HYDROGEN-ION DETERMINATION

PGG305: PETROLEUM ENGINEERING LABORATORY I

A SHORT LABORATORY REPORT

BY
MAFUA, K.K. (Matric No. 120409040)

WITH
GROUP C:
OGUNLEYE, G.O.
OTUNBA, J.O.
ORIGBEMISOYE, B.A.
EZE, A.M.
BABATUNDE, K.A.
OGUNRINADE, O.M.
SMITH, A.B.
OLADIMEJI, I.J.
OYENOWO, O.P.
POPOOLA, M.O
BAMIDELE, B.O.
UDOSEN, J.J.
OSINUGA, V.A.

Date performed: 16-04-2015

Date submitted: 23-04-2015

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ABSTRACT
The hydrogen-ion concentration of the drilling mud is a measure of the degree of
acidity or alkalinity of the drilling mud usually expressed in terms of pH.
In this experiment, the goal was to determine the pH of different samples of
drilling mud. The pHydrion dispenser and pH meter can be used to carry out this
experiment, but the pH meter is preferable as it measures pH to a higher degree
of accuracy.
There are basically two (2) types of drilling mud; “water-based mud (WBM)” and
“oil-based mud (OBM)”. Water-based mud is mud that has majority of its weight
composed of water compared to its other components. Oil-based mud is mud
which has a major weight of oil in its composition compared to its other
components. Different masses of bentonite were mixed with a specific volume of
water in this experiment.
10g, 20g, 30g and 40g of bentonite were mixed with 100ml of water respectively,
and stirred till a homogeneous mixture was obtained. After stirring, the electrode
from the pH meter was inserted into the mixture and the pH was read after the
pH reading was constant over two minutes. The mud was then filtered using a
filter paper and funnel. 1 ml of the filtrate was taken out and poured into a small
conical flask and one (1) drop of phenolphthalein indicator was added to it.
The pH values obtained for the 10g, 20g, 30g and 40g of bentonite were 8.01,
8.04, 8.12 and 8.13 respectively. There was no color change observed on the
addition of phenolphthalein indicator to the filtrates from the different samples of
the mud used. The pH values obtained from the experiment indicate that the
drilling mud samples were “basic” (i.e pH values above 7)
In the petroleum industry, measuring the pH value of drilling mud is very
important as its value enables a mud or drilling engineer to work with standard
operating conditions. Also, if the pH of the drilling mud sample is below 7 (which
implies an acidic mud), the drilling engineer would be able to adjust this pH value
as an acidic mud would have corrosive effects on the drilling equipment, since
most parts of the drill assembly are made up of metals.

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 TABLE OF CONTENT
TITLE PAGE
ABSTRACT
INTRODUCTION
THEORETICAL PRINCIPLES
EXPERIMENTAL APPARATUS
EXPERIMENTAL PROCEDURE
EXPERIMENTAL RESULTS
DISCUSSION
CONCLUSION
REFERENCES

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INTRODUCTION
In 1909, Danish biochemist, S.P.L Sorensen proposed the use of a logarithmic
scale to express the concentration of hydrogen ions (H +) and hydroxide ions (OH-).
This scale has become known as the pH scale.
It is difficult to give an exact definition of pH. A couple of simple descriptions
offered are, “power of Hydrogen” and “potential Hydrogen” ion concentration.
Neither are perfect descriptions. Both present a way of remembering the
significance of “p” and “H”. Simply stated, pH tells us whether a solution is acidic,
alkaline or neutral. It does not tell us how much acid or alkali is present. It is a
good “warning sign” (Proceed with Caution), but it does not establish whether
the compound is corrosive or dangerous.
pH is a critical measurement. Life depends upon it. For instance, human blood is
basic with a pH between 7.3 and 7.5. If the pH of blood drops below 7.3, acidosis
occurs. If the pH of blood rises above 7.5, alkalosis occurs. Death will occur if the
pH of blood goes below 7.0 or above 7.8. Our human existence depends upon a
balanced and buffered blood pH.
There are several methods used to measure pH. Two of the simplest are litmus
paper and liquid acid-base indicators. The most widely used method is the pH
meter. These meters are easy to use and very accurate. When chemists want to
measure the amount of alkali or acid in a solution, they use a process called
titration. Titration measures the amount of alkali and/or acid in a solution. pH
measures the concentration of hydrogen ions present in a solution. Both are
important.
The pH measurement is used as an aid in determining the need for chemical
control of the mud as well as indicating the presence of contaminants such as
cement, gypsum e.t.c. The optimum pH for any drilling mud is dependent upon
the type of mud being used.
The satisfactory methods of measuring the pH of a drilling mud are in use: a
modified colorimetric, such as the pHydrion Dispenser, and an electrometric
method using a glass-electrode instrument such as the Beckman or analytical pH
meter.

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THEORETICAL PRINCIPLES
pH is a value representing the hydrogen ion concentration in a liquid. We use it to
indicate acidity or alkalinity of drilling mud, especially water based mud. The pH is
presented in a numerical value (0-14) which means an inverse measurement of
hydrogen concentration in the fluid.
The pH value of a solution is the negative log of its hydrogen-ion activity (α),
which is the product of hydrogen ion concentration [H +] and the activity
coefficient of hydrogen (βH+) at that concentration.
The pH formula is as shown below;
pH = -log α = -log βH+ [H+]
In pure water and in dilute solutions, the H + activity can be considered the same
as the H+ concentration

pH = -log βH+ [H+] = -log10[H+]

pH = -log10[H+]
where;
H+ = hydrogen ion concentration in mol
βH+ = activity coefficient of hydrogen at H+
The pH of a solution measures the degree of acidity or alkalinity relative to the
ionization of water. Pure water dissociates to yield 10-7 M of [H+] and [OH-] at
25oC; thus, the pH of water is 7, which is the point of neutrality.

pHwater = -log [H+] = -log 10-7 =7

According to the pH formula, the more hydrogen atoms present, the more acidity
of substance is but the pH value decreases. Generally speaking, the pH of 7
means neutral. Fluids with a pH above 7 are considered as alkaline. On the other
hand, the fluids with pH below 7 are defined as acidic.

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In the drilling mud, there are three (3) main chemical components involved in
alkalinity of drilling fluid which are bicarbonate ions (HCO3-), hydroxyl ions (OH-),
and carbonate ions (CO32-). As we know, the alkalinity means ions that will reduce
the acidity.

MEASURING pH
Measuring pH involves comparing the potential of solutions with unknown [H +] to
a known reference potential. In order to get accurate measurements for the pH of
drilling mud, we need to use a pH meter instead of using a pH paper because the
pH meter can give us more accurate figures compared to a pH paper. However,
there is need to ensure that the pH meters are calibrated frequently.
pH meters convert the voltage ratio between a reference half-cell and a sensing
half-cell to pH values. Today, most electrodes are combination electrodes with
both the reference and sensing half-cells in the same body.
Reference half-cells contain a conductor (usually silver with a silver chloride
coating) immersed in a solution with known [H +]. The potential between this
internal conductor and the known solution is constant, providing a stable
reference potential.
Sensing half-cells (measuring half-cells) are made of a non-conducting glass (or
epoxy) tube sealed to a conductive glass membrane. Like the reference half-cell,
the sensing half-cell also contains a conductor immersed in a buffered electrolyte
solution, ensuring constant voltages on the inner surface of the glass membrane
and the sensing conductor.

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When the pH electrode is immersed in the solution to be measured, a potential is
established on the surface of the sensing glass membrane. If the unknown
solution is neutral, the sum of fixed voltages on the inner surface of the glass
membrane and on the sensing conductor approximately balances the voltage on
the outer surface of the glass membrane and the reference half-cell. This results
in a total potential difference of 0 mV and pH value of 7.
In acidic or alkaline solutions, the voltage on the outer membrane surface
changes proportionally to changes to changes in [H +]. The pH meter detects the
change in potential and determines [H+] of the unknown by the Nernst Equation:
2.3 RT
E = E0 + nF
log unknown¿ ¿

where;
E = total potential difference (measured in mV)
Eo = reference potential
R = gas constant
T = temperature in Kelvin
n = number of electrons
F = Faraday’s constant
[H+] = hydrogen ion concentration

pH TEMPERATURE COMPENSATION
The pH of any solution is a function of its temperature. Voltage output from the
electrode changes linearly in relationship to changes in pH, and the temperature
of the solution determines the slope of the graph. One pH unit corresponds to
59.16 mV at 25oC, the standard voltage and temperature to which all calibrations
are referenced. The electrode voltage decreases to 54.20 mV/pH unit at 0.0 oC and
increases to 74.04 mV/pH unit at 100.0oC as shown below:

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Since pH values are temperature dependent, pH applications require some form
of temperature compensation to ensure standardized pH values. Meters and
controllers with automatic temperature compensation (ATC) receive a continuous
signal from a temperature element and automatically corrects the pH value based
on the temperature of the solution. Manual temperature compensation requires
the user to enter the temperature. ATC is considered to be more practical for
most pH applications.

pH INDICATORS
A pH indicator is a halochromic chemical compound added in small amounts to a
solution so the pH (acidity or basicity) of the solution can be determined visually.
Hence, a pH indicator is a chemical detector for hydronium ions (H 3O+) or
hydrogen ions (H+). Normally, the indicator causes the color of the solution to
change depending on the pH. Indicators can also show change in other physical
properties; for example, olfactory indicators show change in their odor.
In and of themselves, pH indicators are frequently weak acids or weak bases. The
general reaction scheme of a pH indicator can be formulated as;

HInd + H2O ↔ H3O+ + Ind-

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Here, HInd stands for the acid form and Ind - for the conjugate base of the
indicator. The ratio of these determines the color of the solution and connects the
color to the pH value. pH indicators that are weak protolytes, the Henderrson-
Hasselbalch Equation for them can be written as:
pH = pKa + log ¿ ¿
For optimal accuracy, the color difference between the two species should be as
clear as possible, and the narrower the pH range of the color change, the better.
In some indicators such as phenolphthalein, one of the species is colorless,
whereas in other indicators, such as methyl red, both species confer a color.
While pH indicators work efficiently at their designated pH range, they are usually
destroyed at the extreme ends of the pH scale due to undesired reactions.

BUFFER SOLUTIONS
A buffer solution (more precisely, pH buffer or hydrogen ion buffer) is an aqueous
solution consisting of a mixture of a weak acid and its conjugate base, or vice
versa. Its pH changes very little when a small or moderate amount of strong acid
and base is added to it and thus it used to prevent changes in the pH of a solution.
Buffer solutions are used as a means of keeping pH at a nearly constant value in a
wide variety of chemical applications. Many life forms thrive only in a relatively
small pH range so they utilize buffer solutions to maintain a constant pH.

DRILLING MUD

Drilling mud, also called “drilling fluid”, in petroleum engineering, is a heavy,

viscous fluid mixture that is used in oil and gas drilling operations to carry rock
cuttings to the surface and also to lubricate and cool the drill bit.

Drilling muds are traditionally based on water, either fresh water or sea water,
naturally occurring brines, or prepared brines.

TYPES OF DRILLING MUD

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Many types of drilling fluids are used on a day to day basis. Some wells require
that different types be used at different parts in the hole, or that some types be
used in combination with others.

There are basically two types of drilling mud namely;

 Water-based drilling mud

 Oil-based drilling mud

WATER-BASED DRILLING MUD

Water-based drilling mud is mud that has water as the major component of its
weight compared to its other constituents.

A typical water-based drilling mud consists of;

 Liquid water, continuous phase

 Reactive solids, for viscosity and yield point
 Inert solids, for density
 Chemical additives, to control properties

A most basic water-based mud system begins with water, then clays and other
chemicals are incorporated into the water to create a homogeneous blend
resembling something between chocolate milk and a malt (depending on
viscosity). The clay (called “shale” in its rock form) is usually a combination of
native clays that are dissolved into the fluid while drilling, or specific types of clay
that are processed and sold as additives for the water-based mud system.

The most common of these is “bentonite”, frequently referred to in the oilfield as

“gel”. Gel likely makes reference to the fact that while the fluid is being pumped,
it can be very thin and free-flowing (like chocolate milk), though when pumping is
stopped, the static fluid builds a “gel” structure that resists flow. When an
adequate pumping force is applied to “break the gel”, flow resumes and the fluid
returns to its previously free-flowing state. Many other chemicals (e.g. Potassium
Formate) are added to a water-based mud system to achieve various effects,

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including: viscosity control, shale stability, enhance drilling rate of penetration,
cooling and lubricating of equipment.

REACTIVE SOLIDS

 Clays are added to provide viscosity and yield strength

 Mechanism is very complex
 Internal structure of clay particles and electrostatic forces develop viscosity
 Two types of clay are available
 Bentonite Clay, montmorillomite (smecite) group of clay used with fresh
water
 Attapulgite Clay, salt gel (playgorskite) group of clay used in fresh and salt
water

NATURE OF CLAY

 Defined as natural, earthy, fine-grained material that develops plasticity

when wet
 Formed from chemical weathering of igneous and metamorphic rocks
 Mainly formed from volcanic ash
 Wyoming bentonite is the famous one
 Atoms form layers
 There are three atomic layers: tetrahedral layer, octahedral layer, and
exchangeable layer
 Tetrahedral layer is made up of flat honeycomb sheet made up of silicon
atom surrounded by four oxygen atoms
 Tetrahedral are likely to form sheet by sharing three of their four oxygen
atoms
 Octahedral layer are sheets composed of linked octahedral, each made up
of an aluminium and magnesium atom surrounded by six oxygen atoms
 They linked through oxygen making three octahedral layers
 Exchangeable layers of atoms or molecules bound loosely into the structure
giving the clay its physical properties

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  The nature of theses layers stacked together on top of one another defines
the type of clay
 The sandwiches of tetrahedral and octahedral layer are joined with the
exchangeable layer
 Distance between layers is 0.9 -1.5mm
 In some clays, the exchangeable layer is relatively tightly bound in the
structure
 Cation Exchange Capacity (CEC) measure how readily exchange can take
place
 CEC is measured by dispersing a known amount of clay in a solution of
magnesium chloride to replace as much as possible the exchangeable layer
with magnesium
 It is then transferred to a solution of potassium or calcium chloride
 The amount of potassium or calcium absorbed by clay is measured
 The amount is expressed in milli-equivalents per 100g of dry clay and called
CEC
 Typical values of bentonite are 70-130 and for attapulgite, 5-99
 CEC is used as guide to determine the quality of clay

HYDRATION OF CLAY

 Clays with high CEC exchange large amount of water into the exchangeable
layer and adsorb water onto the outer surface of plates
 This effect gives high viscosity and yield point
 Adsorption of water causes a very sticking expansion of clay
 For sodium bentonite, the distance between layers increased from 9.8 to
40 A ngstrom
 For calcium bentonite, from 12.1 to 17 A
 Overall hydration transforms clay from powder to plastic slurry
 The effectiveness is measured by yield of clay

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  Yield of clay is defined as the number of barrels of 15 CP mud obtained
from 1 ton (2000 lb) of dry clay
 Clay yield depends upon purity, nature of atoms in exchangeable layers and
salinity of water

BENTONITE

 Bentonite consists primarily of montmorillonite

 Came from French town Montmorillon, where first mining occurred in 1874
 Basic structure is close to pyrophillite
 There are a small number of exchangeable ions, sodium, calcium and
magnesium
 Most common bentonite are those with sodium and calcium as
exchangeable ions

INERT SOLIDS

 Includes low gravity and high gravity

 Low gravity includes sand and chert
 High gravity are added to increase mud weight or density
 They are referred to as weighting materials
 Mud name as weighted mud, they are:

- Barite (barium sulphate, BaSO4) sp.gr. 4.2

Used to prepare mud in excess of 10 ppg
Referred to as weighting agent for low cost and high purity
- Lead Sulphides (galena) sp.gr. 6.5 – 7.0
Allowing mud weight up to 35 ppg
- Iron Ores, sp.gr. 5+
More erosive
Contain toxic materials

CHEMICAL ADDITIVES
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  Used to control mud properties
 Divided into thinners and thickeners

MUD THINNERS

 Reduce viscosity by breaking attachment of plate through edge or face by

attacking the clay plates

MUD THICKENERS

 Lime or cement: Increase viscosity by flocculation resulting from

replacement of Na+ cations and Ca2+ cations
 Polymers
 Large molecules made up of many repeated small units called monomers
 Used for filtration control, viscosity modification, flocculation and shale
stabilization
 Causes little change in solid contents of mud
 Polymer-mud have high shearing-thinning ability at high shear rate
 This reduces viscosity and in turn frictional pressure loss

TYPES OF WATER-BASED MUD

Clear Water

 Fresh or saturated brine water can be used to drill hard, compacted and
near-normally pressured formation

Native Mud

 Water pumped down letting it react with formation containing clay or shale
 Water dissolves clay and returns to the surface as mud
 Characterized by high solid content and high filter loss resulting in thick
filter cake

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Calcium Mud

 Reduce clay and shale swelling

 Superior to fresh water mud for drilling gypsum and anhydrite

In general, water-based muds are satisfactory for the less demanding drilling of
convectional vertical wells at medium depths.

OIL-BASED DRILLING MUD

Oil-based drilling mud is mud that has oil as the major component of its weight
compared to its other constituents.

 Water in oil emulsion

 Diesel or crude oil forms its continuous phase
 Sometimes called invert emulsion
 Water droplets are emulsified in oil
 Water is used for gel strength
 Agitation is required to break the water into small droplets
 Oil/water ratio determine the final properties
 Higher oil water increases resistance to contamination and temperature
stability
 Used to drill hole with severe stability
 More stable at high temperatures

Many muds are oil-based, using direct products of petroleum refining such as
diesel oil or mineral oil as the fluid matrix. In addition, various so-called synthetic-
based muds are prepared using highly refined fluid compounds that are made to
more-exacting property specifications than traditional petroleum-based oils.
Synthetic-based muds were developed in response to environmental concerns
over oil-based fluids, though all drilling muds are highly regulated in their

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composition, and in some cases, specific combinations are banned from use in
certain environments.
Oil- and synthetic-based muds contain water (usually brine), bentonite, and
barite for viscosity and weight, and various emulsifiers and detergents for
lubricity.
Oil-based muds are better for greater depths or in directional or horizontal
drilling, which place greater stress on the drilling apparatus.

PROPERTIES OF DRILLING MUD

The properties of drilling mud includes

 Mud weight or density

 Rheological properties
 Filtrate and mud cake
 pH value

MUD WEIGHT OR DENSITY

 Weight or mass per unit volume

 Depends on solids in the liquid, either in solution or suspended
 Calculated by sum of weights over some of volumes
 It increases by adding solid materials
 Decreased by adding water or oil or aerating the liquid
 Measured by mud balance: a steel cup filled with fresh mud sample and
balanced on a knife edge
 Expressed in ppg, pcf or kg/m3

RHEOLOGICAL PEOPERTIES
They are;

 Plastic Viscosity

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  Yield Point and
 Gel Strength

PLASTIC VISCOSITY

 Controls the magnitude of shear stress developed as one layer of fluid

slides over another
 It is a measure of friction between layers
 Its provides a scale of the fluid thickness
 It decreases with increasing temperature with liquids. For gases, the
reverse is the case
 Effective viscosity depends on fluid velocity flow pattern, which is difficult
to measure
 Plastic viscosity is measured by Viscometer

YIELD POINT

 A measure of the attractive forces between particles due to positive and

negative charges
 A measure of the forces causes mud to gel in case of motionless mud
 This shows that a minimum level of stress must be provided before mud
flow
 Yield point is expressed in lb/100ft2
 Yield point is also measured by a Viscometer
GEL STRENGTH

 This is the ability of mud to develop structure

 It defines the ability of mud to hold solids and measure thixotropy
 It is determined using the Viscometer
 The mud sample is stirred at a high speed and then allowed to rest for 10
seconds or 10 minutes
 It is expressed in lb/ft2

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FILTRATION AND FILTER CAKE

 Fluid loss against porous and permeable rock is called “filter loss”
 A layer of solids deposited on the rock is described as “filter cake”
 Loss occurs when mud pressure is higher than formation pressure
 Quantity of mud loss depends on volume of filtrate, thickness and strength
of filter cake, and differential pressure
 It can be determined by filter press, called “API filter press”
 Bentonite, emulsified oil, dispersant, and starch are used to reduce filter
loss. Starch is used with pH > 11.5
 Ideal mud gives small filter loss and thinand tough mud cake
pH OF MUD

 Describes the acidity or alkalinity of mud

 It is defined as the negative logarithm of the hydrogen ion concentration
[H+]
 It is measured by pH meter or strips

MUD CONTAMINANTS
Sodium Chloride

 Enters mud during drilling salt domes, rock salt beds, evaporates or any bed
containing salt water
 Increases viscosity, yield strength and gel strength of bentonite mud due to
flocculation
 Salt decreases pH value
 Salt solution cause hole enlargement, so salt saturated mud is
recommended

Anhydrite and Gypsum

 Forms of calcium sulphate (CaSO4)

 Formation containing anhydrite and gypsum are common in massive or
interbedded wells
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  Contamination leads to clay flocculation, increase in viscosity, yield
strength, filtrate loss and gel strength
 Sodium Carbonate (Na2CO3) can be added to treat mud
Cement

 Enters mud from poor cement jobs or squeeze cementing

 Increase viscosity, yield point and gel strength
 Mud used to drill cement is discarded
Mud contaminated with cement can be treated with sodium bicarbonate

FUNCTIONS OF DRILLING MUD

The main functions of drilling mud can be summarized as follows;
1) Remove cuttings from well
2) Suspend and release cuttings
3) Control formation pressures
4) Seal permeable formations
5) Maintain wellbore stability
6) Minimize formation damage
7) Cool, lubricate and support the bit and drilling assembly
8) Transmit hydraulic energy to tools and bits
9) Ensure adequate formation evaluation
10) Control corrosion (in acceptable level)
11) Facilitate cementing and completion
12) Minimize impact on environment

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EXPERIMENTAL APPARATUS
The apparatus used in carrying out the experiment include:
1. Weighing balance
2. Laboratory cup mixer
3. Beaker
4. Measuring cylinder
5. pH meter
6. pHydrion Dispenser

WEIGHING BALANCE
This is used to weigh accurate measurements of mud or additives. It has a
precision value of 0.1g.

CARE OF WEIGHING BALANCE

The weighing balance is switched off from the power source after use, and
cleaned.

LABORATORY CUP MIXER

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This instrument is used to mix the clay, additives and water/oil into a thick
consistency. It uses a rotary effect on the heterogeneous mixture to form a
homogenous mud mixture.

CARE OF LABORATRORY CUP MIXER

The laboratory cup mixer is cleaned to remove mud that must have stickled to it

BEAKER
It is a measuring instrument. It is used to measure and quantify the amount of a
liquid in ml. it is used for only small liquids and has a limit of 500 ml.

MEASURING CYLINDER
This instrument is used to measure correct amounts of water that is needed to be
mixed with the mud.

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pH METER
A pH meter is an electronic device used for measuring the pH (acidity or alkalinity)
of a liquid (though special probes are sometimes used to measure the pH of semi-
solid substances). A typical pH meter consists of a special measuring probe (a
glass electrode) connected to an electronic meter that measures and displays the
pH reading.
The pH probe measures pH as the activity of the hydrogen cations surrounding a
thin-walled glass bulb at its tip. The probe produces a small voltage (about 0.06
volt per pH unit) that is measured and displayed as pH units by the meter. For
more information about pH probes, see glass electrode.
CALIBERATION:
For very precise work the pH meter should be calibrated before each
measurement. For normal use calibration should be performed at the beginning
of each day. The reason for this is that the glass electrode does not give a
reproducible e.m.f. over longer periods of time. Calibration should be performed
with at least two standard buffer solutions that span the range of pH values to be
measured. For general purposes buffers at pH 4 and pH 10 are acceptable.
The pH meter has one control (calibrate) to set the meter reading equal to the
value of the first standard buffer and a second control (slope) which is used to
adjust the meter reading to the value of the second buffer. A third control allows
the temperature to be set. Standard buffer sachets, which can be obtained from a
variety of suppliers, usually state how the buffer value changes with temperature.
For more precise measurements, a three buffer solution calibration is preferred.
As pH 7 is essentially, a "zero point" calibration (akin to zeroing or taring a scale or
balance), calibrating at pH 7 first, calibrating at the pH closest to the point of

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interest (e.g. either 4 or 10) second and checking the third point will provide a
more linear accuracy to what is essentially a non-linear problem. Some meters
will allow a three point calibration and that is the preferred scheme for the most
accurate work. Higher quality meters will have a provision to account for
temperature coefficient correction, and high-end pH probes have temperature
probes built in.
The calibration process correlates the voltage produced by the probe
(approximately 0.06 volts per pH unit) with the pH scale. After each single
measurement, the probe is rinsed with distilled water or deionized water to
remove any traces of the solution being measured, blotted with a scientific wipe
to absorb any remaining water which could dilute the sample and thus alter the
reading, and then quickly immersed in another solution.
pH meters range from simple and inexpensive pen-like devices to complex and
expensive laboratory instruments with computer interfaces and several inputs for
indicator and temperature measurements to be entered to adjust for the slight
variation in pH caused by temperature. Specialty meters and probes are available
for use in special applications, harsh environments, etc

pHYDRION DISPENSER
The pHydrion dispenser provides a series of paper indicator strips that determine
pH from 1.0 to 14.0. Changes in color to color intensity over the range of each
indicator should be sufficient to allow the operator to read within 0.5 pH unit.
The report of pH is in units 0 to 14 in the nearest 0.5 estimated pH. The pHydrion
dispenser does not give an accurate pH measurement in muds having a high salt

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concentration. The electronic pH meter is recommended for testing muds with
salt concentrations in excess of 10,000 ppm cl.
It should be noted that, although pHydrion dispenser is a good instrument for
measuring pH, is is not very accurate.

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EXPERIMENTAL PROCEDURE
PROCEDURE FOR THE DETERMINATION OF pH OF MUD USING pHYDRION
DISPENSER
1. A one-inch strip of indicator paper was removed from the pHydrion
Dispenser which was judged to be within the required, and was placed
gently on the surface of the mud.
2. Sufficient time (from a few seconds to a couple of minutes) was allowed to
elapse for the paper strip to soak up filtrate and change colour.
3. The colour of the strip was matched with the chart on the side of the
dispenser from which the strip was taken and the pH of the mud was read.
4. In a situation where the colour was off the scale and could not be matched,
the test was repeated with a different indicator strip judged to be closer to
the pH range required.

PROCEDURE FOR THE DETERMINATION OF pH OF MUD USING pH METER (TWO-

ELECTRODE INSTRUMENT)
1. The instrument was turned on and standardized according to detailed
directions.
2. The tips of the electrode were washed under a stream of running water and
was gently wiped dry with a piece of tissue.
3. The electrodes were inserted into a 100ml beaker containing the sample of
mud to be tested. The mud was stirred around electrodes by rotating the
beaker.
4. The pH was measured according to detailed instructions attached to the
instrument. The pH was recorded after the meter reading became constant.

INSTRUCTIONS FOR USE OF ANALYTICAL pH METER

The pH meter should be buffered before each use. For a more complete check,
two or more buffer solutions should be used.

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 A. Instruction given on meter using buffer solution pH 9 should be followed
for buffering.
B. Buffer solution pH 7.0 should be poured into sample holder. The meter
should read 7.0(+-)0.3 without any readjustment.
C. Step B should be repeated using buffer solution pH 12.0. The meter should
read 12.0(+-)0.3 without any readjustment.

If the meter checks from one buffer solution to another, it may be considered to
be in good operating condition. If an attempt is made to check the pH of distilled
water with the meter, results may not be consistent. An accurate pH
measurement of distilled water is not possible due to the low hydrogen ion
concentration.
For best results, the meter should be buffered with a buffer solution near the
same value of sample being tested. Electrode should soak in buffer for five (5)
minutes or longer before making test.

PROCEDURE FOR DETERMINING THE pH OF MUD FILTRATES

1. The mud filtrate was collected.
2. One (1) ml of mud filtrate was added to a clean titration dish.
3. Two (2) drops of phenolphthalein solution was added. No colour change
was observed.

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EXPERIMENTAL RESULTS

S/N MASS OF VOLUME OF pH OF MUD PHENOLPHTHALEIN T (OC)

BENTONITE (g) WATER (mL) INDICATION OF
FILTERATE

1 10 100 8.01 NO COLOUR CHANGE 29.5

2 20 100 8.04 NO COLOUR CHANGE 29.4
3 30 100 8.12 NO COLOUR CHANGE 29.8
4 40 100 8.13 NO COLOUR CHANGE 29.9

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 A GRAPH OF WEIGHT OF BENTONITE AGAINST pH OF MUD
45

40

35

30
WEIGHT OF BENTONITE (g)

25

20

15

10

0
8 8.02 8.04 8.06 8.08 8.1 8.12 8.14

pH OF MUD

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EXERCISE
1) What is the purpose of hydrogen-ion determination by the pH meter
method?

ANSWER
The main purpose of hydrogen-ion determination by the pH meter method is to
get pH values which are more accurate as the pH meter offers a greater degree of
accuracy in terms of pH values. It does this with the aid of potential differences
(voltage) to measure the hydrogen-ion concentration of solutions.

2) What is the name of the instrument used for electrometric hydrogen-ion

determination?

ANSWER
The name of the instrument used for electrometric hydrogen-ion determination is
the pH meter.

3) What effect does each of the following have on pH?

a) Passing of Time: It increases the pH.
b) CO2: It is an acidic gas, hence, it reduces pH.
c) H2S: It is also an acidic gas and hence, it reduces pH.
d) Saltwater Flows: This is alkaline in nature. It therefore increases pH.
e) Dilution: Dilution causes the pH of the solution to shift closer to the center
of the pH scale. i.e. to become closer to neutral.
f) Cement Contamination: It increases pH.

4) Why is it important to know and control the pH of mud?

ANSWER

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The knowledge and control of the pH of drilling mud is relevant in order to have a
smooth and more efficient drilling process.
pH measurements indicate the presence of contaminants in the drilling mud such
as cement and gypsum.
Mud with pH values below 7 indicates a drilling mud that is acidic. Drilling mud
with high acidity tends to have a corrosive effect on drilling tools (drill pipe, drill
bits e.t.c) as they are mostly made of metals, and this corrosive effect damages
the drilling equipment and incurs more operational cost in the long run. It is
therefore important to have knowledge of the mud pH in order to ascertain
whether the mud is acidic, and if acidic, appropriate treatment would be carried
out on the mud in order to prolong the life of the drilling assembly and save cost.
The knowledge of the pH of drilling mud would also enable the drilling or mud
engineer to control the values in order to work with specified standard operating
conditions.

5) Plot the graph of weight of bentonite against pH.

ANSWER
Page 31

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DISCUSSION
As we know, this experiment is determining the hydrogen-ion concentration of
different samples of drilling mud. The most basic water-based mud systems begin
with water, bentonite and other chemicals are incorporated into the water to
make a homogeneous blend resembling something between chocolate milk and a
malt.
The data taken in this experiment was measured by the pH meter. The pH meter
provides a simple, practical method for accurate determination of mud pH.
As seen from the data obtained above, as the mass of bentonite that was mixed
with the constant volume of water increased (i.e from 10g – 40g), the pH values
of the mud increased pH also increased. This showed that there exists a direct
proportionality between the weight of bentonite and the pH of the mud.
The pH values obtained for the 10g, 20g, 30g and 40g of bentonite were 8.01,
8.04, 8.12 and 8.13 respectively. There was no color change observed on the
addition of phenolphthalein indicator to the filtrates from the different samples of
the mud used. The pH values obtained from the experiment indicate that the
drilling mud samples were of a “basic” nature, since solutions that have pH values
above 7 are basic from the conventional pH scale.
There were some dissimilarities between results between the pH meter
readings and the indicator solution, and these dissimilarities can be
attributed to the fact that the indicator solutions were not accurate.
The experiment was carried out observing basic precautions so as to obtain
reliable results.
The efficiency of the drilling fluid to perform its functions is based on flow
behavior or rheological properties of the fluid system. The rheological indication is
an indication of the ability of drilling fluid in hole and hole erosion, suspension of
drill cuttings, hydraulic calculations and requirement of drilling fluid treatment.
These rheological properties in turn are dependent on the pH values of the

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drilling mud and so it can be said that the efficiency of the drilling process as a
whole depends on the pH of the mud since the pH of the mud controls these
rheological properties.

CONCLUSION
As said earlier, it is difficult to give an exact definition of pH. A couple of simple
descriptions offered are, “power of Hydrogen” and “potential Hydrogen” ion
concentration. Neither are perfect descriptions. Both present a way of
remembering the significance of “p” and “H”.
pH is a value representing the hydrogen ion concentration in a liquid. We use it to
indicate acidity or alkalinity of drilling mud, especially water based mud. The pH is
presented on a numerical scale of 0-14.
pH value < 7 = acidic
pH value > 7 = basic
pH value = 7 = neutral
Instruments such as the pH meter and pHydrion dispenser are used in measuring
pH values, but the pH meter is more accurate and thus preferable.
At different stages during drilling processes, the ionic composition of the drilling
mud changes from its original formulation at the different stages. The
effectiveness of the drilling process is affected by the pH of the drilling mud as
increasing the pH of drilling mud will increase the rheological properties (plastic
viscosity, apparent viscosity, Yield Point and Gel Strength) of the drilling mud. It is
probably due to increasing flocculation of clay platelets as a result of increasing
cation concentration in the mud.
In the drilling process, it is very necessary to determine the pH value of the mud
sample. The knowledge and control of the pH of drilling mud is relevant in order
to have a smooth and more efficient drilling process.
pH measurements indicate the presence of contaminants in the drilling mud such
as cement and gypsum. Mud with pH values below 7 indicates a drilling mud that
is acidic. Drilling mud with high acidity tends to have a corrosive effect on drilling

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tools (drill pipe, drill bits e.t.c) as they are mostly made of metals, and this
corrosive effect damages the drilling equipment and incurs more operational cost
in the long run. It is therefore important to have knowledge of the mud pH in
order to ascertain whether the mud is acidic, and if acidic, appropriate treatment
would be carried out on the mud in order to prolong the life of the drilling
assembly and save cost.
The knowledge of the pH of drilling mud would also enable the drilling or mud
engineer to control the values in order to work with specified standard operating
conditions in order to achieve optimum production from drilled wells.
The relevance of determining the hydrogen-ion concentration of drilling mud
cannot be over emphasized. The knowledge of mud pH is essential to every mud,
drilling, petroleum engineer, and the oil drilling team as a whole. Experts are
employed in the industry to carry out the duties as the whole drilling process is
quite dependent on the hydrogen-ion concentration values.

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RECOMMENDATIONS
Since too high a pH value (too basic) or too low a pH value (too acidic) of a drilling
mud sample isn’t proper for well drilling, it is recommended that frequent tests
on the mud to be used for drilling be carried out in order to ascertain the pH
value and to correct it to get optimum pH values for the mud.
The cost of drilling fluid is typically about 10% (may vary greatly) of the total cost
of well construction and demands competent mud engineers. This makes it
necessary to recommend that competent mud engineers be employed on the
field so as to ensure large cost savings when the mud engineer performs
adequately.

CARE OF INSTRUMENTS
 Instruments should always be cleaned and dried after use.
 Upon completion of experimental measurements, the pH meter should be
buffered.
 The experimental equipment should not be bent. They should be handled
with care.
 The electrodes should be cleaned after the pH meter has been used.
 The tips of the electrode should not be touched.
 Electrical equipment should not be operated in very high or very low
currents.
 Electrical apparatus should be turned off after use.
 The pHydrion dispenser should be kept in a clean, dry place.

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REFERENCES
1. PGG 305, Petroleum Engineering Laboratory Manual 1, Department of
Chemical Engineering, University of Lagos.
2. Drilling Fluids Processing Handbook, Shale Shaker Committee of the
American Society of Mechanical Engineers, Elsevier, March 15, 2011.
3. Ryan Caenn, Henry C., Darley H., George Robert Gray – Gulf Professional
Publishing, Composition and Properties of Drilling and Completion Fluids.
4. Elton, H. (2001) – Hydraulic Optimization of Foam Drilling For Maximum
Drilling Rate in Vertical Wells.

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