in water; they react with acids (example: NaOH) Salts--- Compounds that make a neutralization reaction of an acid with a base---forming HOH as a byproduct (example: HCl+NaOH=NaCl+HOH)

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Acids, Bases, Salts and Buffered Solutions


Strong acid or base---acid or base that dissolves in water and is almost totally ionized to H+ or OH- (example: HCl, NaOH) Buffers---A buffer is a weak acid(base) plus a salt of that acid(base). Solutions that contain water soluble compounds that ionize to form either H+ or OH- or a weak anion to hold pH nearly constant if an acid or a base is added. Muds often contain buffer compounds. (example lignite)
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Solubility
Solubility
Some chemicals are soluble and often ionize when they dissolve in water (example: NaOH). Ionization is the formation of positive and negative parts of the molecule Soluble does NOT mean Ionize

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How does Solubility Help Us in Muds?


Solubility allows reactions to occur and contaminates to be removed (example: Cl- from formation) Water solubility of chemicals is the key to water mud control because some additives must be soluble in order to be effective (e.g. NaOH, lignosulfonate, polymers). Other additives must be insoluble (e.g. BaSO4). Insolubility of compound is an effective means for removal of unwanted ions from the mud. (example: we add soda ash to remove Ca++ from a mud)
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Chloride Concentration
Salt can enter and contaminate the mud system when salt formations are drilled Determined by titration with silver nitrate solution (AgNO3) Ag+ + Cl- AgCl (white precipitate) Endpoint of titration is detected by using a potassium chromate indicator (K2CrO4) 2 Ag+ + CrO42- Ag2CrO4 (Orange-red precipitate) AgCl is less soluble than Ag2CrO4
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Chloride Concentration
0.0282 N AgNO3 solution is used for titration The concentration of Cl- in the filtrate is given by:
1 cm3 filtrate is used in the titration Ag+ + Cl- AgCl 1 : 1=> 0.0282Vtf moles of Cl- per cm3 Vtf is the volume of AgNO3 required to reach the endpoint 0.0282Vtf N Cl- 0.0282Vtf x 35.46g That is, Vtf g/L or 1000 Vtf mg/L ClPE3043-FALL/2004-Page 38

Chloride Concentration
If the Cl- ions are produced by NaCl, the concentration of NaCl is given:
0.0282Vtf N NaCl 0.0282Vtf x 58.46 Or, 1.648Vtf g/ L1648Vtf mg/L NaCl

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Example 2.6
1 cm3 of mud filtrate is titrated using 0.0282N AgNO3. 9 cm3 of AgNO3 solution are required to reach the endpoint of the titration as indicated by K2CrO4 indicator.
Compute the concentration of Cl If only NaCl was present, compute the salinity of the filtrate in milligrams of NaCl per liter

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Solution 1. Vtf=9cm3
The Cl- concentration =1000Vtf=1000x9=9000mg/L

2. The NaCl concentration is given by


1648Vtf=1648*9=14832 mg/L

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Water Hardness
Water containing large amount of Ca2+ and Mg2+ ions is known as hard water
Ca2+ can enter the mud when anhydrite(CaSO4) or gypsum(CaSO42H2O) formations are drilled Cement also contains Ca2+

Determined by titration with a standard(0.02N) Versenate (EDTA) solution

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EDTA+Ca2+ EDTA chelate ring The chelate ring structure is quite stable Eriochrome Black T +Mg2+ wine-red complex
If a solution contains both Ca2+ and Mg2+, Versenate first forms a Calcium complex then Magnesium complex.--depletion of Mg2+ from Eriochrome Black T dye causes the color change from wine-red blue

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The equivalent weight of CaSO4 is 68.07 Using 0.02 N EDTA,


0.35lbm / bbl 0.02 gew / L 68 .07 g / gew 0.477 lbm / bbl 1g / L

The total CaSO4 concentration is given by 0.447Vtm Where Vtm is the titration volume in cm3 per cm3 of mud sample The Free CaSO4 in pound per barrel is given by 0.477(Vtm-fwVtf) Vtf is the titration volume in cm3 per cm3 of mud filtrate
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Example 2.7
Compute the total calcium concentration of the mud expressed as pounds per barrel of CaSO4 if 10 ml of 0.02N Versenate solution was required to titrate a 1 cm3 sample of mud.

Solution The total CaSO4 concentration is given by 0.477Vtm=0.477*10=4.77lbm/bbl

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Dispersion
Oil disperses into water, but requires a specific type of emulsifier (surface-active agent) to generate very small diameter oil droplets which remain permanently dispersed. Volume of oil phase should be less than volume of water phase Water disperses into oil with shearing, but requires its own specific type of emulsifier chemical. (example: oil muds use Fatty Acid emulsifier). Volume of water must be smaller than volume of oil (Usually)
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Clays
Clay behavior is critical to polymer muds Clay in mud strongly influence rheology and filter cake quality Clays in shales dictate needs for special wellbore stability chemicals such as inhibited muds, high density muds, etc. Clays have both positive and negative electrical charges and are therefore chemically reactive. The negative chargeson clay surface The positive chargeson broken crystal edges
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Why do clays have electric charges?


Isomorphous substitution in clay crystal structure gives clays their negative face charge
Cations on the face are exchangeable, one for another, size and hydration state of cations are important factors to how a clay, such as smectite, behaves Na-Smectite clays are mud additives. Called gel or sodium bentonite. Very hydratable and dispersible. Also called sodium montmorillonite

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Thinners
Thinners (deflocculants) are low molecular weight anionic(-) polymer which attach to positive(+) edge charges on clays.
Neutralization prevents flocculation between clay particles Reduces adverse effects such as excessive viscosity and thick, sticky filter cakes Example: Lignosulonates

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Extenders
Extenders (flocculants) are high molecular weight anionic polymers. They attach to the positive edge charges of clays and drill solids forming flocs
Thousands of (-) groups on a polymer can link huge numbers of particles into a network This process will extend Na-Bentonite as a viscosifier (but not as a filtration agent) It provides a means for making a low solids mud for faster drilling

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Cation Exchange Capacity of Clays


Determine the amount of easily hydrated clay present in the solids Sodium montmorillonite was often added to the mud to increase the viscosity and cutting carrying capacity Methylene blue (C16H18N3SCl3H2O) test
The test is only qualitative

Reported in milliequivalent weight (meq) of methylene blue per 100ml of mud 0.01N methylene blue solution was used in titration
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Surfactant Chemicals in Muds


Surfactants change surface tension between gas-oil, oil-water, oil-solid, water-solid, etc. In muds, they serve as :
Emulsifiers Defoamers Foamers Corrosion inhibitors Spotting flluids and Lubiricants
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Emulsifier
Emulsifier molecules have two or more functional group. One group help with hydrocarbon phase (oil phase) and the other with water or brine (water phase) These molecules orient themselves tightly around water droplets or oil droplets

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Chemical Additives
pH control Viscosity control Filtrate control

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pH Control Additive
Caustic(NaOH) pH control A high mud pH is desirable to suppress
corrosion rate Hydrogen embrittlement Solubility of Ca2+ and Mg2+ the high pH is a favorable environment for many organic viscosity control additives

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pH of Mud Additives
Chemical
Slaked lime, Ca(OH)2 gypsum, CaSO4.2H2O Soda ash, Na2CO3 Caustic soda, NaOH

pH of solution
12 6 11.1 12.9

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Deflocculants---Thinners
Table 2.10 Phosphates Tannins Lignins Lignosulfonates

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Deflocculants---thinners
Phosphates should not be exposed to temperature in excess of 175F
Phosphates revert to orthophosphates and become flocculants at high temperature.

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Chemical Removal of Contaminants


Chemical contaminants can cause serious Rheological or drilling problems to develop Common contaminants are:
Calcium Magnesium Carbon dioxide Hydrogen sulfide Oxygen

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Calcium
Sodium montmorillonite calcium montmorillonite flocculationaggregation of montmorillonite Calcium can enter the mud in many different forms:
Soft cement Gypsum Saltwater flows Hard water additions lime

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Calcium
Can be removed by adding soda ash (Na2CO3) Ca2+ + 2OH- +Na2CO3CaCO3 +2 Na+ +2OH Or sodium acid pyrophosphate (SAPP) Ca2+ + 2OH- +Na2H2P2O7 Ca2P2O7 +2 Na+ +2OH- + 2H2O Or sodium bicarbonate Ca2+ + 2OH- +NaHCO3 CaCO3 + Na+ +OH- + H2O
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Magnesium
Can be removed by adding sodium hydroxide (NaOH) Mg2+ + 2NaOHMg(OH)2 +2Na+

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Carbon Dioxide
CO2 + H2O H+ + HCO3- 2H+ + CO32 Can be removed by adding Ca(OH)2 CO32- +Ca(OH)2CaCO3 + 2OH Presence of Calcium is preferred over the presence of carbonate, therefore most operators maintain 50-70 ppm calcium level in water based muds
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Hydrogen Sulfide (H2S)


Cause hydrogen embrittlement of the steel Harmful to personnel working at the surface H2S H+ + HSHS- H+ +S2-

Can be removed by adding Zinc ions S2-+ Zn2+ ZnS


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Oxygen
Accelerate corrosion processpitting of pipe and loss of excessive amount of metal Enters the mud in the surface pits
Can be removed by adding sodium sulfite O2 +2Na2SO3 2Na2SO4

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Example 2.14
A titration test has shown that a drilling mud contains 100mg/L of Calcium. The mud engineer plans to add enough Soda Ash (Na2CO3) to his 1500 bbl system to reduce the concentration to 50mg/L. Determine the amount of soda ash he should add to each barrel of mud for each mg/L of calcium present in the mud. Also determine the total mass of soda ash needed in the desired treatment.
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Solution
Ca2+ CO32-CaCO3 1 : 1 [Ca2+]=1mg/L=0.001/40mol/L=2.510-5mol/L [CO32-]= 2.510-5mol/L Molecular Weight of soda ash (Na2CO3)=2*23+12+3*16=106 [CO32-]= 2.510-5mol/L= 2.510-5106g/L0.35L/eq bbl =9.275 10-4 g/eq bbl For 1500 bbl, the amount of soda ash needed: 9.275 10-4 1500 (100-50)=69.6 lbm

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