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Measurement of density using oscillation-type density meters. Calibration,

traceability and Uncertainties

Conference Paper · June 2009

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 MEASUREMENT OF DENSITY USING OSCILLATION-TYPE DENSITY
METERS
CALIBRATION, TRACEABILITY AND UNCERTAINTIES
A. Furtado, E. Batista, I. Spohr, E. Filipe
Instituto Português da Qualidade (IPQ)
Rua António Gião, 2 – Caparica – Portugal
afurtado@mail.ipq.pt
Résumé
La masse volumique d'un fluide peut être déterminé en
utilisant plusieurs instruments de mesure. Récemment, les
densimètres à oscillations ont montré une grande
polyvalence, ils sont utilisés en différentes branches de
l'industrie. Le Laboratoire des Propriétés des Liquides
(LPL) de l'Institut Portugais pour la Qualité (IPQ) réalise
l'étalonnage de ces instruments par rapport à un étalon de
densimètres à oscillations, dans l’intervalle de mesure de
la masse volumique de (500 à 2 000) kg/m3. La traçabilité
des mesures est assurée par des solutions certifiées du PTB
et de la DKD. La nécessité d'assurer la traçabilité
métrologique à un système de détermination absolue de la
masse volumique des liquides a conduit à des évolutions
récentes dans ce domaine, qui seront décrites dans ce
document. Il sera également décrit le modèle
mathématique et le bilan d’'incertitude de l'étalonnage de
densimètres à oscillations.
Abstract
The density of a fluid can be determined using several
measuring instruments. Recently the oscillation-type
density meters have shown great versatility, being used in
various branches of industry. The Laboratory of Properties
of Liquids (LPL) of the Portuguese Institute for Quality
(IPQ) performs the calibration of these instruments by
comparison with a standard density meter, in the
measuring interval of density from (500 to 2 000) kg/m3.
The metrological traceability is given by Certified
Reference Materials (CRMs) of PTB and DKD. The need
to ensure traceability to a system of absolute determination
of the density of liquids has led to recent developments in
this area which will be described in this paper. It will be
also described the mathematical model and uncertainty
budget of the calibration of the oscillation-type density
meters.
Introduction
The density is defined as the property of a body, given by
the ratio of its mass to its volume (kg/m3). The fluid
density is a major key in the control of most industrial
processes, because it allows not only, a better management
of the process but also the accurate determination of the
quantity and quality of the product. The measurement of
the density is used in drinks industry, to control the alcohol
content in binary mixtures or the sugar content in soft
drinks and fruit juices; in the pharmaceutical industry, to
determine the specific gravity of medicinal preparations; in
the oil industry to determine the API gravity and for the
quality control of fuels and additives; in the chemical and
nuclear, to determine the concentration of acids, bases and
other solutions and to determine radioactive substances
concentration; in the food industry, cosmetics, etc.
This magnitude can be determined using several
measuring instruments, such as pycnometers, hydrometers
and oscillation-type density meters, and also using the
method of hydrostatic weighing. Recently the oscillation-
type density meters have shown great versatility, and are
being used in various branches of industry. The advantages
of using these instruments are its response time, its use
simplicity and the small volume of the needed sample.
Measurement of liquids density
From Archimedes to Hans Stabinger
Formally assigned to Archimedes, but invented by Hipatia
of Alexandria (370-415 DC), the hydrometers are the
oldest, simple, highly effective and widely used tools for
measuring the density with different levels of accuracy.
The method for hydrometers calibration, based on
hydrostatic weighing, was introduced by Cuckow [1] in
1949. This method allows hydrometers of any range to be
calibrated at any point of its scale through the
measurement of the force of buoyancy in the air and when
immersed in the reference liquid (see Figure 1A). This is
the most accurate method and is used in most National
Metrology Institutes, including the IPQ [2]. The
participation in the EURAMET 702 Project, gave LPL the
recognition of its Calibration and Measurement Capability
(CMC) in the calibration of hydrometers by the Cuckow
Method’s, using n-nonane at 20 °C, in a density measuring
interval [3] from (750 to 1 000) kg/m3, with an expanded
uncertainty of 0,1 kg/m3 for an expansion coefficient,
k = 2.
A B
Figure 1. A - System for hydrometers calibration;
B - System for measuring the density of
liquids by hydrostatic weighing.
In 1967, the company Anton Paar GmbH presented the
first digital density meter for liquids and gases. It was the
first instrument to use the principle of the U shaped
vibrating tube, of Stabinger Hans and Hans Leopold for
the determination of the density. These first
oscillation-type density meters were subject to errors
induced by the viscosity in most of the samples. These
errors were usually higher than 0,7 kg/m3 in instruments
with a resolution of 0,1 kg/m3. In 1998, Hans Stabinger
developed a density meter (Paar DMA 5000) with a new
measurement cell which applied the viscosity correction of
the sample, thereby avoiding the systematic errors of the
others instruments.
Oscillation-type density meters
Principle of operation
The working principle of an oscillation-type density meter
is based on the law of harmonic oscillation, in which a U
tube is completely filled with the sample to be analyzed,
and subjected to an electromagnetic force. The
measurement of the frequency and duration of vibration of
the tube filled with the sample, allows the determination of
the density value of the sample. This measuring principle
is based on the Mass-Spring Model.
The measuring cell consists of an oscillator formed by an
hallow U-shaped borosilicate glass tube that comprises
about 0,7 ml of the sample. This tube has double walls and
the space between them is filled with a gas with high
coefficient of thermal conductivity. In that space is also
placed a platinum resistance thermometer that allows the
temperature measurement of the fluid during the density
measurement. The remaining instrumentation consists of a
system of electronic excitement and electrical components
that provide a signal transmission of the period for the
processor unit, free of interferences (see Figure 2).
Evaluation
Display
Coil
Amplifier
Magnet
Frequency oscillator
Glass tube
Figure 2. Measurement cell of an oscillation-type density
meters.
The U tube oscillates at its fundamental frequency, which
is a function of the system mass. If we assume that the
sample volume inside the cell is constant, it can be seen
that the oscillation frequency is therefore a function of the
sample density. The oscillation period , is given by:
v  m
  2 (1)
C using an internal procedure based on the same ISO.
Where is the sample density,  the cell volume, m the
mass cell and C the spring constant. Applying the square
4 2v and 4 2 m we
of Eq. 1, and substituting G H
C C
obtain:
( 2  H )
 (2)
G
During the oscillation of the U tube, the sample shows the
effect of damping of the oscillation. This damping is a
function of the viscosity sample. The sample viscosity will
also have the effect of apparently slightly move the
oscillation nodes, thus increasing the apparent volume of
the cell. When these two effects are combined, the error k ,
in kg/m3, is of the order of k  0,05  , where  is the
viscosity in mPa·s.
The measurement cell oscillates at several frequencies in
two modes. This allows the damping due to the sample to
be measured and properly corrected. When the standard is
calibrated, the density is a function of the oscillation
period,  and the damping.
The internal software of the instrument includes the
assumption that:
  A 2 ( 1  D  damping  E  damping 2 )  B  C 4 (3)
where A, B, C and D are coefficients determined in the
instrument calibration using two substances of known
densities, typically air and water. Studies made in several
instruments of the same type using a wide range of CRMs,
and water suggested that the Eq. 3 with its interaction
between the period and damping is unnecessarily complex
[4]. For samples of density between (690 and 1 620) kg/m3
and viscosity above 600 mPa·s an equation of the form
  A  B 2  C  damping is more appropriate. For
liquids in the same density range, but with viscosities
below 30 mPa·s, the Eq. 4 describes better the cell
behaviour.
C
  A  B 2  (4)
damping
Calibration
Method and Metrological Traceability
The calibrations of oscillation-type density meters held by
LPL are performed at 20 ºC, through a comparative
method, using aqueous solutions in a density measuring
interval from (500 to 2 000) kg/m3. It follows a procedure
which has as a reference document the ISO 15212-1:1998
[5]. The density of the prepared solutions is measured with
the standard density meter of LPL (Anton Paar DMA5000)
and the density meter of the client. The density
measurement of the liquid samples in both density meters
are held almost simultaneously, thus ensuring that the
solution is in the same conditions of homogeneity. The
Certification of density of liquid samples is carried out
The results of calibration, certification and the uncertainty rectangular distribution. Table 1 describes the uncertainty
budget, which will be further presented, are made in an sources mentioned.
Excel sheet previously validated for that purpose. The
results obtained in the calibration are presented in a Table 1- Uncertainty contributions in kg/m3 for the
Certificate of Calibration, that also describes the combined standard uncertainty of oscillation-type density
characteristics of the calibrated instrument, conditions of meters calibration and density certification of liquid
operation, errors and expanded uncertainty associated with samples.
each value of density tested. The results of the certification Uncertainty
of density of liquid samples are presented in a Certificate, Uncertainty Uncertainty
Distribution Contributions
describing the characteristics of the sample, conditions of Components Category
(kg/m3)
the operation and an associated uncertainty. Standard density meter
ucalibration B Normal 2,5×10-2
The metrological traceability [3] of density measurements uCRMs B Normal 2,5×10-2
is achieved through calibration of the oscillation-type uresolution B Rectangular 2,9×10-5
density meter with density standard samples of CRMs urepeatability A Normal variable
utemperature B Rectangular negligible
from PTB and DKD. The traceability of temperature
measurements of the sample is assured by calibration of a urepeatability A Normal variable
platinum resistance thermometer in the Temperature utemperature B Rectangular negligible
Laboratory of IPQ. Client density meter
urepeatability A Normal variable
Uncertainty Budget uresolution B Rectangular 2,9×10-4
The uncertainties were calculated according to the GUM
[6]. The uncertainty associated with the calibration of an
oscillation-type density meter is calculated combining two Concluding Remarks
sources of uncertainty of measurement: one of the client The oscillating tube density meter area of the LPL is
density meter (uclient density meter) and the other of the standard growing in terms of the number of clients that asks for
density meter (ustandard density meter). The uncertainty density certification of liquid samples and calibration of
associated with the certification of density of liquid density meters. The LPL main goal is to complete the
samples is only related with the uncertainty of chain of the metrological traceability of liquid density
measurement of standard density meter (see Figure 3). measurement. Since 2005, LPL has been working to
uclient density meter improve a system that allows the determination of the
liquids density by hydrostatic weighing, using as a density
urepeatability standard, a silicon sphere, which mass and density are
uresolution knew and certified (see Figure 1.B), allowing the decrease
ucalibration of uncertainty in density certification. Up to now, the LPL
ucertification participated in two EURAMET projects, which are still
urepeatability ucalibration on-going. We are looking forward to open new calibration
utemperature uCRMs and certification areas, in particularly, in viscosity and
urepeatability utemperature surface tension, as well as to develop new CRMs for those
ustandard density meter uresolution two properties.

Figure 3. Cause and effect diagram with the uncertainty

contributions for the combined standard
uncertainty of oscillation-type density meters
calibration, by comparative method and
certification of liquid samples density.
The component of the standard uncertainty associated with
the repeatability of the measurements (type A) is obtained
by the standard deviation of the density measurements
average (urepeatability). The other uncertainty components are
evaluated by the type B method, including the uncertainty
related with the resolution (uresolution) of both density
meters, as a rectangular distribution. Usually, the density
meters calibrated at IPQ have a resolution of 1×10-1 kg/m3,
a resolution 100 times higher than the resolution of the
standard density meter. The main contribution to the
measurement uncertainty of the density meter standard is
the uncertainty of the CRMs (uCRMs) used for its
calibration. Finally, the uncertainty component due to the
sample temperature inside the cell (utemperature), has a
References
[1] Cuckow, F.W., “A new method of high accuracy for
the calibration of reference standard hydrometers”, J.
Chem. Ind., Vol. 68, pp. 44-9, 1949.
[2] Ferreira, M.C. e Dias, J.M., “The role of experimental
design in the hydrometer field”, XVIII Imeko World
Congress, Brazil, 2006.
[3] ISO/IEC GUIDE 99:2007, International vocabulary
of metrology - Basic and general concepts and associated
terms (VIM).
[4] Stabinger, H., "Density Measurement using modern
oscillating transducers", South Yorkshire Trading
Standards Unit, Sheffield, 1994
[5] “Oscillation type density meters – Laboratory
instruments. ISO 15212-1, 1998.
[6] “Guide to the Expression of uncertainty in
Measurement.” BIPM et al - 1.ª ed. Genève: International
Organization for Standardization, 1995.

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