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Faculty of Engineering
Mechanical Engineering Department
Triple Point Research
Prepared By
Project Team
Gnl yk Gngr 21001709
Eren zgn 21000526
Onur Albayrak 21002125
Irmak Ece Ulusoy 21001540
mge Karako 20901396
afakcan Uysal 21000680

Instructor: Dr. akir Baytarolu
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1. Introduction

In nature, substances can exist in three different phases. There are some exact temperatures and pressures
which three phases of substance in a thermodynamic equilibrium. These conditions called as triple point
and many materials have their unique triple points. For example, the triple point of ethylene occurs at a
temperature of 38.8344 C and a pressure of 0.2 mPa.
Additionally, the triple point between gas, liquid and solid phases, there may be triple points which
consists more than one solid phase for types of substances with multiple-polymorphs. Generally, a system
with p possible phases, there is a formula in the below which represents the triple points numbers.
In the terminology of measurement, zero celcius measured as 273.16 K and sea level defines as
611.73 pascal. At this condition, liquid water, water vapor and solid ice are occasionaly exist at the same
time because this is a triple point for the water. At this point, changing phases of the substance to a specific
phase is possible by changing the conditions slightly. However, if the total pressure is above the 611.73 Pa,
system can regenaretes itself to triple point for the water. In order to achieve that, the critic surfaces which
divides phases as stable, must be perfect and smooth that removes surface tensions.
Even the water has a strange phase diagram, the definition of triple point is still be valid. At higher
pressure, water has various phases which consist different liquid and ice structures. At lower temperatures
and under compression, the liquid state still exist but water passes directly from gas to solid.
In triple point, boiling ice and soliditiation of water vapor can observable. Data and charts are
available in literature that is fixed for every possible substances.The phenomena of a substance occupying
three phases simultaneously (gas, liquid and solid) while in thermodynamic equilibrium is called the triple
point of that substance. Values of triple points are fixed temperature and pressure values. The triple point
of Carbon(graphite) can be seen at 4.765 K and 10.132 kPa while Oxygen s can be seen at 54.36 K and
0.152 kPa.
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There can be triple points including more than one solid phases, when considered ice having 15
different phases, or in a sulfur system all triple points consists of two solid, one gas, one liquid system. To
define the number triple points in a system with possible n phases, the equation below is useful;


Water has a fairly complex phase diagram at high pressures, and more than one triple
points can be observed above certain pressures , the diagram and various triple points can be
seen below:


Fig. 1: Phases of water at different temparatures and pressures.






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Fig. 2 : Temperature vs Pressure Fig
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(Water at its unique triple point condition when there is ice boiling)


2. Water Triple Point Cell

The triple point of water (TPW) is the unique physical state of water in which all three phases
(solid, liquid and vapour) coexist at thermodynamic equilibrium. The TPW is realized in practice
by using TPW cells in sealed borosilicate glass- or fused-silica- envelopes containing from 400
cm3 to 500 cm3 of high-purity water. A re-entrant well, located along the axis of the cell, allows
for insertion of the Standard Platinum Resistance Thermometer (SPRT) to be calibrated. An ice
mantle is produced around the thermometer well. After creating the ice mantle, the cell is
accommodated in a water maintenance bath controlled at a temperature close to 0.01 C
(typically within few mK) or in a Dewar flask containing crushed ice, and the equilibrium between
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the three phases is automatically established within the cell and can be maintained for many
weeks. [1]

Figure 1 [2]
The Water Triple Point is the most important fixed point, the only point common to the ITS-90 and
the Thermodynamic Temperature Scale. It is an essential reference point for every temperature
laboratory. The Jarrett-Isotech cells are the best standard, all cells are not the same accept no
inferior device.

Triple Point of Water Cells are used in the calibration of thermometers. Although most commonly
used for the determination of the R of platinum resistance thermometers, they are also used for
calibration of quartz thermometers, thermistors, liquid in glass thermometers and as a reference
temperature for thermocouples. They are also used to establish the zero, and evaluate the
stability of other temperature sensing devices.

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The Jarrett-Isotech cells have been in production since 1958. A independent comparison* in
1981 showed the first cell to be within 0.000006C of the reference cell. The most recent
international study organized by BIPM consistently shows labs using both recent and
older Jarrett-Isotech cells tightly grouped, tens of K around the BIPM reference value. [3]

The capability of a triple point of water cell to provide an accurate, stable and reproducible
temperature depends upon the purity of the water in the cell. Jarrett-Isotech cells are carefully
cleaned and aged by a special procedure. They are then filled with water that has been purified
by an elaborate 12 step process designed to eliminate the possibility of contamination while
avoiding change in isotope proportions.

Jarrett-Isotech Cells use water with an isotopic content essentially similar to Standard Mean
Ocean Water. Following research by the international science community into the make up of
Standard Mean Ocean Water, and V-SMOW the BIPM recommended in 2005* that The triple
point of water is now defined as the equilibrium temperature of vapour, liquid and solid water,
with the liquid water having the isotopic composition defined by the following amount of
substance ratios:
0.00015576 mol 2H per mol 1H
0.000379 mol 17O per mol 16O
0.002005 mol 18O per mol 16O

Since early in 2000 Jarrett-Isotech Cells have been made to this definition and our cells have
been within +10 and -40K of it. During 2005, subsequent to the CCT definition, the waterin our
triple point cells has been further enriched and our latest cells meet 20K of the above
definition. Further we can provide Isotopic Analysis giving the exact composition with an
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uncertainty of 3K. Samples of the actual water used in a particular cell can be supplied for
purity analysis.

Cells made from Borosilicate Glass may drift lower in temperature by up to 0.1mK after 10 to 20
years. Cells made from Quartz are expected to last 10 times longer. [3]

Manufacture of a triple point of water cell
The main steps in the manufacture of a TPW cell cover:
- The cell envelope (borosilicate or fused-silica) which is annealed to release strains
and leak-tested to ensure that it is vacuum tight.
- A thoroughly cleaned and pre-conditioned cell-envelope to prevent its inner
surface from dissolution into the water.
- A high-purity source water which is distilled, degassed and transferred into the cell
envelope by distillation or by gravity.
- Flame-sealing of the cell at a constricted section of the filling tube.
- An isotopic and chemical analysis.of a sample of the same water sealed in the cell . [1]

3. Experimental Setup To Obtain Water Triple Point Cell
- A water triple point cell
- A container of crushed ice
- A cooling material
- 8 mm diameter stainless steel rod
- High purity alcohol or acetone
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- A syringe
- A transparent container of water [5]

4. How The Experiment is Done
Firstly, cell should be placed into the crushed ice container. Then, reentrant tube should be half
filled with alcohol or acetone through using syringe. Nextly, cell should be inverted to displace
any water particle that may be present in the reentrant tube. Now disgard this liquid and refill the
tube with fresh alcohol. Next, steel rod will be placed in the cooling material to chill. Then, steel
rod should be placed into reentrant tube. This cooling will cause small shim of ice to form in
reentrant tube. Now, the mantle can be built but first using a syringe to adjust the level of alcohol
in the reentrant tube to just above the meniscus of the water. Then, same procedure will be done
again. Steel should be cooled and placed in the reentrant tube. Appearing ice bridged can be
removed by warm of the hands. Mantle will be progressing by placing it into the water container.
This cancels out the refraction of light caused by the water within the cell and allows us to see the
true size of the mantle. [5]

There are three reasons for uncertainity in a water triple point cell

A) Entrapped Air: A water triple point cell should be at the vapour pressure of the water it
contains.
B) Impurities in Water : All impurities depress the triple point of water. Fortunately when water
is solidified in a triple point cell the ice rejects the impurities, concentrating them in the
remaining water. By turning 50% of the water into ice around the re-entrant tube of the cell,
the impurities within the water are approximately doubled. To measure the temperature within
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the made up water triple point cell, a rod of copper at ambient temperature is placed in the
water filled re-entrant tube and as it cools a thin film of ice is melted around the tube. This thin
film is very pure, being water melted from the ice. After measuring the cells temperature the
cell is inverted three times, allowing the ice mantle to float and suck in impure water from the
cell to replace the clean water from the melted ice.

C) Isotopic Composition : We think of water as H2O, more precisely we should write 1H2
16O. This has been termed light water and is unobtainable. If it were obtainable its triple
point would be approximately +0.008C. In practice what we drink from the tap, and what is in
the ocean is a soup of 1H, 2H with 16O, 17O and 18O. This means real water does not have
a single triple point temperature. Its combination triple point will vary as the isotopic
composition varies. [4]

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Figure 2 [4]

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5. ITS-90
Measurements on the Kelvin and Celsius temperature scales are made with an equipment, ITS-
90 which is The Inernational Temperature Scale of 1990. ITS90 is an approximation of the
thermodynamic temperature scale that enables the similarities and relevance of temperature
measurements internationally. There are predefined calibration points in ITS-90 which has a
range of 0.65 K to 1358 K. The scale is also other points of calibration which other multiple
temperature ranges overlap.ITS-90 is references the absolute zero and it represents the
thermodynamic (absolute) temperature scale as possible inside its range. There are different
thermometer designs which covers the entire range. For instance, helium gas thermometers,
helium vapor pressure thermometers , standard platinum resistance thermometers and
monochromatic radiation thermometers.The triple point of water, temperature scales Celcius and
Kelvin are defined by absolute zero(0 K), unfortunately it is almost illogical to use this use this at
temperatures when the temperature is very different from the triple point of water. ITS90 has
many defined points, these are all based different thermodynamic equilibrium states of fourteen
pure chemical elements and one compound , namely water. Defined points are decided by phase
transitions; such as the melting and freezing points of pure chemical elements. However, the
lowest temperature(cryogenic) points are based exclusively on the vapor pressure and
temperature relationship of helium and its isotopes, the rest of the points that are less than room
temperature are based on triple points. Fixed points on ItS-91 can be seen below;V:vapour
pressure point T:triple point G:Gas thermometer point. M,F: Melting point, freezing
pointThermometers are calibrated by ITS90, one should use formulas for interpolation between
these defined points. ITS90 indicates control over variables to make sure that from lab to lab
there is reproducibility. For example, even a small change in athmospheric pressure has drastic
effects on melting poings, ITS-90 compensates for this. ITS90 also defines freezing and
melting points clearly. This distinction depends on the heat, during measurement it is checked
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whether the heat is going into or out of the sample. There are thirteen elements with triple points
and freezing melting points on the ITS-90 standard and these values are precisely fixed, so for
different temperature measurements these data are known. There maybe small differences
between measurements calibrated by ITS90 and thermodynamic temperature. But in general by
ITS-90 in a lab across the world for example in New Zealand a scientists can simply measure the
very same temperature by the help of international calibration standard, ITS90. Temperatures
measured may be expressed using any temperature scale, Celsius, Kelvin, Fahrenheit, or
Rankine. For example, a temperature can be measured in kelvin-based ITS90 standard, and
then this value can be converted to Fahrenheit scale.











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5. REFERENCES

[1] http://www.bipm.org/utils/common/pdf/its-90/SInf_Section_2_2_2013.pdf
[2] http://nettuno.ogs.trieste.it/jungo/cto/imagini/PTH2O_eng.png
[3] http://www.isotech.co.uk/files/product_file1-10.pdf
[4] http://www.isotech.co.uk/files/document_library_file-50.pdf
[5] https://www.youtube.com/watch?v=RyjOCqSSpuc video recorded by Isote
[6] http://nvlpubs.nist.gov/nistpubs/jres/80A/jresv80An3p505_A1b.pdf
[7] http://www.iapws.org/faq1/temper.htm
[8] http://www.sv.vt.edu/classes/MSE2094_NoteBook/96ClassProj/examples/triplpt.html
[9] http://goldbook.iupac.org/T06502.html
[10] http://www1.lsbu.ac.uk/water/phase.html
[11] https://www.princeton.edu/~achaney/tmve/wiki100k/docs/Triple_point.html
[12] http://en.wikipedia.org/wiki/Triple_point
[13] http://en.wikipedia.org/wiki/Water_(molecule)#Triple_point