Sie sind auf Seite 1von 49

CHAPTER 2

MUD TESTING PROCEDURES

Page 2-1
CHAPTER 2

MUD TESTING PROCEDURES


In order to insure that the mud has optimum properties, certain standard tests are
performed. These tests are used to make sure that the mud properties necessary for a successful
drilling operation are achieved and maintained. The tests are also used as a tool to aid in
diagnosing mud related problems. Detailed procedures concerning most of the following tests
may be found in the American Petroleum Institute publication API RP 13B. If any questions
arise concerning the procedure, this would be an excellent reference to check.

PHYSICAL TESTS

CORROSION TEST:

CORROSION RING

A. Description & Equipment

1. The placement of corrosion ring coupons in the drill string is one of the most common
techniques used to evaluate the corrosiveness of the drilling fluid on the drill string and other
steel components. The rings are used to determine the type of corrosion, whether it is
localized pitting or a generalized attack. This method does not give reliable information
about hydrogen embrittlement, stress corrosion cracking, etc. The corrosion rings are
usually cut from metal similar to that used in making drill pipe.

2. The rings are stamped with a serial number for identification. They should be briefly
inspected for atmospheric corrosion before insertion into the drill string. The rings should
not be removed from the sealed wrappers until immediately before placement into the drill
string.

B. Test Procedures

1. Usually two rings are used for the corrosion determination. They are placed in the box recess
of the tool joint. One is put in the string near the bottom, usually in the crossover sub from
drill collars to drill pipe. The other ring is placed in the string near the surface, usually in the
kelly saver sub. The serial number of each ring and its location should be recorded on the
envelope the rings come in.
2. The rings should be in the drill string for 40 hours minimum and ideally for about 100 hours.
3. When finished, the coupons should be carefully removed from the drill string.
4. The mud should be wiped off each ring and then it should be visually inspected
immediately .
5. The field visual inspection should include determining the type of corrosion present, if any.
This inspection can quickly tell if there is generalized or localized attack as well as some
degree of the severity of attack. The following procedure can be used to determine if the
corrosion by-products are iron sulfide, iron carbonate, or iron oxide:

a. Scrape some of the material from the corrosion ring into a titrating dish.
b. Add a few drops of Iron Sulfide Detecting Solution
Page 2-2
c. If iron sulfide is present, the scrapings will turn bright yellow and a rotten egg odor will
be released
d. If iron carbonate is present, the scraping will effervescence slowly.
e. The absence of a bright yellow color or effervescence indicates the scrapings are iron
oxide.
6. From this test, a quick determination can be made as to whether the corrosion inhibitor
treatments need to be increased or changed.
7. If a more quantitative report on corrosion is required, the coupons should be dipped in light
oil, re-wrapped in the shipping envelope they came in, and submitted to a qualified lab for
detailed inspection. The lab will determine any corrosion by-products and calculate the
corrosion rate due to weight loss.

C. Calculations

a) Corrosion Rate, g/m2×d = wt.loss, mg x 240 / surface area, cm2 x hours exposed

b) Corrosion Rate, mm/a = wt. loss, mg x 11.2 / surface area, cm2 x hours exposed

c) Corrosion Rate g/m2×d = 21.4 x Corrosion Rate, mm/a

d) Corrosion Rate, mm/a = 0.05 x Corrosion Rate, g/m2×d

D. Remarks

1. The importance of the quick field inspection cannot be overstressed. Obvious problems with
corrosion can be kept to a minimum with early treatments, before lab results are obtained.
2. It is also important that extreme care be taken when placing the corrosion rings in the drill
string. Any mechanical damage resulting from improper placement will influence the
corrosion rate calculation since they are based on coupon weight loss. If the plastic coating
on the ring is damaged or absent the ring should not be used.
3. The coupons should be clean before placement in the drill string. Also, if a serial number is
stamped on both the coupon and the envelope it came in, check to see if the two numbers
match. All the information on the envelope should be filled out.

Page 2-3
PRE-STRESSED BEARINGS

A. Description & Equipment

A method to detect the presence of hydrogen sulfide is to use pre-stressed roller bearings.
They measure the hydrogen embrittling tendencies of the mud due possibly to H2S. These
coupons have been pre-stressed with a 280,000 kPa load. When the coupon comes in contact
with H2S, it will crack due to this stressed condition. Unfortunately, they also can crack for
other reasons. However, if they do not crack, then H2S is definitely not present in the mud. So
when pre-stressed bearings are used and one is found to be cracked, this indicates a strong
possibility that H2S is present but it is not a guarantee. If the test indicates the possibility of
H2S, then other tests should be run to confirm the presence of H2S and to determine the amount
present.

B. Procedure

Usually a couple of the coupons are placed into a porous sample bag and anchored in the
mud flow line. Periodic observations will detect any cracks that appear in any of the bearings.
If cracks start to show up, then H2S should be suspected and other tests should be run to confirm
it.

FLUID LOSS:

STANDARD LOW PRESSURE (API)

A. Description & Equipment

The filtration and wall building properties of the mud are determined by means of a filter
press. The volume of filtrate depends on many factors, as is illustrated by the following
equation:

V = KAP / YT

V= flow rate
A= area (cm3) of membrane or cake
P= pressure (kPa) differential across cake or membrane
Y= viscosity (assume 1 mPa.s for water) of fluid passing through the cake
T= thickness (mm) of the cake
K= constant of permeability

Page 2-4
Measurements made with the filter press give an indication as to what is going on down
hole. Due to temperature and pressure differences, cake thickness and permeability variations,
results may be different from what is indicated by surface tests.
Another observation besides filtrate volume is the deposition of a filter cake. The filter
cake results from the suspended solids in the mud being deposited on a porous medium under
pressure. The quality and visual appearance of the filter cake is almost as important as the
filtrate volume.

B. Procedure: Fann MB & 12B Filter Press

1. With the cell (dry) upside down, and a finger over the small hole in the other end, fill the
cell to 0.5 cm from the top with a freshly stirred sample of mud. (This conserves CO2 gas).
2. Check to insure that the rubber O-ring is in place. Place filter paper on top, put cell cap on
and lock. Install cell onto regulator assembly.
3. Place a clean, dry, graduated cylinder under the filtrate drip tube.
4. Apply 700 kPa (100 psi) pressure to the cell and filter for 30 minutes.
5. At the end of 30 minutes, collect the remaining drop on the drip tube, release the pressure
and record the volume in cm3 of filtrate collected.
6. Wash parts thoroughly after each use. (Important when using Inhibitive, Gyp or Saline
fluids)

C. Remarks

These tests are designed to filter for 30 minutes through a filtration area of 45.8 ± 0.6
cm2. The 30 minute fluid loss can be estimated by doubling the filtrate collected in 7.5 minutes.
The mathematical equation below allows an approximation of the filtrate volume at some future
time if the volume collected in some shorter time is known.

Q2 = Q1 x (square root of (T2 / T1))

Q2 = Estimated Filtrate at Time T2, cm3


Q1 = Known Filtrate at Time T1, cm3
T1 = usually 7.5 minutes
T2 = usually 30 minutes

D. Procedure: Mini Press

1. With rubber liner installed, fill the cell (dry) to 0.5 cm from the edge with a freshly stirred
sample of mud. Install screw-on base.
2. Attach to support bracket, and place graduated cylinder under the filtrate drip tube.
3. Apply 700 kPa (100 psi) pressure for 30 minutes. At end of 30 minutes release the pressure
and record the volume in cm3.
4. Wash thoroughly after each use. (Important when using Inhibitive, Gyp or Saline fluids)
5. The Mini-Press has half the area of the regular API Press (22.9 cm2) therefore the volume
collected through the half area or Mini-Press must be doubled to correct it to the standard
full size (API) filter press area. It is not advisable to run this unit for 7.5 or 15 minutes.

Page 2-5
E. Filter Cake

Upon dismantling the cell, the filter cake should be examined. Quality of the cake
should be noted, such as hardness, softness, texture, compressibility and recovery, and flexibility
should be made. The thickness of the cake should be reported in millimeters. A cake thickness
of less than 2 mm is usually considered acceptable.

HIGH PRESSURE / HIGH TEMPERATURE

A. Description & Equipment

The equipment and test is very similar to the standard test except that this test is run at an
elevated temperature (to simulate bottom-hole temperature) and a higher pressure differential
(usually 3500 kPa). Since the test is run at elevated temperature and pressure, the cell
containing the mud must be designed to withstand a working pressure of at least 10350 kPa
(1500 psi). Also due to the elevated temperature, a pressurized collection device that is capable
of withstanding a back pressure of at least 3500 kPa (500 psi) must be used.

B. Test Procedure

1. Connect the heating jacket to a 110V electrical outlet. Place a thermometer in the
thermometer well and preheat the heating jacket to the desired test temperature.
2. Load the cell with mud from the flowline or a freshly stirred sample. Care should be
exercised not to fill the cell closer than 2 cm from the top to allow for expansion as the mud
heats.
3. Insure rubber O ring is in place, then add filter paper on top.
4. After tightening down the end cap, place the cell into the heating jacket with both top and
bottom valve stems closed. Transfer the thermometer to the thermometer well in the cell.
5. Place the pressure regulator on the top valve stem and lock it in place. Place the pressure
receiver on the bottom valve stem and lock it in place. Apply 700 kPa (100 psi) pressure to
the bottom receiver and 1380-2070 kPa (200-300 psi) pressure to the top regulator with both
valve stems closed. Open the top valve stem 1/4 turn, so pressure is applied to the mud
while heating to prevent water from boiling.
6. When the sample reaches the desired test temperature, open the bottom valve stem and
increase the top pressure unit to 4200 kPa (600 psi) to start filtration. Warning: If the
bottom receiver gauge starts to climb rapidly while increasing the pressure on the top
regulator, this indicates a no control situation. Close the bottom valve stem
IMMEDIATELY, as hot mud can spray out the pressure release valve. Collect filtrate
for 30 minutes, maintaining temperature and pressure as accurately as possible. Close bottom
and top valve stems. Record the total cm3 filtrate volume. (NOTE: The actual top and
bottom pressure combination is shown in Table 2.1).
7. Correct the filtrate volume to standard filtration test area by doubling the filtrate
volume collected in 30 minutes.
8. At the end of the test, make sure both valve stems are closed and both regulators backed off.
Bleed pressure from top and bottom pressuring units.

9. CAUTION: The HT-HP cell will still contain approximately 4140 kPa (600 psi) pressure.

Page 2-6
Maintain the cell in an upright position and cool to room temperature. Loosen the valve
stem on the solid end slowly and bleed pressure from the cell. Loosen the end cap locking
screws and then lift the cap out with a rocking motion using the valve stem as a handle.
10.Clean and dry the apparatus thoroughly after use.

C. Calculations

Since the filtration area is 22.9 cm2, the volume collected in 30 minutes must be doubled
in order to correct it to the standard filtration area of 45.8 cm2.

D. Remarks

1. The upper and lower limits of the pressure differential are determined partly by the test
temperature. As the test temperature exceeds 100°C, the back pressure must be increased to
allow for the increased vapor pressure of the water phase at the higher temperature. The
3500 kPa (500 psi) differential must be maintained, so the top pressure must be increased by
the same amount. Figure 2.1 shows the pressures recommended for various temperatures.

Figure 2.1
RECOMMENDED TOP PRESSURE AND BACK PRESSURE

Temperature Top Pressure Back Pressure

Deg C Deg F kPa psi kPa psi


To 90 to 200 3500 500 0 0
90-150 200-300 4200 600 700 100

2. Due to the high temperatures and pressures involved in this test, extreme care must be
exercised at all times. All safety precautions must be met, especially in the cell breakdown
procedure when the filtration is complete.

MBT (CATION EXCHANGE CAPACITY)

A. Description & Equipment

This test is designed to determine the amount of active clays such as Bentonite in a mud.
The cations on the clay particles are replaced with methylene blue cations. When the clays are
unable to exchange any more methylene blue cations, the excess dye left over in solution
indicates that the end point has been reached. The amount of methylene blue needed to reach
the end point for the particular sample is usually expressed as kg/m3 of Bentonite equivalent.

Page 2-7
This test requires the following materials:

Glass Stirring Rod


Pipettes, 1 cm3, 2 cm3, 10 cm3
2 cm3 syringe
Filter paper
Distilled water
Hot Plate
250 cm3 Erlenmeyer Flask
Methylene Blue solution
Hydrogen Peroxide solution (3%)
5N Sulfuric Acid

B. Test Procedure

1. Add 2 cm3 of a freshly stirred sample of mud to 10 cm 3 of distilled water in an Erlenmeyer


flask. Add 15 cm3 of 3% Hydrogen Peroxide and 0.5 cm3 of 5N Sulfuric Acid. Boil gently
for 10 minutes. Dilute to about 50 cm3 with distilled water.
2. Add Methylene Blue solution in 0.5 cm3 increments and swirl the mixture for about 60
seconds between additions of Methylene Blue. While the solids are still suspended, remove
one drop of liquid with a stirring rod and place the drop on a piece of MBT filter paper. The
end point of the titration is reached when dye appears as a greenish-blue halo surrounding
the dyed solids, figure 2.2.
3. When the greenish-blue halo spreading from the dyed solids is detected, shake the flask an
additional 2 minutes without adding any more Methylene Blue and place another drop on the
filter paper. If the greenish-blue halo is again evident, the end point has been reached. If the
halo does not appear after 2 minutes, continue Methylene Blue additions as before until a
drop taken after 2 minutes shows the blue halo.

C. Calculations

1. Methylene Blue Capacity

cm3 of methylene blue added / cm3 mud used in the test

2. Equivalent Bentonite Content,

kg/m3 = Methylene Blue Capacity x 14.25

D. Remarks

1. Muds can contain materials other than Bentonite, that absorb methylene blue. The additions
of Sulfuric Acid with Hydrogen Peroxide are intended to destroy the effects of materials
such CMS, polyacrylates, Lignosulfonates, and lignite’s.

Page 2-8
2. The CATION exchange capacity of clays and shales can be determined directly by the above
method. A weighed amount of clay or shale is dispersed in water with a high speed mixer.
The test then proceeds as above except that the hydrogen peroxide is omitted. The CATION
exchange capacity can then be expressed as mill-equivalents of methylene blue per 100
grams of clay.

Example: Sample Volume, 2 cm3


Endpoint, 7 cm3
Methylene Blue Capacity = 7 / 2
= 3.5

Equivalent Bentonite Content kg/m3 = 3.5 x 14.25


= 49.87
= 50.00 kg/m3

Figure 2.2
METHYLENE BLUE TEST ENDPOINT

Page 2-9
MUD DENSITY:

MUD BALANCE

A. Description & Equipment

Density is expressed in units of kilograms per cubic metro, kg/m3. Any instrument of
sufficient accuracy to permit measurement within +5 kg/m3 may be used. The commercial mud
balance is the instrument generally used. The mass of a mud cup attached to one end of a beam
is balanced on the other end by a counterweight that is free to slide along a graduated scale. A
leveling bubble is mounted on the beam to indicate when the instrument is balanced.

B. Procedure: Mud Balance

1. Set up the instrument case so that it is level.


2. Fill the clean, dry cup with the freshly obtained mud to be weighed.
3. Place the lid on the cup and seal it with a gentle twisting motion being sure some mud runs
out of the hole in the top of the cap.
4. Cover the hole in the cap with a finger, wash or wipe all mud from the outside of the cup and
arm then dry the balance.
5. Set the knife on the fulcrum and move the counterweight along the graduated arm until the
cup and arm are balanced, as indicated by the leveling bubble.
6. Clean and dry balance and lid.

NOTE: Gently tapping the bottom of the cup with the lid may aid in removing air.

C. Calculations

The SI density units are kg/m3 and can be found from three of the four different scales on
the balance by:

kg/m3 = lb/gal x 119.82


kg/m3 = lb/ft3 x 16.02
kg/m3 = Relative Density (g/cm3) x 1000

The fourth scale on the balance is a mud gradient scale with units of psi/1000 ft. The SI
unit for mud gradient is kPa/m.

kPa/m = 22.62 x psi/ft

Page 2-10
D. Precautions

1. Check calibration of the balance

Distilled Water = 1000 kg/m3

2. Make sure air bubbles have not been trapped in the mud. The appearance of a ring on the
bottom side of the lid indicates that the cup was not completely full of mud.
3. Clean and dry the mud balance thoroughly after use.

E. Shale Relative Density

1. Fill the mud balance with clean shale until it balances at 1000 kg/m3 with the cover on.
2. Fill the remainder of the balance with water then put the lid on. Record the total density.
3. The relative density of the shale is calculated from:

Shale Relative Density = 1000 / (2000 - Total Density)

PRESSURIZED MUD BALANCE

A. Description & Equipment

Density is expressed in units of kilograms per cubic metre, kg/m3. The pressurized mud
balance is the instrument used if there is entrained air or gases in the mud. Under pressure the
bubbles are greatly compressed providing an accurate volume. The balance has a lid with a
valve and a retaining ring to hold the lid in place, as well as a pump assembly for providing the
pressure. The mass of a mud cup attached to one end of a beam is balanced on the other end by
a counterweight that is free to slide along a graduated scale. A leveling bubble is mounted on
the beam to indicate when the instrument is balanced.

B. Procedure

1. Set up the instrument case so that it is level.


2. Fill the clean, dry cup with the freshly obtained mud to be weighed.
3. Place the lid on the cup, with the valve pushed down (open), and seal it with a gentle
twisting motion being sure some mud runs out of the hole in the top of the cap. Screw
retaining ring over lid.
4. Fill the pump with mud to be tested. With the balance on a stable surface place the end of
pump assembly on the end of the valve. Press down on the pump assembly firmly, then
force mud into the balance pushing down of the pump knob. While maintaining the pressure
on the knob, slowly pull up on the pump assembly until the valve comes up. Pull back
slightly on the knob, then remove the pump.
5. Wash or wipe all mud from the outside of the cup and arm then dry the balance.
6. Set the knife on the fulcrum and move the counterweight along the graduated arm until the
cup and arm are balanced, as indicated by the leveling bubble.

7. To release the pressure, with the balance on a stable surface, put the end of the pump

Page 2-11
assembly on the valve and push down forcing the valve down. Pull up slightly on the knob,
then remove the pump.
8. Clean and dry balance, lid and valve. To clean pump draw water in and out several times.

C. Calculations

The SI density units are kg/m3 and can be found from three of the four different scales on
the balance by:

kg/m3 = lb/gal x 119.82


kg/m3 = lb/ft3 x 16.02
kg/m3 = Relative Density (g/cm3) x 1000

The fourth scale on the balance is a mud gradient scale with units of psi/1000 ft. The SI
unit for mud gradient is kPa/m.

kPa/m = 22.62 x psi/ft.

D. Precautions

Check calibration of the balance

Distilled Water = 1000 kg/m3

RESISTIVITY

A. Description & Equipment

The measurement of electrical resistivity of a mud sample requires a calibrated resistivity cell,
an instrument for measuring the resistance of the sample in the cell and a thermometer for
measuring sample temperature.

By definition resistivity is the electrical resistance offered to the passage of a current. It is


usually expressed in units of ohm-metres and has a numerical equivalence to the electrical
resistance of a column of fluid one metre long and one square metre in cross section or ohms-
metres2/metre. Two general types of instruments are used to determine resistivity:

a. The direct indicating resistivity meter measures a sample's resistance and then internally
converts resistance to resistivity so that the reading taken from the meter is actually
resistivity.
b. A meter which measures sample resistance which has to be converted to resistivity in
which the cell constant for the instrument must be known. Then the sample resistance, in
ohms, is multiplied by the cell constant, in metres2/metre, to get sample resistivity.

Page 2-12
B. Procedure

1. Fill the clean, dry resistivity cell with a freshly stirred sample of mud or mud filtrate. It is
very important that no air or gas is trapped in the sample.
2. After connecting the cell to the instrument, determine the resistivity of the sample.

C. Calculations

1. Calculate the resistivity of the sample if a resistance-type meter is used. Otherwise, report
the resistivity of the mud, Rm, or filtrate, Rmf, in ohm-metres to the nearest 0.01 ohm-metre
as indicated by the dial. Also record the sample temperature.
2. To find the resistivity at any other temperature, use Resistivity Nomograph for NaCl
Solutions, Figure 2.3.
Figure 2.3

RESISTIVITY NOMOGRAPH for NaCl SOLUTIONS

Page 2-13
RETORT (Liquid & Solids Content)

A. Description & Equipment

A retort is used to determine the amount and types of liquids and the amount of solids in
the mud. Mud is placed in a steel container and then heated until the liquid portion has been
vaporized. The liquid vapor is passed through a condenser and then collected in a graduated
cylinder. The volume of the liquid, both oil and water, is measured. The results are reported as
a volume fraction basis.

B. Test Procedure

Fann MiniStill

1. Fill the lower chamber with a freshly obtained mud sample.


2. Place the calibration lid on the chamber allowing any excess mud to escape.
3. Remove the calibration lid from the chamber being careful not to remove any mud adhering
to the lid.
4. Add 5-6 drops of "liquid steel wool" to the mud in the sample cup, or pack steel wool around
the upper portion of the immersion heater.
5. Screw the lower retort chamber into the upper chamber while maintaining both chambers in
an upright position.
6. Screw the immersion heater into the cup/chamber assembly.
7. Attach the assembled retort to the condenser.
8. Add a drop of wetting agent (Aerosol) to a 100% by volume graduated cylinder and place it
under the drain of the condenser. Heating time is usually 20-30 minutes depending on mud
type.

Removable Retort

1. Lift the retort assembly from the insulator block. Using a spatula as a screwdriver, remove
the sample cup from the retort chamber.
2. Pack the upper chamber with very fine steel wool or add 5-6 drops of "liquid steel wool" to
the mud in the sample cup.
3. Fill the lower sample cup with a freshly stirred mud sample and replace the calibration lid,
allowing any excess to escape.
4. Wipe off any excess mud and screw the lower sample cup (with calibration lid still in place)
into the upper chamber, maintaining both upper and lower chambers in the upright position.
Screw condenser onto outlet hose of upper chamber.
5. Replace the retort assembly in the insulator block and close the insulating cover.
6. Add a drop of wetting agent (Aerosol) to a 10cm3 or 50 cm3 graduated cylinder (depending
of the size of the retort being used) and place it under the drain of the condenser. Plug in the
retort and turn it on. Continue heating until liquid no longer drips from the condenser.
When using a thermostated retort, the light will go out at the end of the test.

Page 2-14
C. Precautions

1. Make sure that the lower chamber is completely full and has no air entrapped.
2. Be sure to unplug the retort after the test. Sample assembly can be cooled in water or snow.
3. Careful when handling retort assembly, as it is HOT! Loosen sample cup from expansion
chamber as soon as possible. It becomes harder to remove over time.
4. Average Relative Density calculations need to be corrected for dissolved salt when the
chloride concentration is greater than 10,000 mg/L. Figure 2.4 shows the volume occupied
by various concentrations of salt in a mud.

D. Calculations

1. If a Fann Ministill is used, the % by volume water and oil is read directly. The volume
fraction of each constituent is the % by volume divide by 100.
2. If a Baroid Retort is used, read the volume of oil and water. Calculate the fractions as
follows

a) if a 10 cm3 retort is used:

volume fraction oil, fo = cm3 oil / 10

volume fraction water, fw = cm3 water / 10

volume fraction solids, fs = 1.00 - total liquid fraction

b) if a 50 cm3 retort is used:

volume fraction oil, fo = cm3 oil / 50

volume fraction water, fw = cm3 water / 50

volume fraction solids, fs = 1.00 - total liquid fraction

3. For complete SOLIDS CALCULATIONS refer to Chapter 10.

Page 2-15
VISCOSITY

FUNNEL VISCOSITY

A. Description & Equipment

The Marsh funnel is a simple device used for routine measurements of mud viscosity.
The Marsh funnel is conical in shape, 152 mm in diameter at the tip and 305 mm long with a
capacity of 1500 cm3. A 10-mesh screen covers half of the top and is designed to remove any
foreign matter and drilled cuttings from the mud. The mud runs through a fixed orifice at the
end of the funnel which is 50.8 mm x 4.76 mm. The test measures the time in seconds it takes
for one litre of mud to drain from a filled Marsh funnel.

B. Procedure

1. Hold the funnel in an upright position with a finger over the outlet.
2. Pour mud to be tested through the screen until the mud level reaches the bottom of the
screen.
3. Remove the finger from the outlet and measure the number of seconds for one litre of mud to
drain from the funnel.

C. Precautions

1. Check the calibration of the Marsh funnel (water at 21°C is 27.5 ± 0.5 seconds).
2. Clean and dry thoroughly after use.
3. Do not bend or flatten the brass orifice in the bottom of the funnel.

D. Remarks

1. Record the temperature when checking the funnel viscosity.


2. Be sure to fill the funnel to the bottom of the screen.

VISCOMETER

A. Description & Equipment

A more scientific means of measuring mud viscosity is by use of direct indicating coaxial
cylinder viscometers. These are rotational type viscometers powered by a hand crank or electric
motor. As the cylinder rotates through the mud, torque arising from the viscous drag of the fluid
is exerted on the bob. The torque is balanced by a helical spring and the deflection, which is
dependent on the mud viscosity, is indicated on a dial. The cylinder usually turns at 600 r/min.
and 300 r/min., but other speeds are available on some instruments. From the dial readings at
the two speeds, the rheological properties are determined. The three basic types of viscometers:
hand crank models, 12 volt two speed and 115 volt six speed, will be discussed separately.

B. Procedure

Page 2-16
Baroid 280 Rheometer

1. Place a recently stirred sample of mud in any suitable container and immerse the rotor sleeve
in the mud exactly to the scribed line. (Tighten the lock nut on the leg of the leg.)
2. With the gear shift all the way down at the high speed (1,100 r/min.) setting, rotate the crank
for about 10 turns or cranks, then release the gear shift to the 600 r/min. setting or one
setting up and continue cranking at a rate such that slippage occurs. Wait for the dial reading
to reach a steady value and record the 600 r/min. reading. (NOTE: The time required to
reach a steady value is dependent upon the mud characteristics but is usually less than
15 seconds.)
3. Move the gear shift all the way up to the 300 r/min. setting while cranking and record a
steady dial reading.
4. In order to measure the 10 second gel strength reading, allow the mud to stand undisturbed
for 10 seconds. It is not necessary to change the gear shift setting. Slowly and steadily turn
the handwheel in a clockwise direction at a speed of about 3 r/min. The maximum
deflection of the dial before the gel breaks divided by 2, is the 10 second gel strength.
5. Restir the mud at the high speed setting for 10 seconds and then let the mud stand
undisturbed for 10 minutes. Repeat the gel measurement as before and report the maximum
reading divided by 2 as the 10 minute gel strength.

Fann Hand Crank VG Meter - Model 34

1. Place a recently stirred sample of mud in a suitable container and immerse the rotor sleeve
exactly to the scribed line. (Tighten the lock nut on the leg.)
2. With the gear selector all the way down, turn the crank until slippage occurs. Continue
turning the crank until a steady dial reading appears. Record the 600 r/min. reading.
3. Pull the gear selector all the way up to the 300 r/min. setting and continue cranking. Record
the steady dial reading as the 300 r/min. reading.
4. To measure the 10 second gel strength, switch the gear selector to the middle position and
allow the mud to remain undisturbed for 10 seconds. Slowly and steadily turn the gel knob
in a counter-clockwise direction at about 3 r/min. and note the maximum dial deflection
before the gel breaks. Divide the maximum reading by 2 to obtain 10 second gels.
5. Re-stir the mud at the high speed setting and then let it remain undisturbed for 10 minutes.
Repeat the measurement as before noting the maximum dial deflection before the gel
breaks. Divide the maximum reading by 2 to obtain 10 minute gels.

Fann 2 Speed VG Meter - Model 34A, 12 V

1. Place a recently stirred sample of mud in a suitable container and immerse the rotor sleeve
exactly to the scribed line. (Tighten the lock nut on the leg.)
2. With the motor running, push the gear shift all the way down (600 r/min.). Push the high
speed stir button and stir the mud for a few seconds. Wait for the dial reading to reach a
steady value and record the 600 r/min. reading. (NOTE: The time required to reach a
steady value is dependent upon the mud characteristics but is usually less than 15
seconds.)
3. With the motor still running, pull the gear shift all the way up (300 r/min.) and record the
steady dial reading.
4. In order to measure the 10 second gel strength, it is necessary to change the gear shift setting
to the neutral or middle position. Stir the mud at high speed for 10 seconds, switch to

Page 2-17
neutral, then shut off the motor. After 10 seconds slowly and steadily turn the handwheel in
a counter-clockwise direction at about 3 r/min. The maximum deflection of the dial
before the gel breaks divided by 2 is the 10 second gel strength.
5. Restir the mud at the high speed setting for 10 seconds and then let the mud stand
undisturbed for 10 minutes. Repeat the gel measurements as before and report the
maximum reading divided by 2 as the 10 minute gel strength.

Fann 6 Speed VG Meter - Model 35A

1. Place a recently stirred sample of mud in a suitable container and immerse the rotor sleeve
exactly to the scribed line. (Tighten the lock nut on the platform.)
2. With the motor running and the motor speed switch in the high position, push the gear shift
all the way down (600 r/min.). Wait for the dial reading to reach a steady value and record
the 600 r/min. reading. (NOTE: The time required to reach a steady value is dependent
upon the mud characteristics but is usually less than 15 seconds.)
3. With the gear shift all the way down, switch the motor speed to the low position (300 r/min.)
and record the steady dial reading.
4. In order to measure the 10 second gel strength (at 3 r/min.) pull the gear shift up to the
middle position and shut the motor off. Then allow the mud to remain undisturbed for 10
seconds. After 10 seconds turn the motor on the low speed position and measure the
maximum dial deflection before the gel breaks. Divided by 2 to obtain the 10 second gel
strength.
5. For the 10 minute gel strength, re-stir the sample at high speed (600 r/min.) before allowing
it to remain undisturbed for 10 minutes. Repeat the gel measurement as before and report
the maximum dial deflection divided by 2 as the 10 minute gel strength.

C. Reporting Results From All Instruments

Plastic Viscosity, mPa.s = 600 r/min. reading - 300 r/min. reading

Yield Value, Pa = 300 r/min. reading - Plastic Viscosity / 2

10 second gel strength, Pa = half of the maximum dial deflection after 10 seconds.

10 minute gel strength, Pa = half of the maximum dial deflection after 10 minutes.

Apparent Viscosity, mPa.s = 600 r/min. reading / 2

D. Precautions

1. Sleeve and bob should be washed and dried after each operation.
2. Keep viscometer upright when cleaning so that water does not get up into the bearings.
3. If the unit is electric, do not supply more voltage than the unit was designed to handle.
4. Do not use a hollow bob in a heat cup.

E. Remarks

1. Record the test temperature when measuring rheological properties of a mud, especially
with oil muds and on water muds used in deep wells.
2. On the hand crank models, the correct speed is achieved by turning the crank as fast as

Page 2-18
possible. A slipping clutch mechanism will then maintain the selected r/min.
3. When measuring gel properties, the dial does not have to return to zero during the
undisturbed period. Therefore, it should not be forced back to zero if it does not freely
return to zero. When determining the maximum dial deflection, no allowance needs to
be made if the dial did not start at zero. The properties and characteristics of the mud will
determine if the dial returns to zero during the undisturbed periods of the gel
measurements.

F. Viscometer Check

The viscometer should have a zero dial reading when placed in an upright position in air
prior to running any test. With the instrument in this position, rotate the sleeve at 600 r/min.
The dial reading in air should not exceed one. Place water in a suitable container and immerse
the rotor sleeve to the scribed line. Rotate the sleeve at 600 r/min. The dial reading in water
should be between 1.5 and 3. Rotate the sleeve at 300 r/min. The dial reading in water should
be between 0.5 and 2. The light on the front of the Fann Model 34A viscometer should be on
when the instrument is being operated. Failure of the viscometer to pass any one of the above
tests indicates that the bearings are bad and should be replaced by a qualified instrument
technician.

BROOKFIELD VISCOMETER

A. Equipment

The Brookfield Viscometer is used for measuring mud viscosity at very low shear rate
ranges. The principal of operation is to drive a spindle in the test fluid with a calibrated spring.
The viscous drag of the fluid against the spindle is measured in centipoise viscosity or
milliPascal seconds by the spring deflection and a rotary transducer. The spindle can run from
0.3 r/min to 100 r/min. The low shear rate ranges attained by the Brookfield allows the
monitoring of drilling fluid properties very close to the well bore wall or drill string. This is
critical in monitoring polymer systems for optimum performance, by maintaining correct
polymer levels without overtreatment causing possible shear thinning effects.

B. Procedure

1. In an area free of vibration or movement, mount the Brookfield on the stand. Tighten the
knob with the bullseye bubble as level as possible. Level the unit with the adjustable feet.
2. Make sure power switch is off, then plug in the Brookfield. Plug in temperature probe if it is
to be used.
3. Turn power switch on. Wait until you see display "REMOVE SPINDLE PRESS ANY
KEY"
4. Remove spindle, if there is one installed, and press any key to autozero the unit. (VERY
IMPORTANT)

5. Follow instructions on the display.


6. Install spindle #4, LEFT HAND THREAD, on the lower shaft. Hold the lower shaft firmly
with one hand, lifting up slightly, while screwing the spindle on with the other. Finger tight
only, USE NO TOOLS.
7. Lower the unit with knob on the stand, submerging the spindle up to the raised line on the
cut out section, in the fluid to be tested .

Page 2-19
8. Press Select Display pad once to show cP in the upper left hand corner.
9. Pressing up or down arrows, selects the speed to be run. Press Set Speed to run that speed.
10. Allow reading to stabilize, record reading then proceed to next speed.
11. After analysis is complete, shut down Brookfield and remove spindle carefully, remembering
it is a left hand thread. Clean the Brookfield.

C. Precautions

1. If cP result shows "EEEE" this indicates the sample is over-range, continue with other
speeds. If "?" is displayed the sample is under-range.
2. Make sure upper right hand corner of display shows "SP64" indicating Spindle #4.
3. Be very careful when installing or removing spindle.
4. Refer to Brookfield Manual for further information.

Page 2-20
CHEMICAL TESTS

ALKALINITY:

ALKALINITY MUD, Pm

A. Description & Equipment

This test measures the alkalinity of the whole mud. When used in conjunction with the
filtrate alkalinity determination, the amount of excess lime present in the mud can be determined

This test requires the following materials:

Titration Dish
Syringe
Distilled Water
Phenolphthalein Indicator
N/50 (0.02 N) Sulfuric Acid

B. Procedure

1. Measure 1 cm3 of a freshly stirred sample of mud into a titration dish using a syringe.
2. Dilute the mud in the dish with about 50 cm3 of distilled water.
3. Add 4 or 5 drops of Phenolphthalein.
4. If the sample does not change color, record the Pm as 0.
5. If the sample turns pink, titrate rapidly with N/50 Sulfuric Acid until the pink color
disappears.

C. Calculations

Report the Phenolphthalein alkalinity of the mud, Pm, as the number of cm3 of N/50
Sulfuric Acid added to until the pink color disappears.

D. Remarks

1. If the mud sample is deeply colored and the color change is hard to see, use 0.5 cm 3 of mud
and report the Pm as the volume of acid added times 2. If N/10 (0.1 N) Sulfuric Acid is
used, the Pm is reported as volume of acid added to 1 cm3 of mud times 5.

Page 2-21
ALKALINITY: FILTRATE, Pf & Mf

A. Description & Equipment

These tests are designed to measure the alkalinity contributions from soluble mud
constituents. These two tests together can be used to determine the hydroxide ion (OH -), the
-
bicarbonate ion (HCO3 ) and the carbonate ion (CO3=) concentration. Also the Pf can be used
with the Pm to determine the excess amount of lime present in the mud.

This test requires the following materials:

Titration Dish
Pipettes
Distilled Water
Phenolphthalein Indicator
N/50 (0.02 N) Sulfuric Acid
Bromo Cresol Green-Methyl Red Indicator

B. Procedure: Pf

1. Pipette 1 cm3 of filtrate into a titration dish.


2. Add 2 to 3 drops of Phenolphthalein indicator solution. If no color develops Pf is 0 (and pH
is <8.4). If a pink color develops, add N/50 Sulfuric Acid until the color changes from pink
to that of the original sample.

C. Calculations: Pf

1. Pf is the amount of N/50 Sulfuric Acid required to discharge the pink color. Reported in
cm3.
2. Excess lime content

Lime, kg/m3 = 0.74 (Pm - Pf)

D. Procedure: Mf

1. To the same sample used for the Pf determination, add 2 or 3 drops of Bromo Cresol Green-
Methyl Red indicator.
2. Add N/50 Sulfuric Acid until the color changes from a blue-green to a pink color.

E. Calculations: Mf

Mf = cm3 acid for Pf + cm3 acid for Mf

An estimation of hydroxide ion, bicarbonate ion and carbonate ion concentrations can be
determined by use of Figure 2.4.

Page 2-22
Figure 2.4
CALCULATIONS OF ALKALINITY

Test Results Calculation

where Pf = Mf Pf x 340 = mg/L OH-


(indicates OH- only)

where 2Pf - Mf is a positive number (2Pf - Mf) x 340 = mg/L OH-


(indicates OH- and CO3= only) [2 (Mf - Pf)] x 600 = mg/L

where 2Pf = Mf Mf x 600 = mg/L CO3=


(indicates CO3= only)

where 2Pf - Mf is a negative number 2Pf x 600 = mg/L CO3=


(indicates CO3= and HCO3=) (Mf - 2Pf) x 1220 = mg/L

where no Pf reading or very low Pf Mf x 1220 = mg/L HCO3=


(indicates HCO3= only)

Nomenclature

Pf = Phenolphthalein end point of the sample using N/50 Sulfuric Acid


Mf = Bromo Cresol Green Methyl Red end point of sample using N/50
Sulfuric Acid
OH- = Hydroxide ion
CO3= = Carbonate ion
HCO3= = Bicarbonate ion

F. Procedure: P, P1 and P2

If the filtrate is dark due to lignite or lignosulfonate, the following procedure can be used:

1. Add 2 to 4 drops of Phenolphthalein indicator to 1 cm 3 of filtrate in a titrating dish and


titrate to the end point with N/50 Hydrochloric Acid. Record the cm3 of acid as P.
2. Place 1 cm3 of filtrate into a titrating dish and add 24 cm3 of distilled water.
3. Add a measured amount (2 to 5 cm3) of N/10 Sodium Hydroxide to convert the bicarbonates
to carbonates.
4. Add a measured amount (2 to 4 cm 3) of Barium Chloride solution to precipitate the
carbonates.
5. Add 2 to 4 drops of Phenolphthalein indicator and stir with a stirring rod.
6. Titrate immediately to the end point with N/50 Hydrochloric Acid.*

7. Place exactly the same amounts of Sodium Hydroxide solution, Barium Chloride solution,

Page 2-23
and indicator into 25 cm3 of distilled water and titrate to the end point with N/50
hydrochloric acid. Record the cm3 of acid used as P2.
8. The carbonates, hydroxides and bicarbonates are estimated from the following calculations:

P2 greater than P1 Bicarbonates (eq/m3) = 20 x (P2 - P1)


Carbonates (eq/m3) = 40 x P

P1 greater than P2 Hydroxides (eq/m3) = 20 x (P1 - P2)


Carbonates (eq/m3) = 40 x [P (P1 - P2)]

*NOTE: Hydrochloric Acid must be used at this point. Attempts to use Sulfuric Acid will
result in solubilization of the carbonates.

G. Remarks

1. Other indicators can be used for the Mf end point. Some are listed below together with their
end point colors.

Indicator End Point

Methyl Orange red


Bromo Cresol Green yellow

2. Care must be taken when the filtrate is deeply colored as this will mask the end point (see P,
P1, and P2 titrations). In a case like this, the test may have to be run several times to insure
that the answer obtained is correct.

AMMONIUM

A. Description & Equipment

The ammonium test is used to determine the amount of ammonium ion in DAP or
Ammonium Sulfate muds. It is the equivalent of the Potassium test for KCl muds. The former
DAP test (now called the phosphate test) had the drawback of testing the phosphates which are
not responsible for preventing shale hydration. Therefore, the ammonium test was developed to
more accurately determine the effectiveness of the mud to prevent shale hydration and the
realistic concentration of DAP or Ammonium Sulfate in the system.
The test involves the reaction of formaldehyde with ammonium and the determination of
the amount of acid formed when the reaction is complete. The ammonium ion is then calculated
and the amount of DAP or Ammonium Sulfate is calculated from this value for ammonium.

Page 2-24
This test requires the following materials:

10 cm3 Graduated Cylinder


Titration Dish
Pipettes
Ammonium Detection Solution
N/10 Sodium Hydroxide
N/10 Sulfuric Acid or Hydrochloric Acid
Phenolphthalein

B. Procedure

1. Measure out 5 cm3 of Ammonium Detection Solution in the graduated cylinder.


(CAUTION: Do not pipette this solution.) Place the solution in the titration dish.
2. Add a 1 cm3 sample of filtrate into the titration dish. Add 2-3 drops of Phenolphthalein
indicator and titrate with N/10 Sodium Hydroxide until the solution turns faint pink.
3. Add 2 cm3 of N/10 Sodium Hydroxide after the end point has been reached, record the total
volume used and allow the solution to stand for ten minutes.
4. Titrate the solution after this time with N/10 acid until the sample just becomes colorless.

C. Calculations

Ammonium ion (NH4+), mg/L = 1800 x (cm3 of Sodium Hydroxide - cm3 of acid)

DAP, kg/m3 = 0.00367 x NH4+, mg/L

Ammonium Sulfate, kg/m3 = 0.00367 x NH4+, mg/L

D. Remarks

1. Be sure to allow the full ten-minute waiting period as this reaction takes place slowly.
2. Under no circumstances should the Ammonium Detection Solution be pipetted by mouth.

Page 2-25
BIOCIDE

A. Description & Equipment

When a preservative is being used it is imperative that the level be maintained adequately
to prevent fermentation of products. This test offers a simple means of monitoring the level of
Biocide in a mud system.
This test involves a reaction between sodium sulfite and glutaraldehyde that results in a
change of pH. The amount of change is related to the amount of Biocide in the system.

This test requires the following materials:

Titration Dish
Pipettes
Sodium Sulfite solution
N/50 Sodium Hydroxide
N/50 Sulfuric Acid
Phenolphthalein

NOTE: The Sodium Sulfite solution deteriorates rapidly. If older than 30 days it should
be replaced with fresh solution.

B. Procedure

1. Pipette 2 cm3 of filtrate into the titration dish.


2. Add 2-3 drops of Phenolphthalein indicator.
3. Titrate with N/50 Sulfuric Acid (if pink or red), or N/50 Sodium Hydroxide (if colorless), as
required until a faint pink color remains. Add one or two drops of acid to dispel the color.
4. To the neutralized filtrate add 1 cm3 of Sodium Sulfite solution. A red color will develop.
5. After approximately 30 seconds, titrate with N/50 Sulfuric Acid until the color just
disappears.
6. Repeat steps 3 and 4 using distilled water instead of filtrate.

C. Calculations

Biocide, kg/m3 = (cm3 acid for filtrate - cm3 acid for distilled water) / cm3 of filtrate

Page 2-26
CARBONATES

GARRETT GAS TRAIN

A. Description & Equipment

This test is run on a sample of mud filtrate. It uses an apparatus called a Garrett Gas
Train. In general, it consists of a transparent plastic gas train, an inert gas supply and pressure
regulator, a floating-ball flowmeter, collection bag, hand pump and a Dräger tube. The carrier
gas used is Nitrous Oxide.

The Garrett Gas Train separates the gas from the liquid, thereby preventing
contamination of the CO2 detector by the liquid phase. A Dräger tube responds to CO 2 by
progressively turning purple along its length, as the CO2 reacts with the reagent. The stain
length is primarily sensitive to the amount of CO2 present, but also to the total gas volume
passed through the tube. For reliable results, the gas exiting from the gas train must first be
captured in a one litre gas bag to allow the CO2 to mix uniformly with the carrier gas. The
contents of the gas bag are drawn through the Dräger tube, using ten strokes of the Dräger hand
pump (10 strokes = 1 litre).

This test requires the following materials:

Garrett Gas Train


CO2 Dräger tubes 0.01%/A
Dräger one litre gas bag
Dräger hand pump
Stopcock, 2-way bore
5N Sulfuric Acid
Defoamer
2 x 10 cm3 syringe with 21 gauge needle
N20 gas cartridges

B. Procedure

1. With the regulator T-screw backed off, install and puncture a N20 cartridge.
2. Add 20 cm3 of distilled water to the largest chamber, Chamber 1.
3. Add 5 drops of defoamer to Chamber 1 in order to minimize carry over the next chamber.
4. Install the top of the gas train and hand tighten all screws evenly to seal.
5. Attach the flexible tubing to the dispersion tube.
6. Adjust the dispersion tube in Chamber 1 to about 0.5 cm above the bottom.
7. Gently start flow of N20 for a 1 minute period to purge any air from the system. If no leaks
are detected, shut off N20.

Page 2-27
8. Fully collapse the gas bag and check the system for leaks. To do this, connect the gas bag
and stopcock to the hand pump. Fully compress and release the hand pump. When the bag
is completely empty and free of leaks, the pump will remain compressed for several minutes.
If leakage is detected, check the pump and all connections. To check the pump alone, insert
a sealed Dräger tube into the pump and compress the bellows. It will remain compressed if
the pump does not leak.
9. With the bag fully collapsed, install the flexible tubing from the stopcock and bag onto the
outlet of Chamber 3.
10. Inject a measured volume of filtrate into Chamber 1, through the rubber septum with a
syringe and needle.
11. Slowly inject 10 cm3 of sulfuric acid into Chamber 1, through the rubber septum with a
syringe and needle .
12. Open the stopcock on the gas bag, and restart the gas flow. Adjust the gas flow to fill the gas
bag over a 20 minute period so it is firm to the touch (do not burst the bag). Shut off the gas
flow and close the stopcock.
13. Break the tip off each end of the Dräger tube.
14. Remove the tubing from the Chamber 3 outlet and immediately install it onto the "top" end
of the Dräger tube. Attach hand pump to the "bottom" end of the Dräger tube.
15. Open the stopcock and fully compress and release the hand pump so gas flows through the
Dräger tube. Repeat this until a total of ten complete strokes of the hand pump has been
counted. The gas bag should be virtually empty. (if bag is somewhat full, there is a leak and
the results are not accurate)
16. Observe any changes in the appearance of the Dräger tube color. Note and record the
maximum stained length in the same units marked on the tube

Dräger Tube Information

Carbon Dioxide Dräger Tube, 0.01%/A

Carbonate Range Sample Volume Tube Factor = 25000


mg/L cm3

25-750 10.0
50-1500 5.0
250-7500 2.5

C. Calculations

The carbonates in the sample are calculated as follows:

CO2, 0.01%/A: marked 100 - 2000 ppm

Carbonates, mg/L = (Darkened Length x 25000) / Sample Volume, cm3

Page 2-28
D. Remarks

The entire assembly should be thoroughly cleaned and dried before and after each use.

NOTE: For accurate results, use a sample size that will cause at least half of the tube to
darken.

CHLORIDE

CHLORIDE: SILVER NITRATE METHOD

A. Description & Equipment

This test measures the soluble chloride ion concentration in the mud filtrate. The
chlorides can come from Sodium Chloride, Calcium Chloride or Potassium Chloride. Also, for
the titration to work correctly the pH of the filtrate needs to be near neutral. This is the reason
for the first step in the procedure.

The silver ion combines with free chloride to form Silver Chloride. This can appear as a
white precipitate with higher concentrations. When all free Chloride is used, the silver ion reacts
with the Potassium Chromate to form Silver Chromate which produces the orangish-red
endpoint (first detectable permanent color change).

This test requires the following materials:

Titration Dish
Pipettes
Silver Nitrate - two concentrations
a. 1 cm3 = 1000 mg/L Cl ion (weak solution, 0.0282 N)
b. 1 cm3 = 10000 mg/L Cl ion (strong solution, 0.282 N)
Potassium Chromate indicator
Distilled Water
Phenolphthalein
N/50 Sulfuric Acid

B. Procedure

1. Pipette 1 cm3 of filtrate or sample to be tested into a titration vessel.


2. If needed, add distilled water to dilute the dark color of a deeply colored filtrate. Dilution
does not influence the test in any way if there are no chlorides present in the distilled water.
If any water other than distilled water is used, the chloride in it must be analyzed by titration
before adding the filtrate to it, (determine chloride in the water and subtract from total
result).
3. Add 2-3 drops of Phenolphthalein indicator to the filtrate.

4. If a pink color appears, titrate with N/50 Sulfuric Acid until the color changes from pink to

Page 2-29
that of the original sample. If no pink color appears, the test can be continued.
5. Add enough Potassium Chromate indicator to give the filtrate a bright yellow color.
6. Add Silver Nitrate from a pipette dropwise, stirring or swirling, until the sample just turns
from yellow to orangish-red (the first detectable permanent color change).

C. Calculations

Chloride content in mg/L = cm3 of Silver Nitrate x 1000 (1 cm3 = 1,000 mg/L)

Chloride content in mg/L = cm3 of Silver Nitrate x 10000 (1 cm3 = 10,000 mg/L)

D. Remarks

1. mg/L salt (NaCl) = mg/L chloride x 1.65.


2. The chloride test may be run on the same sample used in the Pf determination if the Mf test
was not performed.
3. Avoid contact with Silver Nitrate. Wash immediately with water if Silver Nitrate gets on
skin or clothing.
4. The end point of the reaction is when the Silver Chromate is first formed. It is the first
detectable permanent color change from yellow to orangish-red. When using the weak
Silver Nitrate, the end point is approached very gradually. Therefore, the formation of the
Silver Chromate can be seen by a color change from yellow to orangish-red. If the strong
silver nitrate is used, the end point is approached much more rapidly. Hence the early
formation of the Silver Chromate and its orangish-red color may be missed due to the larger
amounts of Silver Nitrate being added. The color change will go from yellow to red. As
soon as the red color is seen, the titration is complete.
5. White lumps of Silver Chloride form when titrating high concentrations of salt. This should
not be mistaken for the end point.
6. High pH will precipitate Silver Oxide.

MERCURIC NITRATE METHOD

A. Description & Equipment

This test measures the soluble chloride ion concentration in the mud filtrate. The
chlorides can come from Sodium Chloride, Calcium Chloride or Potassium Chloride. Also, for
the titration to work correctly the pH of the filtrate needs to be acidic (pH < 3.0)
The mercury combines with free chloride to form Mercuric Chloride. When all free
Chloride is bound, the mercury reacts with the Diphenylcarbazone-Bromophenol Blue to
produce the violet endpoint (first detectable permanent color change).

Page 2-30
This test requires the following materials:

Titration Dish
Pipettes
Mercuric Nitrate - two concentrations
a. 1 cm3 = 1000 mg/L Cl ion (weak solution, 0.0282 N)
b. 1 cm3 = 10000 mg/L Cl ion (strong solution, 0.282 N)
Diphenylcarbazone-Bromophenol Blue (DBB) indicator
Distilled Water
5 N Sulfuric Acid

B. Procedure

1. Pipette 1cm3 of filtrate or sample to be tested into a titration vessel.


2. If needed, add distilled water to dilute the dark color of a deeply colored filtrate. It does not
influence the test in any way if there are no chlorides present in the distilled water. If any
water other than distilled water is used, the chloride in it must be zeroed out by titration
before adding the filtrate to it, (determine chloride in the water and subtract from total
result).
3. Add enough Diphenylcarbazone-Bromophenol Blue indicator to give a strong color, pH>3
blue or pH<3 yellow. (As most muds are neutral or higher, you can expect a blue color)..
4. Add 5N Sulfuric Acid dropwise to produce a strong yellow color. If necessary, you can add
additional DBB indicator to produce a stronger yellow color.
5. Add Mercuric Nitrate from a pipette dropwise, stirring or swirling until the sample just turns
from yellow to a violet color (the first detectable permanent color change).

C. Calculations

Chloride content in mg/L = cm3 of Mercuric Nitrate x 1000 (1 cm3 = 1000 mg/L)

Chloride content in mg/L = cm3 of Mercuric Nitrate x 10000 (1 cm3 = 10000 mg/L)

D. Remarks

1. mg/L salt (NaCl) = mg/L chloride x 1.65.


2. The chloride test may be run on the same sample used in the Pf determination if the Mf test
was not performed.
3. Avoid contact with Mercuric Nitrate. Wash immediately with water if Mercuric Nitrate gets
on skin or clothing.
4. The endpoint is the first detectable permanent color change from yellow to violet. When
using the weak Mercuric Nitrate, the end point is approached gradually. If the strong
Mercuric Nitrate is used, the end point is approached much more rapidly. As soon as the
first permanent color change is seen, the titration is complete.
5. Ferric and Chromate ions can react with diphenylcarbazone.

LIGNOSULFONATE

Page 2-31
A. Description & Equipment

The lignosulfonate test is designed to monitor the amount of free lignosulfonate in a mud
filtrate. It is a precipitation reaction in which the sample must be centrifuged and the precipitate
volume measured.

This test requires the following materials:

Lignofloc solution
Hand Crank Centrifuge
2-15 cm3 Centrifuge Tubes.

B. Procedure

1. Place 4 cm3 of filtrate in each of the two centrifuge tubes.


2. Add 4 cm3 of Lignofloc solution and stir occasionally for 2-3 minutes with a stirring rod.
3. Centrifuge the samples for one minute at approximately 1800 r/min.
4. Measure the volume of sediment at the bottom of the tubes.

C. Calculations

The amount of lignosulfonate in the system can be determined from the standard graph in
Figure 2.5.

D. Remarks

1. It is important to remember that the results obtained refer to the amount of free
lignosulfonate in the filtrate. This does not include the amount attached to solids particles or
bound up in the filter cake.
2. If possible, Lignofloc solution should be kept cold to prolong its usefulness.

Hand-crank centrifuge speed calculation for 1800 r/min: (see 2.19 Polyacrylamide)

Page 2-32
Figure 2.5

PLOT OF LIGNOSULFONATE CONCENTRATION VS. SEDIMENT VOLUME

Lignosulfonate vs. Sediment


Volume

2.5

1.5

0.5

0
0 10 20 30 40 50

Page 2-33
NITRATE TRACER

A. Description & Equipment

The nitrate ion can be used as a tracer in a mud in order to distinguish mud filtrate from
formation water. Since no nitrates are known to exist in uncontaminated formation water, the
nitrate content of liquids recovered from drill stem tests and from wireline formation tests can be
used to determine the fraction of mud filtrate in the liquid.

This test requires the following materials:

Hach 0-50mg Nitrate Test Kit


Pipette
Distilled water (nitrate free).

B. Procedure

1. Rinse two sample cells thoroughly with distilled water.


3. Add mud filtrate to each cell (to get in the 5 - 40 mg/L range).
2. Add distilled water to 5 cm3 line in sample cells if dilution needed.
4. Add the contents of a NitraVer powder pillow to one of the cells.
6. Shake for 1 minute.
7. Let stand for 5 minutes. If nitrate present, an amber color will develop.
8. Place the blank cell into the left cell holder and the sample cell into the right cell holder.
Hold the color comparator up to good light or bright surface. Rotate the nitrate nitrogen
color disc (0-50 mg/L) until the color of the blank cell closely matches the sample color.
10. Multiply mg/L of nitrogen by dilution factor then 4.4 to obtain mg/L of nitrate.

C. Calculations

The result shown on the color comparitor (mg/L Nitrogen) must be multiplied by the
dilution factor, if dilution was done, then multiplied by 4.4 to convert to mg/L Nitrates.
The nitrate content is maintained at a fixed level, i.e., 200 mg/L, in the mud filtrate while
drilling through the zone in question. The volume fraction of mud filtrate in a sample of
produced water can then be determined by measuring the nitrate content of the produced water.
The volume fraction of mud filtrate is equal to the following:

mg/L Nitrates = mg/L Nitrogen x dilution factor (if used) x 4.4

Fraction Filtrate = produced water nitrate / mud filtrate nitrate

Page 2-34
D. Example:

The nitrate in the mud filtrate is maintained at 200 mg/L. A drill stem test contains water
with a nitrate content of 55 mg/L. The volume fraction of mud filtrate in the D.S.T. water is
calculated as follows:

Sample diluted x2 (2.5 cm3 sample diluted to 5 cm3 with distilled water)
Color Comparator = 6 mg/L Nitrogen

mg/L Nitrates = 6 x 2x 4.4


= 52.8

Fraction Filtrate = 52.8 / 200


= 0.264

pH (STRIP AND METER)

A. Description & Equipment

There are two generally accepted methods for measuring mud pH. These are the pH
meter and the pH test strips. Each has its own advantages and disadvantages. Both methods will
be discussed.

B. pH Strip Method

1. Dip a pH strip the mud or filtrate. The pH of the filtrate may differ from that of the mud.
2. Allow sufficient time for the color indicators to soak up liquid (from a few seconds to a
couple of minutes).
3. Match the colors of the strip with the chart on the side of the dispenser to determine the pH.
4. Remarks
a. Report pH to the nearest 0.5.
b. pH paper does not give an accurate measurement when the chloride concentration is
greater than 10000 mg/L.

C. pH Meter Method

1. This is a delicate instrument so it should be handled carefully.


2. Make the necessary adjustments to calibrate the pH meter with standard pH buffer solutions
according to instructions supplied with the instrument.
3. Wash the tip of the electrode with distilled water, then insert it into the mud and swirl once
or twice.
4. Determine the mud pH according to the instructions supplied with the unit. Read the
constant meter reading after it has stabilized, which usually takes less than 15 seconds.
5. The pH of the mud can now be reported to the nearest 0.1 unit.
6. The calibration of the instrument depends both on correct buffer calibration solutions and on
the temperature.

Page 2-35
PHOSPHATE

A. Description & Equipment

The concentration of phosphate in a mud may be determined by reversing the total


hardness test. The same indicator is used and a standard 2% Calcium Chloride solution is
prepared for titrating the filtrate. The phosphate will react with the added calcium chloride to
sequester the calcium. When all the phosphate present in the filtrate is consumed, the excess
calcium turns the solution from blue to red.

This test requires the following materials:

Total Hardness Buffer


Total Hardness Indicator Solution
2% Calcium Chloride Solution
Distilled Water
Titration Dish
Pipettes

B. Procedure

1. Pipette a 1 cm3 sample of filtrate into a titrating dish. Add 25 cm3 of distilled water.
2. Add 20-40 drops (2-4 cm3) of Total Hardness Buffer solution and 10-15 drops of Total
Hardness Indicator Solution.
3. Titrate with 2% Calcium Chloride until the solution changes from blue to wine red.

C. Calculations

Phosphate, mg/L = 11400 x cm3 CaCl2 / cm3 of sample

D. Remarks

This test was formerly called the DAP test. To determine the amount of DAP in a
system, please refer to the Ammonium Test.

Page 2-36
POLYACRYLAMIDE

A. Description & Equipment

This test can be used to determine the amount of any polyacrylamides that may be in a
mud or sump water sample. The calculations are divided for both solid products and liquid
products. The procedure forms a precipitate and the solution is centrifuged to determine the
volume of precipitate. The test is accomplished by neutralizing the sample and flocculating the
polymer with a Tin Chloride solution. The volume of precipitate formed is directly related to
the amount of polyacrylamide in the system.

This test requires the following materials:

Hand Crank Centrifuge


2, 15 cm3 Graduated Centrifuge Tubes
Stir Rods
Pipettes
Acrylofloc Solution
N/50 Sodium Hydroxide
N/50 Hydrochloric Acid
Phenolphthalein

B. Procedure

1. Pour 10 cm3 of filtrate into each of the centrifuge tubes. If only limited filtrate is available
then one tube may be used provided the other is filled with an equal volume of water.
2. Add 2-3 drops of Phenolphthalein. Titrate with N/50 Hydrochloric Acid (if pink or red), or
N/50 Sodium Hydroxide (if colorless), as required until a faint pink color remains. Add one
drop of acid to dispel the color.
3. Add 2 cm3 of Acrylofloc solution to each of the tubes and gently invert several times to
ensure thorough mixing. If polyacrylamide is present, large white flocs will being to form
immediately.
4. Allow the sample to age for five minutes while occasionally agitating with the stirring rod to
break up the flocs.
5. Centrifuge the sample for one minute at 1800 r/min

Hand-crank centrifuge speed calculation for 1800 r/min:

1. Determine the number of revolutions of the rotor for each complete turn of the crank.
2. Determine the number of cranks to get 1800 revolutions. The rotary speed will be 1800
r/min. if the crank is turned the calculated number of times in one minute.
3. To maintain a constant speed for 1 minute, take the required number of crank turns and
divide by 12. This will give the number of crank turns needed per 5 seconds.

Page 2-37
4. Start cranking the centrifuge rapidly and count the number of crank turns in 5 seconds. If
the number of turns is greater or smaller than required per 5 seconds, adjust your speed
accordingly and count turns for the next 5 seconds. Usually, with a little practice, the
required number of turns per 5 seconds can be achieved within 15-20 seconds. Maintain the
speed for the remainder of the minute.

C. Calculations

Dry Polyacrylamide

kg/m3 = 2.0 x average floc volume, cm3

Liquid Polyacrylamide

L/m3 = 5.0 x average floc volume,cm3

D. Remarks

1. Lignosulfonates will interfere with this test. If present they must be removed. This may be
accomplished as follows:
a. Place 10 cm3 of filtrate in each centrifuge tube.
b. Add 2 cm3 of Lignofloc solution and mix.
c. Centrifuge the sample to remove the flocs.
d. Pour the clear fluid into a graduated cylinder, clean the tubes and proceed with the test in
the usual manner.
2. Salts, calcium and other polymers do not interfere with the test.
3. Be sure to centrifuge the sample for the full time.

POTASSIUM

A. Description & Equipment

This test is used to determine the potassium content in mud filtrate by centrifuging
precipitate formed in a reaction with Sodium Perchlorate. The result is read from a previously
prepared standard curve. This test requires the following materials:

Hand Crank Centrifuge


2, 15 cm3 Graduated Centrifuge Tubes
Standard Sodium Percholate solution (150 grams in 100 cm3 distilled water).
Standard Potassium Chloride solution (14.00 grams dry KCl dissolved in distilled water and
made up to 100 cm3 in a volumetric flask) [0.5 cm3 KCl solution diluted to 7.0 cm3 = 1.0%
KCl.
Standard Curve for Potassium Chloride.

Page 2-38
B. Preparation of Standard Curve for Potassium Chloride

1. Prepare standards over the range of 1 to 8% KCl by adding 0.5 cm 3 per 1% KCl required of
Standard Potassium Chloride solution to centrifuge tubes and diluting to the 7.0 cm3 mark
with distilled water.
2. Add 3 cm3 of Sodium Perchlorate solution to each tube.
3. Centrifuge for one minute at 1800 r/min. and read precipitate volume immediately.
4. Plot cm3 of precipitate versus per cent Potassium Chloride, using rectangular graph paper.
See the example plot, Figure 2.6.

C. Field Procedures

1. Measure 7cm3 of filtrate into the centrifuge tube.


2. Add 3 cm3 of Sodium Perchlorate solution to the tube. Precipitation occurs immediately,
3. Centrifuge for one minute at 1800 r/min. and read the precipitate volume immediately.
4. Determine Potassium Chloride concentration by comparing precipitate volume measured
with the Standard Curve for Potassium Chloride.
5. Immediately dispose of precipitate by rinsing from tube into a bucket of water.

Hand-crank centrifuge speed calculation for 1800 r/min: (see 2.19 Polyacrylamide)

D. Remarks

1. The perchlorates are not hazardous if kept water wet. They will decompose harmlessly if
dispersed in a bucket of water.
2. Potassium test must be made with the same centrifuge used to construct the Standard Curve.
Run the centrifuge at a constant speed of 1800 r/min.
3. Salts, lignosulfonates, polymers, clays and pH do not interfere with the test.
4. The precipitate may become slightly discolored in high lignosulfonate concentrations, but the
test is not affected.
5. Only the Kolmer-type clinical centrifuge tubes are satisfactory for the test.
6. A new standard graph must be prepared if a different model of centrifuge is used.

Page 2-39
Figure 2.6
STANDARD PLOT EXAMPLE for KCl DETERMINATION

Sample Plot

Page 2-40
QUALITATIVE SULFATE

A. Description & Equipment

This test is designed to determine the presence of any sulfates. It does not determine the
amount of sulfates present.

This test requires the following materials:

Test Tube
Barium Chloride solution
5N Nitric Acid

B. Test Procedures

1. Add 1 cm3 of mud filtrate to a test tube.


2. Add a few drops of the Barium Chloride solution.
3. The formation of a white precipitate or a milky white color indicates the presence of sulfates
and/or carbonates.
4. Add a few drops of the 5N nitric acid. If the precipitate or milky color disappears, it is
carbonates. If it remains, it is sulfates.

C. Calculation

Report the sulfate amount as light, medium, or heavy, after the acid treatment.

SULFATE REDUCING BACTERIA

A. Description & Equipment

This test is used to determine the concentration of sulfate reducing bacteria present in a
drilling fluid. Sulfate reducing bacteria can convert sulfate ions to sulfide ions which can cause
the pipe and casing to corrode rapidly. A biocide treatment such as glutaraldehyde is effective in
eliminating bacteria from these type fluids.

This test requires the following materials:

Sulfate Reducing Vials (5)


Syringe (2 cm3 with 20 gauge needle)
Felt tip marker

Page 2-41
B. Procedure

1. Number the sulfate reducing vials from 1 through 5.


2. Inject Vial No. 1 with 1 cm3 of mud to be tested.
3. Invert the vial several times with the needle still in the vial to homogenize the mud into the
serum broth.
4. Remove 1 cm3 of liquid from Vial No. 1 and inject in Vial No. 2.
5. Invert the vial several times.
6. Remove 1 cm3 of liquid from Vial No.2 and inject into Vial No.3.
7. Continue until all five vials have been injected.
8. Incubate the vials at room temperature for 1 to 3 weeks.

C. Results

Formation of a black precipitate or a gray to black clouding indicates the presence of


sulfate reducing bacteria in the mud. The number of microorganisms present per cm 3 of mud is
determined by noting which of the vials contain the black precipitate or clouding. Figure 2.7
shows the range of concentrations of Sulfate Reducing Bacteria for the various combinations
where the black precipitate or clouding appears:

Figure 2.7

Vial Number Containing Black Range of Concentration of Sulfate


Precipitae or Dark Clouding Reducing Bacteria Organisms, cm3

1 1-9
1 and 2 10-99
1,2 and 3 100-999
1,2,3 and 4 1000-9999
1,2,3,4 and 5 >10,000

If no precipitate or black clouding forms in the vials, there are no sulfate reducing
bacteria present in the mud.

D. Remarks

1. Additions of 3-6 kg/m3 of glutaraldehyde are effective in eliminating bacteria from most
mud systems.

Page 2-42
SULFIDES

HACH H2S TEST KIT

A. Description & Equipment

This is basic test to determine the presence of H2S and the approximate amount in small
concentrations. This test uses a container with the filtrate sample and Alka-Seltzer to drive out
any H2S that may be present. The gas, if present, goes through a lead acetate disc causing
discoloration. This is matched to a color chart with low concentration ranges.

GARRETT GAS TRAIN

A. Equipment & Description

This test is run on a sample of mud filtrate. It uses an apparatus called a Garrett Gas
Train. In general, it consists of a transparent plastic gas train, an inert gas supply and pressure
regulator, a floating-ball flowmeter and a Dräger tube. The carrier gas used is usually Carbon
Dioxide.
The Garrett Gas Train separates the gas from the liquid, thereby preventing
contamination of the H2S detector by the liquid phase. A Dräger tube responds to H 2S by
progressively darkening along its length as the H2S reacts with the reagent. The two types of
Dräger tubes used will span a sufficiently wide range for sulfide analysis of mud filtrates. The
low-range Dräger tube, H2S 100/a, is white while the high-range Dräger tube, H2S 0.2%/A, is
blue until H2S turns them black. No known common mud component or contaminant causes this
coloration of the Dräger tubes as does H2S.

This test requires the following materials:

Garrett Gas Train


H2S Dräger tubes - two ranges
a) low range, H2S 100/a, marked 100 - 2000 ppm
b) high range, H2S 0.2%/A, marked 0.2 - 7.0 vol %
5N Sulfuric Acid
Defoamer
10 cm3 syringe with 21 gauge needle
CO2 gas cartridges

Page 2-43
GARRET GAS TRAIN

B. Procedure

1. With the regulator T-screw backed off, install and puncture a CO2 cartridge.
2. Add 20 cm3 of distilled water to the largest chamber, Chamber 1.
3. Add 5 drops of defoamer to Chamber 1 in order to minimize carry over the next chamber.
4. A volume of mud filtrate is added to chamber 1 based upon an estimation of the
concentration
of sulfides present.
5. After breaking the tips off of both ends of the Dräger tube, gently push the tip of the Dräger
tube with the arrow pointing downward into the bored receptacle at the other end from
Chamber 1. Also, install the flowmeter tube, making sure all O-rings seal around the body
of each tube.
6. Install the top of the gas train and hand tighten all screws evenly to seal.
7. Attach the flexible tubing to the dispersion tube and to the Dräger tube.
8. Adjust the dispersion tube in Chamber 1 to about 0.5 cm above the bottom.
9. Gently start flow of CO2 for a 10-second period to purge any air from the system. If no
leaks are detected, shut off CO2.
10. Slowly inject 10 cm3 of sulfuric acid into Chamber 1 with a hypodermic syringe and needle
through the rubber septum.

Page 2-44
11. At the same time, immediately restart CO2 flow. Adjust the rate to about 200-400 cm3 per
minute (ball in flow meter is between the two lines). One cartridge should provide about 15-
20 minutes of flow at this rate.
12. Observe any changes in the appearance of the Dräger tube color. Note and record the
maximum darkened length in the same units marked on the tube. The CO2 should be flowed
for a total of 15 minutes, even though the front of the darkening area may become diffused.
In the high-range tube an orange color may appear ahead of the black front if any sulfides or
sulfites are present in the sample. This orange region should be ignored and only the
darkened length recorded.

Dräger Tube Information

Low Range Dräger Tubes High Range Dräger Tubes

Sulfide Range Sample Volume Sulfide Range


Sample Volume cm3 mg/L
cm3
mg/L

1.2-24 10.0 30-1050 10.0


2.4-48 5.0 60-2100 5.0
4.8-96 2.5 120-4200 2.5

C. Calculations

The soluble sulfides in the sample are calculated as follows:

NOTE: The DRÄGER tubes have recently been changed, so know which ones you
are working with for the calculations.

Previous Dräger tubes

Low Range H2S 100/a: marked 1 - 20 tube factor = 12


Sulfides, mg/L = (Darkened Length x 12) / Sample Volume, cm3

High Range H2S 0.2%/A: marked 1 - 17 cm tube factor = 600 (*batch factor / 0.4)
Sulfides, mg/L = (Darkened Length x tube factor) / Sample Volume, cm3

Present Dräger tubes

Low Range, H2S 100/a: marked 100 - 2000 ppm

Sulfides, mg/L = (Darkened Length x 0.12) / Sample Volume, cm3

High Range, H2S 0.2%/A: marked 0.2 - 7 vol %

Sulfides, mg/L = (Darkened Length x 1500) / Sample Volume, cm3

Page 2-45
D. Example

Low Range H2S 100/a: marked 100-2000 ppm


5 cm3 of sample
darkened length = 1000 ppm

Sulfides, mg/L = (1000 x 0.12) / 5


= 150 / 5
= 30

High Range H2S 0,2%A: marked 0.2-7 vol%


5 cm3 of sample
darkened length = 2.5 %

Sulfides, mg/L = (2.5 x 1500) / 5


= 3750 / 5
= 750

E. Remarks

1. The entire assembly should be thoroughly cleaned and dried before and after each use.
2. All flexible tubing and gas train components must be H2S resistant.
3. Due to changes in tube graduation, be sure of which type you are using.

NOTE: For accurate results, use a sample size that will cause at least half of the tube to
darken.

SULFITE: Hach Sulfite Test Kit

A. Procedure

Low Range [1 drop = 1 mg/L Sodium Sulfite (Na2SO3)]

1. Measure a sample by filling the flask to the 100 cm3 mark.


2. Add the contents of one Sulfite 1 Reagent Powder Pillow. Swirl to mix.
3. Add the contents of one Sulfamic Acid Powder. Swirl to mix.
4. Add Sulfite 3 Reagent dropwise (with constant swirling of the mixing bottle and counting
the drops) until a permanent gray-blue color appears. Each drop of Sulfite 3 Reagent is
equal to 1 mg/L Sodium Sulfite (Na2SO3).

Page 2-46
High Range [1 drop = 10 mg/L Sodium Sulfite (Na2SO3)]

1. Measure a sample by filling the square mixing bottle to the 10 cm3 mark.
2. Add the contents of one Sulfite 1 Reagent Powder Pillow. Swirl to mix.
3. Add the contents of one Sulfamic Acid Powder. Swirl to mix.
4. Add Sulfite 3 Reagent dropwise (with constant swirling of the mixing bottle and counting
the drops) until a permanent gray-blue color appears. Each drop of Sulfite 3 Reagent is
equal to 10 mg/L Sodium Sulfite (Na2SO3).

NOTE: To express as mg/L Sulfite (SO3=), multiply the result in Step 4 by 0.64.

TOTAL HARDNESS

CALCIUM AND MAGNESIUM

A. Description & Equipment

This test measures the amount of soluble magnesium and calcium ions in the mud
filtrate. When measured simultaneously, the result is called total hardness. The calcium ion
concentration can be determined separately and when it is subtracted from the total hardness, the
magnesium ion concentration can be determined. Different buffer-indicator combinations are
used in these determinations. It is imperative not to intermix the various buffers and
indicators.

This test requires the following materials:

Titration Dish
Pipettes
Buffer
Indicator
Total Hardness Titrating solution (1 cm3 = 20 eq/m3 of hardness)
Distilled Water

B. Procedure

1. Add 1 cm3 of filtrate to a titration dish. Add 3-4 drops of Total Hardness Buffer solution
and 3-4 drops of Total Hardness Indicator solution. If a wine red or purple color develops,
the filtrate contains hardness. Add Total Hardness Titrating solution dropwise while stirring
until the water turns to blue.
2. Add Total Hardness Titrating solution , stirring continuously, until the sample turns blue,
and record end point.

Page 2-47
C. Calculations

The total hardness is calculated as:

eq/m3 Calcium and Magnesium = cm3 of total hardness titrating solution x 20

Sometimes the total hardness is reported as calcium. If this is the case:

mg/L Calcium = eq/m3 total hardness x 20

D. Various Buffer-Indicator Combinations

1. Baroid Versenate Buffer (Ammonium Hydroxide, pH = 12-13) with Baroid Versenate


Indicator (Calgamite).
2. Manver Indicator with Ammonium Hydroxide Buffer (pH = 12-13).
3. Eriochrome Black T indicator with Ammonium Hydroxide Buffer (pH = 12-13).
4. All of these are used to determine total hardness.

CALCIUM AND MAGNESIUM SEPARATELY

A. Description & Equipment

This test is run identically to the total hardness test except that a special indicator and
buffer system is used. The buffer is a Potassium Hydroxide (pH = 14) and the indicator is the
Calver II powder.

This test requires the following materials:

Titration Dish
Pipettes
Calver Buffer
Calver II indicator
Total Hardness Titrating solution (1 cm3 = 20 eq/m3 of hardness)
Distilled Water

B. Procedure

1. Pipette 1 cm3 of filtrate into the titration dish.


2. Dilute with a small amount of distilled water.
3. Add 5-6 drops of Calcium Buffer to raise the pH.
4. Add a few grains of Calver II indicator and mix to produce a strong wine red color. If no
calcium is present the sample will be blue.
5. Add Total Hardness Titrating solution, stirring continuously, until sample turns blue.

Page 2-48
C. Calculations

Calcium concentration eq/m3

eq/m3 Calcium = cm3 of Total Hardness Titrating Solution x 20

Magnesium concentration eq/m3

eq/m3 Magnesium = eq/m3 Total Hardness minus eq/m3 Calcium

Calcium concentration mg/L

mg/L Calcium = eq/m3 Calcium x 20

Magnesium Concentration

mg/L Magnesium = eq/m3 Magnesium x 12.1

D. Remarks

1. This test actually measures several metal ions simultaneously: calcium, magnesium, lead,
iron, aluminum, zinc, and manganese. Usually the results are reported as being all from
calcium and/or magnesium since the quantity of the other metal ions is usually negligible.

Page 2-49