A Comprehensive Look At the Acid Number Test

1 dari 6

http://www.machinerylubrication.com/Read/1052/acid-number-test

Current Issue
Archive
Subscribe

Search:
Home | Buyers Guide | Jobs | Glossary | Events | Bookstore | Newsletters | Browse Topics

GREASES

HYDRAULICS

INDUSTRIAL LUBRICANTS

SYNTHETICS

FILTRATION

STORAGE/HANDLING

A Comprehensive Look At the Acid

Number Test

OIL ANALYSIS

Related Articles
Keys for Testing Transformer Oils
The Benefits of Route-Based Oil Analysis

Noria Corporation

Tweet

Like

Share

The Truth About Additive Depletion

Tags: oil analysis

Additive depletion, contamination and oxidation are common pathways of lubricant

degradation. The acid number (AN) test is one of the methods available in the oil analysis field
used to estimate the amount of additive depletion, acidic contamination and oxidation. AN does
not directly measure the rate of oxidation, it merely measures the by-product of oxidation. It is
also beneficial to trend AN to determine the rate of depletion of certain additives. The purpose
of this article is to attempt to answer the following questions:
What are the main objectives of measuring AN?
What nomenclature is being used in industry? (strong acid number (SAN), total acid
number (TAN), etc.)?
What standardized methods are currently used in the industry?
What modified tests exist and why?
What are the advantages and disadvantages of each test (reproducibility, repeatability,
etc.)?

What Exhaust Gas Can Indicate About Engine

Oil Health

White Papers
H-1/Food Grade Lubricants:The Pure, Safe,
High-Tech, Sustainable Approach to Food,
Beverage and Pharmaceutical Plant
Lubrication
A Roadmap for World-Class Ultrasound
On-Site Trace Metal Analysis For Gas Turbines
Understanding Oil Analysis: How It Can
Improve Reliability of Wind Turbine Gearboxes

Job Board

What are the dos and don'ts of comparing results?

Lubrication

How is AN trended and what are the common trends?

Oil Analysis

Once these questions are answered, a better understanding of how to use AN results will be
achieved.

More...

Buyers Guide
Oil Analysis Laboratories
Oil Analysis Instruments
Oil Sampling Hardware

Poll

Begin a free subscription to Machinery Lubrication Magazine.

5/20/2015 10:10 AM

A Comprehensive Look At the Acid Number Test

2 dari 6

http://www.machinerylubrication.com/Read/1052/acid-number-test

Exit this survey

Figure 1. Correlating Changes in RUL to Oxidation Life Cycle8

Objectives of Measuring AN
AN is the measure of acid concentration in a nonaqueous solution. It is determined by the
amount of potassium hydroxide (KOH) base required to neutralize the acid in one gram of an oil
sample. The standard unit of measure is mg KOH/g. AN does not represent the absolute acid
concentration of the oil sample. The AN measurement detects both weak organic acids and
strong inorganic acids. A change in the acid concentration of an oil can originate from multiple
sources. Acidic contaminants, wrong oil, alkaline-reserve depletion and oxidation by-products
can cause an increase in acid concentration. Table 1 lists common acids that can be detected.
Understanding the extent of additive depletion is key in determining the RUL of an oil. Some
additives are weakly acidic and can elevate the oil's initial AN. As the lubricant ages these
additives deplete, thereby reducing the acidity created by the additives. The common antiwear
additive, zinc dialkyl dithiophosphate (ZDDP), produces certain AN trends during lubricant
aging. Concurrently, the oil is possibly being contaminated with acidic constituents, increasing
the acid content in the oil. The combined effects of additive depletion, acidic contamination and
other acidic-affecting events create a challenge in determining what the AN represents. Figure
1 shows the underlying components that affect the AN during lubricant aging. It can be seen
that during an induction period the antioxidant additives are depleting; once these additives are
depleted, the base oil begins to oxidize if the stressing conditions are sufficiently high. By
trending the AN, this increase can be detected.

Does your plant use funnels

for topping up machines?
Yes
No

Vote

Create your own user feedback survey

Table 1. AN May Detect These Corrosive Oils

Nomenclature Used in Industry Total Acid Number vs. Acid Number

Currently in North America, the term total acid number (TAN) is being replaced with acid
number (AN). This change is based on the fact that AN tests do not detect the total acid
concentration of the lubricant. The acid concentration of the lubricant contains both strong and
weak components. Strong acidic components are referred to as SAN. The weak components
and the strong components are typically combined as AN. Even though AN is comprised of both
acidic components, it does not represent all acidic components in the lubricant. For instance,
the AN and base number (BN) tests are not affected by extremely weak acids and bases that
have a dissociation constant of less than 10-9. This is the reason that TAN is being replaced by
AN.
pH vs. AN
The pH and AN test methods measure different aspects of the oil's acidic or alkaline character.
The pH test method measures the apparent pH of the oil. The apparent pH is a representation
of how corrosive the oil may be, but it does not indicate the concentration of acidic or alkaline
constituents. The pH test method is useful in applications where corrosive oil could cause
considerable damage. It is also valuable in lubricant systems with a high potential for the
formation or the contamination of strong acids.
The AN and BN test methods respectively measure the concentration of acidic and alkaline
constituents. Both acidic and alkaline constituents can exist in oil at the same time. In fact,
some additives are amphoteric, meaning they can behave as either a base or an acid. In some
oils, it is important to monitor both the AN and BN to determine the reactions in the oil. AN and
BN do not indicate the strength of the acidic or alkaline constituents in the lubricant, which
reduces their ability to indicate the oil's corrosiveness. AN has a better ability than pH to detect
and monitor weak acids, which do not readily dissociate in water. This prevents the pH test
method from obtaining a good indication of how the weak acid concentration is changing in the
lubricant.

Begin a free subscription to Machinery Lubrication Magazine.

5/20/2015 10:10 AM

A Comprehensive Look At the Acid Number Test

3 dari 6

http://www.machinerylubrication.com/Read/1052/acid-number-test

Table 2 lists the current ASTM standard test methods for determining AN. Each test has been
designed for specific purposes, with ASTM D664 and ASTM D974 being the two most commonly
used tests. ASTM D1534 and ASTM D3339 are similar versions of D974, used for special cases.
AN tests can be broken up into two titration categories: potentiometric or colorimetric. The
potentiometric method uses a potentiometer to detect the acidic constituents and coverts it to
an electronic read out. The output is plotted and analyzed to determine the inflection of the test
method. The colorimetric method uses paranaphthol-benzene, which responds to a change in
the pH indicator that has been added to the solution. Once the acidic constituents have been
neutralized by the KOH, the sample will change from orange to blue-green, indicating the end
point.

Table 2. Common ASTM AN Test Methods

ASTM AN Tests
ASTM D664 measures acidic constituents by using a potentiometer to determine an end point.
This method can be used to measure both AN and SAN. To prepare the sample a mixture of
toluene, isopropyl alcohol and water is dissolved into a sample. Potassium hydroxide is then
titrated into the solution using a burette. The potentiometer output is monitored while the KOH
is titrated into the solution. If the inflection is indistinguishable, the buffer potential will be
considered the AN. The inflection point is commonly used on new oil; however, for used oils the
inflection may become indistinguishable requiring the use of the buffer potential as the end
point.
ASTM D974 is the measure of acidic constituents using a color change to indicate the
inflection. The sample is dissolved into a solution of toluene, p-naphtholbenzne, and isopropyl
alcohol containing water. The solution is titrated with KOH while the color is monitored. This
test is used on new oils and oils that are not excessively dark.
ASTM D1534 is similar to ASTM D974 in that they both use a color change to indicate the end
point. ASTM D1534 is designed for electric insulating oils (transformer oils), where the viscosity
will not exceed 24 cSt at 40C. The standard range of applications is for oils with an AN
between 0.05 mg KOH/g and 0.50 mg KOH/g, which is applicable to the transformer oils.
ASTM D3339 is also similar to ASTM D974, but is designed for use on smaller oil samples.
ASTM D974 and D664 roughly use a 20 g sample; ASTM D3339 uses a 2.0 g sample, as shown
in Table 2.

Table 3. D974 Repeatability from ASTM Standard

Modified Tests
AN tests are typically conducted to obtain an accurate indication of additive depletion and
possible contamination of ingressed acids. The standard ASTM methods are time consuming,
have relatively poor reproducibility and utilize hazardous materials. In an effort to control the
source of these issues, many modified versions of the AN test are currently being used. Each
test is specific to its application. For example, a lab may automate the test to reduce labor and
increase throughput.
For Used Oil Analysis Labs
Laboratories modify tests to improve throughput while decreasing the use of hazardous
materials and their cost. Throughput, or speed, is important to larger laboratories because it is
necessary to find the fastest test that does not sacrifice quality. Cost also plays a major role. A
standard test slate provided by a lab may also include particle count, viscosity at 40C, etc. The
cost of this standard test slate needs to be affordable for the end user; therefore, each
individual test performed may need to be streamlined to ensure both quality and economy are
achieved.

Begin a free subscription to Machinery Lubrication Magazine.

5/20/2015 10:10 AM

A Comprehensive Look At the Acid Number Test

4 dari 6

http://www.machinerylubrication.com/Read/1052/acid-number-test

Field test kits are often used as a first-line AN test. They typically contain premeasured
reagents that allow for convenient field testing. Some of the field kits use a pass/fail test, which
involves adding a preset amount of KOH to the solution. This indicates whether the AN has
reached a specific point. Field tests can also report actual results. For example, one such kit
uses a volume-sampling syringe to ensure that the oil samples are the same size. A disposable
burette is used to titrate the KOH. Because the oil sample is a specific size, the burette has
been scaled to indicate the AN. Once the color has changed, the user only can read the acid
number from the burette.

Table 4. D974 Reproducibility from ASTM Standard

Advantages and Disadvantages Repeatability

ASTM defines repeatability as "the difference between successive test results obtained by the
same operator with the same apparatus under constant operating conditions on identical test
material". Based on this definition, using D664, data was found to be within +/- 7 percent of
the mean 95 percent of the time for fresh oils using the inflection point method or +/- 12
percent of the mean for used oils with the buffer end point method. ASTM D974 has the
repeatability as stated in Table 3. For example, a sample that has a 0.15 AN could vary from
0.10 AN to 0.20 AN for ASTM D974 and could vary 0.17 to 0.13 AN for ASTM D664.
Repeatability can be obtained on a modified test. A good lab should be able to tell how reliable
its modified version is. This confirms that comparing results from one single lab or test
procedure is best.
Reproducibility
ASTM's definition of reproducibility is "the difference between two single independent results
obtained by different operators working in different laboratories on identical test material."
Ninety-five percent of the time, the reproducibility of ASTM D664 is +/- 20 percent of the mean
for fresh oils using the inflection point method or +/- 44 percent of the mean for used oil using
the buffer end point method. For example, if a mean AN was 0.10 you could expect results
from 0.14 to 0.06 95 percent of the time. The reproducibility of ASTM D974 is shown in Table 4.
Consider that you received an oil analysis report from multiple labs on the same oil. It has a
mean AN of 0.05, and the results could vary from 0.09 to 0.01.
It is hard if not impossible to compare results between labs when modified AN tests are used.
Quality labs will likely have a correlation to the ASTM standard; unfortunately, this would also
incorporate more error. It is best practice to compare only results from the same test for
trending purposes.
According to ASTM, "the AN obtained by this standard (D664) may or may not be numerically
the same as that obtained in accordance with test methods D974 and D3339." However, the
magnitude of the results should be the same. By trending results from one specific test
method, additive depletion and contamination can be detected.

Figure 2. Variations in AN Trends by Oil Type11

Dos and Don'ts of Comparing Results

Comparing results between samples can become complicated if proper control is not used.
There are many aspects which may and normally will affect the results from an AN test. As
stated previously, there are multiple test methods used. Some of the methods are within ASTM
standards and some are modified. The average AN result from a laboratory will likely be from a

Begin a free subscription to Machinery Lubrication Magazine.

5/20/2015 10:10 AM

A Comprehensive Look At the Acid Number Test

5 dari 6

http://www.machinerylubrication.com/Read/1052/acid-number-test

Dos
Compare results to historical results on the lubricant (trending).
Verify which lab has analyzed the lubricant and the test used.
Consistently use the same lab and test method for a specific lubricant.
Ensure a representative sample is provided to the lab.
Don'ts
Don't switch back and forth between methods.
Don't switch back and forth between labs. Don't delay oil analysis; instead, provide the
sample to the lab as soon as possible.
Don't compare results between different methods.

Common Trends of AN Trending

In the world of AN tests, there is a current state of disillusionment. Each laboratory provides
results from its own modified test methods, which forces the end user to rely on precision over
accuracy. First, the user must be wary of comparing results between labs. In an ideal
environment, both accuracy and precision would be provided. In a next-to-ideal world, only
accuracy would be provided. Simple mathematics could be used to determine the exact value,
but in the real world of AN tests, the precision of each individual labs is what can be counted
on. The results are not on the true mark, but relative to each other they are good. Comparing
results from different labs would result in values all over the board. By focusing on the
precision of one lab or test procedure, a trend emerges. Trending can enable the end user to
properly evaluate his/her lubricant with greater confidence.
General Trends
Trending results is the best way to work around the accuracy discrepancies that come from
using AN results in machine condition monitoring. By using results from one specific test or lab,
the ability to trend is good. Figure 2 illustrates the common trends found in lubricants. Linear
trends are for some ester-based synthetics and oils going through oxidation. It represents the
linear oxidation of the base oil. The parabolic curves may characterize rust and oxidized (R&O)
oils. The AN remains constant during the additive depletion induction phase. Once the R&O
additives have depleted, the base oil will begin to oxidize. The switching trend is representative
of EP oils, where some of the additives are acidic. As additives deplete and react, the AN varies.
These effects make it hard to trend EP oils unless the normal switching pathway is known in
advance.
AN is an important tool in the oil analysis industry when used properly. Understanding how the
AN is calculated and what variances exist will help in interpreting the results. SAN is usually not
tested, but it may be useful to an oil analysis program if protection from corrosion is important
or if there is a possibility of contamination from an inorganic acid. The two commonly used
ASTM test methods both exhibit issues that create the need for modified tests. With the
modified tests currently being used in industry, it is important to remember why they are in
place and the implications when comparing results. Being able to properly trend results will
enable end users to adequately evaluate their oil condition.
References
1. ASTM D664: Standard Test Method for Acid Number of Petroleum Products by
Potentiometric Titration. American Society of Testing and Materials International, West
Conshohocken, Pa.
2. ASTM D974: Standard Test Method for Acid Number and Base Number by Color-Indicator
Titration. ASTM Intl., West Conshohocken, Pa.
3. ASTM D1534: Standard Test Method for Approximate Acidity in Electrical Insulating
Liquids by Color-Indicator Titration. ASTM Intl., West Conshohocken, Pa.
4. ASTM D3339: Standard Test Method for Acid Number of Petroleum Products by
Semi-Micro Color Indicator Titration. ASTM Intl., West Conshohocken, Pa.
5. Finch, Stephen. "Evaluation of New Field Test Methods for Base Number and Acid Number
in Lubricating Fluids." Dexsil.
6. Smart, Clifford L. "Get Smart with Improved TAN Titrations." Practicing Oil Analysis
magazine. October 2000.

Begin a free subscription to Machinery Lubrication Magazine.

5/20/2015 10:10 AM

A Comprehensive Look At the Acid Number Test

6 dari 6

http://www.machinerylubrication.com/Read/1052/acid-number-test

Samples." Practicing Oil Analysis magazine. May 2003.

8. Kauffman, R.E. "Rapid Determination of Remaining Useful Lubricant Life." Handbook of
Lubrication and Tribology, Volume III. E. Richard Booser, Editor. CRC Press, Boca Raton,
Fla. 1994.
9. Snook, Willet A. "Used Engine Oil Analysis." Lubrication, Volume 54, Number 9, 1968.
10. Ball, Peter G. "New pH Test Offers Benefits over TAN/TBN." Practicing Oil Analysis
magazine. September 1998.
11. Oil Analysis Level I Course Manual, Noria Corporation. 2006.
Practicing Oil Analysis (7/2007)

Related Articles
Keys for Testing Transformer Oils
The Benefits of Route-Based Oil Analysis
The Truth About Additive Depletion
What Exhaust Gas Can Indicate About Engine Oil Health

Services Subscribe | Contact Us | Privacy Policy | RSS | Advertise

Quick Links Home | Buyers Guide | Jobs | Glossary | Events | Bookstore | Newsletters | Browse Topics

NORIA CORPORATION

MACHINERY LUBRICATION | RELIABLE PLANT

Begin a free subscription to Machinery Lubrication Magazine.

5/20/2015 10:10 AM