331.

0 INTRODUCTION

pH OF CRUDE OIL

The pH value is a measure of the acidity or alkalinity of a solution. It approximates but is not
equal to p[H], the negative logarithm (base 10) of the molar concentration of dissolved
hydrogen ions (H+). In a solution pH approximates but is not equal to p[H], the negative
logarithm (base 10) of the molar concentration of dissolved hydronium ions (H3O+); a low pH
indicates a high concentration of hydronium ions, while a high pH indicates a low
concentration. When the H+ and the H3O+ ions exist in equal quantities, the solution is said to be
neutral. When the H+ and the H3O+ exists in larger quantities respectively, th e solution is said
to be either acidic or alkaline.

TEMPERATURE AND pH DEPENDENCE

Temperature plays a significant role in pH measurement. All solutions will change their pH value
with temperature. This is the result of the shifting of the chemical equilibrium of the
components mainly of dissociation. An increase in any solutions’ temperature will cause a
decrease in its viscosity and an increase in the mobility of its ions in solution. An increase in
temperature may also lead to an increase in the number of ions in solution due to the
dissociation of molecules (this is particularly true for weak acids and bases). As pH is a measure
of the hydrogen ion concentration, a change in the temperature of a solution will be reflected
by a subsequent change in pH.
Overall, the effects of temperature can be divided into two main categories:
• Temperature effects that diminish the accuracy and speed of response of the electrode.
• Temperature Coefficient of Variation effects on the material being measured by the sensor,
whether it be calibration buffer or sample.
The automatic temperature compensation (ATC) in a pH meter corrects for the change in mV
per pH unit generated by the glass electrode, as given by the Nernst equation.
E = EO – 2.3 (RT/nF) log aH+
where,
E = total potential (in mV) developed between the sensing and reference electrode
Eo = standard potential of the electrode at aH += 1 mol/l
R = Gas constant
T = temperature
n = valency of ion
F = Faraday constant
aH+= activity of the hydrogen ion in solution
However, the slope or the Nernst factor (2.3RT/nF) will change when temperature changes.

For the ideal electrode,

Temperature ℃ Nernst slope (mV/pH)
0 54.20
10 56.18
20 58.17
25 59.16
30 60.15
40 62.14
50 64.12
60 66.10
70 68.09
80 70.07
90 72.06

The pH change with temperature is not an error rather; it is the true pH of the solution at the
new temperature. For highly basic solutions, the effect of temperature on pH is greatest.

When the pH of a sample (such as oil) is taken from a process tank (such as from within a
reservoir) to be tested in the laboratory, the measured temperature differs hence the pH value
also differs.

Therefore, if two pH values of the same solution measured at different temperatures are to be
compared, it’s usually desirable to use a function known as the solution temperature
compensation which converts the pH at the measured temperature to the pH at the reference
temperature. The reference temperature is almost always 25℃.
The change in pH with temperature is called the solution temperature coefficient (pH/℃). For
example, if a solution has a temperature coefficient of -0.035(pH/℃), the pH decreases
0.035units for every ℃ rise in temperature.
PRINCIPLE OF OPERATION OF THE pH METER
The hand held pH meter found in many mud kits uses the potential differences (Voltage) to
measure the hydrogen ion concentration of solutions. The theory that enables us to measure
pH uses an equation with the voltage, a standard value called "emf", temperature, the number
of electrons transferred in one reaction, and the ion-exchange equilibrium constant.
The important thing to note is that concentrations of ions can be related to a measured voltage.
Voltage is a relationship which, in order to be measured, must be taken with some frame of
reference. Similar to elevation, where the reference point is sea level and all measurements of
elevation are given in relation to sea level, voltage must also have a reference point. From this
reference point, it is possible to measure all other voltages in relation to the reference.
The inside of the pH meter houses two electrodes, a glass electrode and a reference electrode.
Because they have been made in one body, the electrode is referred to as a combination
electrode. The reference electrode contains a solution of known ionic concentration (and thus
known voltage) which is used as a reference. The other electrode, the glass electrode, also
contains hydrogen ions of known concentrations. Part of the glass electrode can be seen as the
glass bubble at the bottom of the pH meter. This is the pH sensitive part of the meter, and here
is how it works:
Glass is a non-crystalline (amorphous) compound composed of Silicon and Oxygen (SiO4)
tetrahedral structure. On the surface of the glass, there are negatively charged oxygen atoms
that can bond to cations in a solution.
Inside the glass, the oxygen atoms bind to Cations that can fit in between the SiO4 framework.
Although many Cations are of the proper size and charge to fill the inner glass network, the
cation that is normally most abundant in glass is Sodium (Na+). Sodium Cations can slowly move
through the nonhydrated tetrahedral framework. When glass is immersed in water, the silica
network begins to hydrate. Typically, after several hours in immersion, water can penetrate up
to 10 nm into a sheet of glass. By comparison, the thickness of the glass bulb is approximately
ten thousand times larger (.1mm). In the swollen area where water has been absorbed, the
Cations diffuse out into the solution; at the same time, hydrogen ions (H+) diffuse into the
spaces vacated by the Cations ions. The higher the concentration of H+ ions that are present,
the more this exchange will take place. This continues until equilibrium is reached for the inner
and outer surfaces of glass. This is similar to the ion-exchange equilibrium taking place in an
MBT titration. If, in the likely case, the ion exchange equilibrium is not the same on the inside
surface of the glass as it is on the outside surface , there is a difference in potential between the
surfaces. The potential is not carried directly by H+ ions, but can be “felt” electrically because
the Na+ Cations in the glass carry a charge. Consequently, the difference in hydrogen ion
concentration between the inner and outer surfaces of glass creates a potential. This voltage is
measured to determine the pH of a solution. This is possible because the potential difference
between the reference electrode and the glass electrode depends only on the ionic
concentrations inside the electrodes (a known quantity) and the potential difference across the
glass membrane (a function of the pH of the outside solution).
RESISTIVITY OF CRUDE OIL

Resisitivity 𝜌(𝛺-m) is an electrical property. It is the reciprocal of conductivity (𝛺-m)-1.

Mathematically, it can be expressed thus:

𝑅. 𝐴
𝜌=
𝑙
Resistivity is a fundamental parameter of crude oil as it describes how readily it will allow
electric current to be transmitted through it. High values of resistivity implies that the material
is very resistant to the flow of electrical current through it. In practice, resistivity is difficult to
measure due to its strong dependence on temperature.

The resistivity (𝜌m) of a drilling mud is influenced by the dissolved salts (ppm) or (gpg, grain per
gallon) in the water portion and the insoluble solid material contained in the water portion. The
greater the concentration of dissolved salts, the lower resistivity (i.e the higher the
conductivity) of the solution. Unlike metals, the resistivity of a solution decreases as
temperature increases. This is because increasing the temperature of a solution will lead to an
increase in the mobility of its ions. As a result, conductivity of the solution to electric flow
increases leading to a consequent decrease in resistivity. Water has a low resistivity and electric
current will follow the path of least resistance. Whereas the presence of water will reduce
resistivity, the presence of gas bubbles in crude oil should increase subsurface resistivity. It is
necessary to measure resistivity because the mud, mud cake, mud filtrate resistivity exert a
strong effect on the electric logs taken in that mud. The mud resistivity varies greatly from the
actual resistivity values due to the various factors encountered in the actual operation.

TEMPERATURE COEFFICIENT OF RESISTANCE

Temperature co-efficient of a resistance is the amount by which the resistance changes when
temperature changes per degree centigrade. It’s represented by 𝛼. For solutions, 𝛼 is negative
because increasing the temperature decreases the resistivity. The relationship between ,
resistance and temperature is given by the equation below:
RT = RO(1+ 𝛼t)
Where,
RT : resistance of a conductor at t ℃
RO: resistance of a conductor at 0 ℃
t: Temperature (℃)
𝛼: TEMPERATURE COEFFICIENT OF A RESISTANCE
2.0 APPARATUS/ EQUIPMENT USED
1. ACL 380 Resistivity Meter: It is designed to test conductive , anti-static and static
dissipative surfaces for electrical resistivity.

2. pH Meter: Used to measure the hydrogen ion concentration H+ of the crude oil solution
3. Beaker: Contains the crude oil solution
3.0 EXPERIMENTAL PROCEDURE
 400ml of the crude oil sample was measured into a beaker and then placed on a
heating arrangement.
 The probe of the pH meter was then inserted into the sample and as the heating
continued over temperature ranges between 40℃ - 80℃, the pH and resistivity
readings were taken simultaneously.
 The equipment used was then turned off and the values obtained were then
tabulated.
4.0 RESULTS AND CALCULATIONS
Volume of crude oil used = 400Ml
Temperature ℃ pH Conductivity (𝛺-m)-1 Resistivity (𝛺-m)
40 6.09 38 0.026
45 6.02 40 0.025
50 5.96 43 0.023
55 5.65 62 0.016
60 5.46 77 0.013
65 5.22 92 0.011
70 5.16 100 0.010
75 5.11 104 0.009
80 5.09 120 0.008

CALCULATIONS
From Table 1, the slope can be calculated thus,
∆𝑦 5.1−6.09
Slope = ∆𝑥 = = -0.032pH/℃
71−40
PRACTICE EXERCISE

1. The pH value of a liquid is a measure of the acidity or alkalinity of a solution. It

approximates but is not equal to p[H], the negative logarithm (base 10) of the molar
concentration of dissolved hydrogen ions (H+).
2. Shallow reservoir. This is because as seen from the experimental result, a higher
temperature reduces the pH and in reservoir wells, temperature increases with depth.
So for shallow reservoirs, the pH value is higher.
3. Other factors affecting pH include:
 Temperature
 Salinity
 Fluid concentration
4. Resistivity of a substance is the property that describes how readily it will allow electric
current to be transmitted through it. Mathematically, it can be expressed thus:

𝑅. 𝐴
𝜌=
𝑙
5. As temperature increases, the resistivity of crude oil decreases.
5.0 DISCUSSION

As seen from the experimental results, as temperature increases, both the pH and resistivity of
crude oil decrease. Based on the theoretical overview, corrections must be made for
temperature effects on these values in order to obtain as accurate results as possible.

The following precautions should also be taken:

 Avoid zero error when reading from the resistivity and pH meters
 Take lower reading from the meniscus of the thermometer
6.0 CONCLUSION

Temperature has a number of significant effects on pH measurement. Analysts must have an

appreciation of these effects so that they can improve and maximise the accuracy of their pH
measurements. Automatic Temperature Compensation (ATC) should always be utilised during
calibration to correct for the non-Nernstian slope of electrodes. For pH meters that feature
automatic buffer recognition, the correct calibration buffers, as specified by the instrument
manufacturer, must always be used as the meter has the temperature profile for these buffers
stored in memory. Additional sources of error include the calibration isopotential point,
thermal or chemical equilibrium effects on the electrode and the temperature coefficient of
variation on buffers and samples. To reduce these potential errors, instrument calibration and
sample measurement should be performed at the same temperature ideally using a water bath.
Also, as the pH of solutions is temperature dependent, the measurement temperature should
always be recorded.

Implementation of these simple guidelines will lead to either a reduction or elimination of the
problems associated with temperature. This will result in improved accuracy in pH results thus
giving the user greater confidence in their pH measurements. Depending on the decisions made
based on the pH readings the consequences of inaccurate pH measurement can be more than
just a waste of the analysts’ time.

The same considerations should be kept in mind while measuring crude oil resistivity as it’s also
temperature-dependent.
ABSTRACT

The objective of the experiment was to consider pH and resistivity measurements dependence
on temperature. These two values were observed to decrease as the temperature was
increased over the range 40℃-80℃. The pH and resistivity measurements were made using the
pH meter and resistivity meter respectively. The report seeks to develop the basis for factoring
the effects of temperature on the two measured quantities namely resistivity and pH.
TABLE OF CONTENTS

TITLE PAGE

ABSTRACT ……………………………………………………………………………………i

SECTIONS

1.0 INTRODUCTION/THEORETICAL PRINCIPLES ……………………….

2.0 EQUIPMENT USED …………………………………………………………….
3.0 EXPERIMENTAL PROCEDURE ……………………………………………..
4.0 RESULTS AND CALCULATIONS …………………………………………..
5.0 DISCUSSION ……………………………………………………………………...
6.0 CONCLUSION/RECOMMENDATIONS …………………………………

REFERENCES ……………………………………………………………………………….
REFERENCES

 Helmuth Galster, “pH Measurement:Fundamentals, Methods, Applications,

Instrumentation”. VCH Publishers Inc., 1991, p21.
 Steven S. Zumdahl, Chemistry 3rd Edition.
 D.C. Heath & Co., 1993, p645. PGG415 lab manual(March 2014) p.20
EFFECT OF TEMPERATURE ON pH AND RESISTIVITY OF CRUDE

OIL

PGG415: PETROLEUM ENGINEERING LABORATORY III

A LABORATORY REPORT
BY
ENIGBOKAN TITILAYO (MATRIC NO. 110409026)
WITH
GROUP I:
ETUKENO, M.A.
DARAMOLA, O.O.
JOHNSON, T.M.
KANU, V.C.
MOSURO, O.A

DATE PERFORMED: 09-04-2014

DATE SUBMITTED: 23-04-2014