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17th INTERNATIONAL CONFERENCE ON THE PROPERTIES OF WATER AND STEAM (17th ICPWS)

PROGRAMME & ABSTRACT BOOK

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2 – 6 SEPTEMBER 2018PRAGUE MARRIOTT HOTEL, PRAGUE, CZECH REPUBLIC

www.ICPWS2018.com

THE INTERNATIONAL ASSOCIATION FOR THE PROPERTIES OF WATER AND STEAM

S I L V E R P A R T N E R

Sentry Equipment Corporation

SIGMA GROUP a. s.

P A R T N E R S

B R O N Z E P A R T N E R

SWAN Analytical Instruments Institute of Thermomechanics

International Association for the Properties of Water and Steam (IAPWS)

2 – 6 September 2018, Prague, Czech Republic

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CONTENT

Welcome Word 2

Committees 3

Programme at a Glance 4

Presentation Guidelines 6

Detailed Scientific and Workshop Programme 7

Poster session 15

List of Posters 15

Index of Authors 16

Social Programme 18

Company Profiles 20

Floorplan 23

General Information 24

Abstract book 26

Index of Authors 73


2

Dear participant of the 17th International Conference on the Properties of Water and Steam,

This booklet contains ICPWS17 programme and abstracts of presented talks and posters. We thank you for providing interesting contributions.

This conference is the 17th meeting in a series originated in 1929 by the First International Steam-Table Conference held in London in 1929. Since then, the scope of the meetings much broadened. Besides being a forum for presenting research of various properties of water and steam, the conference is a top meeting for chemistry of power cycles, the proper-ties of seawater and numerous other topics of research and technology related to aqueous systems. The International Association for the Properties of Water and Steam (IAPWS) charged its member, the Czech Society for the Properties of Water and Steam, to organize ICPWS17. Besides organising conferences, IAPWS develops Releases and Guidelines con-taining recommendations for computing properties of aqueous systems and Technical Guidance Documents providing guidelines for modern power cycle chemistry. Please visit www.iapws.org to learn more about IAPWS.

The Conference Programme has been elaborated by the International Programme Commitee (IPC) including Andre Anderko, chair of the IAPWS Working Group Physical Chemistry of Aqueous Solutions (PCAS), Jeff Cooper, the chair of ICPWS16, Barry Dooley, the IAPWS Executive Secretary, Allan Harvey, the chair of WG Thermophysical Properties of Water and Steam (TPWS), Hans-Joachim Kretzschmar, the IAPWS President, Nabuo Okita, the chair of WG Industrial Requirements and Solutions (IRS), Rich Pawlowicz, the chair of Subcommittee on Seawater (SCSW), Michael Rziha, the chair of WG Power Cycle Chemistry, and Jan Hrubý, the chair.

Technically, the conference is organized by the Local Organising Committee seated at the Institute of Thermomechanics of the Czech Academy of Sciences, and agency C-IN providing the conference services.

On behalf of the IPC and LOC I wish you inspiring discussions at ICPWS17 and a pleasant stay in Prague.

Jan Hrubý

WELCOME WORD


3

COMMITTEES

International Programme CommitteeJan Hrubý (chair), Institute of Thermomechanics of the CAS, Prague, Czech Republic

Andre Anderko, OLI Systems Inc., Cedar Nolls, NJ, USA

Jeff Cooper, University of London, London, UK

Barry Dooley, Structural Integrity Associates, Inc., Southport, Merseyside, UK

Allan Harvey, National Institute of Standards and Technology, Boulder, USA

Hans-Joachim Kretzschmar, Zittau/Goerlitz University of Applied Sciences, Germany

Nobuo Okita, Toshiba Corporation, Yokohama, Japan

Rich Pawlowicz, University of British Columbia, Vancouver, Canada

Michael Rziha, Siemens AG Energy Sector, Germany

Local Organising CommitteeJan Hrubý, Institute of Thermomechanics of the CAS, Prague

Michal Blaháček, Institute of Thermomechanics of the CAS, Prague

Michal Duška, Institute of Thermomechanics of the CAS, Prague

Tomáš Němec, Institute of Thermomechanics of the CAS, Prague

Pavel Šafařík, Institute of Thermomechanics of the CAS, Prague

Lucie Veselá, Institute of Thermomechanics of the CAS, Prague

Patrik Zima, Institute of Thermomechanics of the CAS, Prague

Ondřej Bartoš, Czech Technical University in Prague

Ivo Jiříček, University of Chemistry and Technology Prague

Adam Nový, Doosan Škoda Power, Pilsen

Josef Šedlbauer, Technical University of Liberec

Vladimír Majer, Technical University of Liberec

Jana Kalová, University of South Bohemia


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PROGRAMME AT A GLANCE

Sunday2 September

Monday 3 September

Tuesday4 September

Wednesday 5 September

Thursday6 September

8:30 Welcome Address

PCC2Cycle Chemistry

IRS1Computational Fluid Dynamics and Calculations

SWW2pH of Seawater

PCC5Film Forming Substances

TPWS3Molecular Theory and Simulation

SWW4Joint Committee

on Seawater (JCS): Where Next?

PCC7Flue Gas Condensation

8:308:45

IAPWS Gibbs Lecture8:45

9:00 9:009:15

Keynote Lecture I.Susanne Picard

9:159:30 9:309:45 9:45

10:00Keynote Lecture II.

Attila G. Csázár

10:0010:15 10:1510:30

Coffee Break Coffee Break Coffee Break10:30

10:45 Coffee Break 10:4511:00

Keynote Lecture III.Roland SpanMartin Trusler

PCC3Flow-accelerated Corrosion and

Corrosion Products

SW2TEOS-10 Applications

SW3Physical Porperties

of Seawater

PCAS2Electrochemistry and Corrosion

PCC8Flue Gas Condensation and Water Purification

PCAS3Thermodynamic and Transport

Properties

11:0011:15 11:1511:30 11:3011:45 11:4512:00

LunchLunch Lunch

12:0012:15

ICPWS Conference Closing12:15

12:30 12:3012:45 12:4513:00

Lunch

13:0013:15 13:1513:30

PCC4Flow Accelerated

Corrosion

TPWS2Surface Tension

and Sound Speed, Miscellaneous

SWW3Relative Humidity

IRS2Non-Equilibrium Wet Steam

Flow and Engineering Requirements

TPWS4Models and Formulations

13:3013:45 13:4514:00

PCC1Technical Guidance Documents (TGD)

SW1Effects of Seawater Salt Composition

14:0014:15 14:1514:30 14:3014:45 14:4515:00

Coffee Break Coffee Break

Technical Tours

15:0015:15

Coffee Break + Poster Session

15:1515:30

TPWS1Metastable Water

PCAS1Aqueous Solution

ChemistrySWW1

Salinity and Density of Seawater

PCC6Cycle Checmistry in Various Plants

TPWS5Heavy Water

15:3015:45 15:4516:00 16:0016:15 16:1516:30

IAPWS Helmholtz Award Lecture

16:3016:45 16:4517:00

Registration Open

17:0017:15 17:1517:30

IAPWS General Meeting 17:30

17:45 17:4518:00

Ice-Breaker Cocktail

18:0018:15 18:1518:30 18:3018:45 18:4519:00

IAPWS Dinner

19:0019:15 19:1519:30 19:3019:45 19:4520:00 20:0020:15 20:1520:30 20:3020:45 20:4521:00 21:0021:15 21:1521:30 21:3021:45 21:4522:00 22:00


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Sunday2 September

Monday 3 September

Tuesday4 September

Wednesday 5 September

Thursday6 September

8:30 Welcome Address

PCC2Cycle Chemistry

IRS1Computational Fluid Dynamics and Calculations

SWW2pH of Seawater

PCC5Film Forming Substances

TPWS3Molecular Theory and Simulation

SWW4Joint Committee

on Seawater (JCS): Where Next?

PCC7Flue Gas Condensation

8:308:45

IAPWS Gibbs Lecture8:45

9:00 9:009:15

Keynote Lecture I.Susanne Picard

9:159:30 9:309:45 9:45

10:00Keynote Lecture II.

Attila G. Csázár

10:0010:15 10:1510:30

Coffee Break Coffee Break Coffee Break10:30

10:45 Coffee Break 10:4511:00

Keynote Lecture III.Roland SpanMartin Trusler

PCC3Flow-accelerated Corrosion and

Corrosion Products

SW2TEOS-10 Applications

SW3Physical Porperties

of Seawater

PCAS2Electrochemistry and Corrosion

PCC8Flue Gas Condensation and Water Purification

PCAS3Thermodynamic and Transport

Properties

11:0011:15 11:1511:30 11:3011:45 11:4512:00

LunchLunch Lunch

12:0012:15

ICPWS Conference Closing12:15

12:30 12:3012:45 12:4513:00

Lunch

13:0013:15 13:1513:30

PCC4Flow Accelerated

Corrosion

TPWS2Surface Tension

and Sound Speed, Miscellaneous

SWW3Relative Humidity

IRS2Non-Equilibrium Wet Steam

Flow and Engineering Requirements

TPWS4Models and Formulations

13:3013:45 13:4514:00

PCC1Technical Guidance Documents (TGD)

SW1Effects of Seawater Salt Composition

14:0014:15 14:1514:30 14:3014:45 14:4515:00

Coffee Break Coffee Break

Technical Tours

15:0015:15

Coffee Break + Poster Session

15:1515:30

TPWS1Metastable Water

PCAS1Aqueous Solution

ChemistrySWW1

Salinity and Density of Seawater

PCC6Cycle Checmistry in Various Plants

TPWS5Heavy Water

15:3015:45 15:4516:00 16:0016:15 16:1516:30

IAPWS Helmholtz Award Lecture

16:3016:45 16:4517:00

Registration Open

17:0017:15 17:1517:30

IAPWS General Meeting 17:30

17:45 17:4518:00


18:0018:15 18:1518:30 18:3018:45 18:4519:00

IAPWS Dinner

19:0019:15 19:1519:30 19:3019:45 19:4520:00 20:0020:15 20:1520:30 20:3020:45 20:4521:00 21:0021:15 21:1521:30 21:3021:45 21:4522:00 22:00

COFFEE BREAKS ARE SPONSORED BY SIGMA GROUP.


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This year’s scientific programme has been compiled from more than 120 received abstracts. There will be 3 keynote lectures and more than 85 oral presentations presented within four conference days.

Oral PresentationsOral presentations are always accompanied by PowerPoint presentations. The speakers are entirely responsible for the presentation content (order, graphics etc…). Once on-site every speaker should also verify in the Final pro-gramme that the name of the room and the time of the session have not changed.All presentations and questions must be delivered in English, as English is the official language of the Conference. Time reserved for one presentation is:

• 20 minutes

Presentation formatAll speakers should make sure their presentation is in a commonly compatible format. Please prepare your pre sentation preferably using PowerPoint version 2010 – 2016 in 16:9 aspect ratio (versions 2007 / 2003 are also sup ported).

Supported file types:• Presentation: TXT, DOC, XLS, XLSX, PPT, PPA, PPTA,

PPTX, PDF• Video: AVI, MPG, MKV, MOV, MP4, WMV• Audio: WMA, MP3, WAV• Pictures: JPG, GIF, BMP, TIFDo not forget, when saving the final presentation on a USB stick, to make sure to include video files if having any and all links to these multimedia files.

Depositing the filePresentation must be handed over on a USB stick to the personnel directly in the lecture room in which your pres-entation will take place, as far in advance as possible and two hours BEFORE the beginning of dedicated session AT THE LATEST. Once the first speaker from your session starts their presentation, you will not be able to upload your presentation for that session. The presentation for an early morning session should be handed over the evening before.In the lecture room, speakers will be assisted by a tech-nician, who will help them to download the presentation to the internal network. The lecture room opens each morning 30 minutes before the start of the first session and remains open throughout the day until the end of the last session.

In the lecture roomOnce the presentation is launched on the computer in the respective lecture room, speaker will advance the slides using the remote control. For all speakers: Please, do NOT come at the last minute with your own computer into the lecture room: you will NOT BE ABLE to connect it. All presentations must be down-loaded in advance.

Poster presentation guidelines Each poster board will be given a specific poster number. Please make sure to mount your poster on the poster board with the number corresponding to the number assigned to your poster presentation (e. g. P 01, P 02). In order to fit the poster board, your poster should not exceed the recommended size. Prepare your material beforehand so that it will fit neatly into the space available and can be easily attached to the board. Thin cardboard is more suitable than paper. The Conference organizers will provide suitable fixing materials, and on site assistance (registration desk) will be available to help you to display your poster.

Mounting and removing your posterPoster Area will be open for poster mounting from Monday, 3 September, 08:30. All posters should be set up by Tuesday, 4 September, 15:10, prior to the scheduled Poster session. All posters will be displayed for the whole Conference period and must be removed by the owner of the poster by Thursday, 6 September, 13:00.

PRESENTATION GUIDELINES


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Monday, 3 September, 08:40–09:20 BOHEMIA 2SS2 IAPWS Gibbs Award LectureSL 01 Molecular Conformation of Long Chain n-Alkanes (LCA’s): from gas phase to bulk water through

the interface: the Gibbs and the Instantaneous Interfaces Roberto Fernandez-Prini

Monday, 3 September, 09:20–10:00 BOHEMIA 2KL1 Keynote LectureKL 01 International metrology and the redefinition of the International System of Units (SI) Susanne Picard

Monday, 3 September, 10:00–10:40 BOHEMIA 2KL2 Keynote LectureKL 02 Ideal ideal-gas thermochemical functions Attila G. Császár

Monday, 3 September, 11:00–12:00 BOHEMIA 2KL3 Keynote LectureKL 03 Capture, transport and storage of carbon dioxide – Thermodynamic property models for different tasks

in an integrated chain of processes Roland Span and J.P. Martin Trusler

Monday, 3 September, 14:00–15:00 BOHEMIA 2PCC1 Technical Guidance Documents (TGD) Chair: Barry Dooley

Introduction to TGD Barry Dooley

Importance of TGD Michael Rziha

O 01 Field-tests on the route towards a corrosion product sampling and analysis TGD covering flexible plants Karsten Normann Thomsen

Film forming substances Wolfgang Hater

Air in-leakage Luis Carvalho

Monday, 3 September, 14:00–15:00 BOHEMIA 1SW1 Effects of Seawater Salt Composition Chair: Stefan Weinreben

O 02 The absolute salinity of seawater, its real components and its measurands Marc Le Menn

O 03 Composition changes in sea salt and their effect on conductivity/salinity/density relationships in seawater Rich Pawlowicz

O 04 A modified algorithm for estimating Absolute Salinity Hiroshi Uchida

DETAILED SCIENTIFIC AND WORKSHOP PROGRAMME


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Monday, 3 September, 15:30–17:30 BOHEMIA 2TPWS1 Metastable Water Chair: Simona Lago

O 05 Measurements of density for supercooled ordinary water, heavy water, and seawater at high pressures Aleš Blahut

O 06 Measurements of the surface tension of the supercooled ordinary water substance down to -32 °C Radim Mares

O 07 Seven years of measurement of the surface tension of supercooled water and aqueous mixtures at IT CAS Václav Vinš

O 08 Viscosity of supercooled water under pressure and two-state interpretation of water anomalies Bruno Issenmann

O 09 Equation of state of water at negative pressure and relations between lines of thermodynamic anomalies Frédéric Caupin

O 10 Application of quintic and quasi-quintic equation of states to describe some pecularities of metastable water

Attila R. Imre

Monday, 3 September, 15:30–16:50 BOHEMIA 1PCAS1 Aqueous Solution Chemistry Chair: Josef Šedlbauer

O 11 Uranyl sulfate complexation under hydrothermal conditions by quantitative Raman spectroscopy and density functional theory calculations

Peter Tremaine

O 12 Modeling phase equilibria and solution chemistry in complex aqueous systems containing rare earth elements

Andre Anderko

O 13 Unimolecular pyrolysis of dimethyl ether: Elementary fragmentation into methane and formaldehyde evidenced by gas 1H NMR

Ken Yoshida

O 14 Nucleation rates of carbon dioxide gas-hydrates Bernd Rathke

Monday, 3 September, 15:30–17:30 STUDIO DSWW1 Salinity / Density Workshop Chair: Rich Pawlowicz

Introduction Rich Pawlowicz

Progress towards SI traceability Steffen Seitz

Absolute density measurements of seawater Yohei Kayukawa

Discussion Rich Pawlowicz


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Tuesday, 4 September, 08:30–10:30 BOHEMIA 2PCC2 Cycle Chemistry Chair: David Addison

O 15 The status of cycle chemistry worldwide for fossil and combined cycle plants Barry Dooley

O 16 An electrochemical investigation of the effect of impurity concentration on the corrosion of boiler steels William Cook

O 17 Alkalizing treatment with lithium hydroxide – practical examples in CCGTs and industrial plants Christiane Holl

O 18 Operation and maintenance of process and cooling water systems in a renewable world Ludwin Daal

O 19 The future of chemistry for AGL in a changing electricity market Hayden Henderson

O 20 Intelligent chemistry alarms John Powalisz

Tuesday, 4 September, 08:30–10:10 BOHEMIA 1IRS1 Computational Fluid Dynamics and Calculations Chair: Nobuo Okita

O 21 Numerical modeling of three-dimensional cavitating flow of air-saturated water around hydrofoil Milan Sedlar

O 22 The localised thinning of pipe walls by disturbed flows Derek Lister

O 23 Water hammer analyses using characteristic method Alireza Lavaei

O 24 Hybrid calculations of the thermodynamic properties of substances Konstantin Orlov

O 25 The IAPWS Guideline on the Fast Calculation of Steam and Water Properties with the Spline-Based Table Look-Up Method (SBTL)

Matthias Kunick

Tuesday, 4 September, 08:30–10:30 STUDIO DSWW2 pH Workshop Chair: Andrew Dickson

Introduction Andrew Dickson

Traceability of spectrophotometrically measured pHT values of TRIS buffered artificial seawater in the salinity range 5 – 20

Frank Bastkowski

A traceable thermodynamic speciation model, with quantified uncertainties, of pH in Tris buffers in artificial seawaters

Simon Clegg

Discussion Andrew Dickson


10

Tuesday, 4 September, 11:00–12:00 BOHEMIA 2PCC3 Flow-accelerated Corrosion and Corrosion Products Chair: Andy Witney

O 26 Toward a resolution of the amines vs. hydrogen cation exchanged conductivity question James Bellows

O 27 Distribution of organic anions in the secondary side and their influence on Monel 400 steam generator tubing at Pickering Nuclear Generating Station Unit 4

Dennis Moghul

O 28 UNB’s CANDU-6 primary heat transport system code: implications of corrosion product transport on heat transfer degradation and activity fields

Olga Palazhchenko

Tuesday, 4 September, 11:00–12:00 BOHEMIA 1SW2 TEOS-10 Applications Chair: Rich Pawlowicz

O 29 A thermodynamic potential of seawater as a function of potential enthalpy Trevor McDougall

O 30 Salinity/density anomalies in the deep North Pacific – Evidence of a hydrothermal vent signal? Ryan Woosley

O 31 Comparability of seawater pH values – definition and measurand Maria Filomena Camoes

Tuesday, 4 September, 13:30–15:10 BOHEMIA 2PCC4 Flow-accelerated Corrosion Chair: Michael Rziha

O 32 Flow-accelerated corrosion – theory and practice: The latest understanding of the fac mechanism Derek Lister

O 33 Flow-accelerated corrosion – theory and practice: The experience in fossil and combined cycle plants Barry Dooley

O 34 Analytical method for iron tracing in boiler feedwater using filter concentration method Tetsuya Sawatsubashi

O 35 Integrated corrosion products sampling and case study John Powalisz

O 36 Corrosion product transport monitoring using corrosion product sampler, particle counter, and particle monitor in the water and steam circuit

Sabelo Kanyile

Tuesday, 4 September, 13:30–14:50 BOHEMIA 1TPWS2 Sound Speed, Miscellaneous Chair: Andreas Jäger

O 37 Speed of sound measurements in subcooled water Simona Lago

O 38 Speed-of-sound measurements and derived thermodynamic properties of liquid water Karsten Meier

O 39 Densities of the liquid and the gas: some modern models and numerical data in the critical region of H2O Evgueny Ustyuzhanin

O 40 Temperature of supercooled water droplets evaporating in vacuum Claudia Goy


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Tuesday, 4 September, 13:30–15:30 STUDIO DSWW3 Relative Humidity Workshop Chair: Olaf Hellmuth

Summary of Aims Olaf Hellmuth

Progress in development of RH Rainer Feistel

Relationship between RH and SI metrology Stephanie Bell

Discussion Olaf Hellmuth

Tuesday, 4 September, 16:30 – 17:30 BOHEMIA 2SS3 IAPWS Helmholtz Award LectureSL 02 Thermodynamic and transport properties of dilute aqueous electrolytes under nuclear reactor primary

coolant conditions by flow ac conductivity methods Hugues Arcis

Tuesday, 4 September, 17:30 – 18:00 BOHEMIA 2 IAPWS General Meeting

Wednesday, 5 September, 08:30–10:30 BOHEMIA 2PCC5 Film Forming Substances Chair: Paul McCann

O 41 Fate and distribution of film forming and alkalizing amines in steam-water cycles Yu Xue

O 42 The effect of boiler conditions on the thermolysis of film forming amines Evelyn De Meyer

O 43 Distribution ratios of polyamines present in Helamin chemical between boiling water and saturated steam Tamara Petrova

O 44 AVT vs FFAP treatment: comparison of key indices Filipp Dyachenko

O 45 Adsorption of oleyl propylenediamine on metal surfaces Duygu Disci-Zayed

O 46 Thermal decomposition of film forming amines in the power generating cycle Sonja Vidojkovic

Wednesday, 5 September, 08:30–10:10 BOHEMIA 1TPWS3 Molecular Theory and Simulation Chair: Karsten Meier

O 47 Cross second virial coefficient and dilute gas transport properties of (water vapor + carbon dioxide) mixtures from ab initio intermolecular potentials

Robert Hellmann

O 48 Ab initio calculation of the second and third virial coefficients for H2O and D2O Allan Harvey

O 49 Isothermal-isometric molecular dynamics approach for prediction of three-phase equilibrium conditions of methane hydrate system

Daisuke Yuhara

O 50 Evaluating the methodology of classical nucleation theory using large scale molecular dynamics simulation Sho Ayuba


12

Wednesday, 5 September, 08:30–10:30 STUDIO DSWW4 JCS – Where Next? Chair: Rich Pawlowicz

Introduction Rich Pawlowicz

Review – History and need for JCS: an oceanographers viewpoint Trevor McDougall

JCS terms of reference Rich Pawlowicz

Discussion Rich Pawlowicz

Wednesday, 5 September, 11:00–11:40 BOHEMIA 2SW3 Physical Properties of Seawater Chair: Ryan Woosley

O 51 Comparison between TEOS-10 estimated density and experimental density measured in IAPSO standard seawater by a single sinker hydrostatic balance.

P. Alberto Giuliano Albo

O 52 Absolute density measurements for sea-water by a hydrostatic weighing method Yohei Kayukawa

Wednesday, 5 September, 11:00–11:40 BOHEMIA 1PCAS2 Eletrochemistry and Corrosion Chair: Andre Anderko

O 53 In-situ electrochemical impedance measurements of corroding steel in supercritical water Jan Macák

O 54 Corrosion behavior of STBA24 steel and its weldment in the simulated boiler water added chloride ions and formic acid

Li-Bin Niu

Wednesday, 5 September, 13:30–14:50 BOHEMIA 2IRS2 Non-Equilibrium Wet Steam Flow and Engineering Requirements Chair: Adam Nový

O 55 Cluster distribution and nucleation in steam over a broad temperature range Jan Hrubý

O 56 A formation of the coarse droplets from the liquid films in steam turbine Ondrej Bartos

O 57 Non-condensable gas effects on geothermal plants Nobuo Okita

O 58 Acid dew of low sulfur flue gas causes corrosion on GTCC-HRSG Nobuo Okita


13

Wednesday, 5 September, 13:30–14:50 BOHEMIA 1TPWS4 Models and Formulations Chair: Allan Harvey

O 59 A theoretically based departure function for multi-fluid mixture models applied to mixtures containing water

Andreas Jäger

O 60 A new model for mixed hydrates consistent with multiparameter equations of state Sebastian Hielscher

O 61 Development of viscosity formulations for working fluids using a structure-optimization method Sebastian Herrmann

O 62 Review of the humidity formulations for dew point temperatures above 100 °C Shahin Tabandeh

Wednesday, 5 September, 15:30–16:50 BOHEMIA 2PCC6 Cycle Chemistry in Various Plants Chair: Hayden Henderson

O 63 Sulphate adsorption on magnetite under steam generator chemistry conditions Liyan Qiu

O 64 Makeup water treatment systems in nuclear power plants Hideo Hirano

O 65 Geothermal steam turbine deposition mechanisms David Addison

O 66 The application of an environmental friendly scale-Inhibitor to mitigate deposit formation in the Soultz geothermal power plant

Wolfgang Hater

Wednesday, 5 September, 15:30–16:30 BOHEMIA 1TPWS5 Heavy Water Chair: Allan Harvey

O 67 Deuterium oxide density in stable and metastable states at pressure up to 400 MPa Raffaella Romeo

O 68 Vapour pressure measurements over liquid heavy water in the temperature range from 260 K to 285 K Vito C. Fernicola

O 69 A new reference equation of state for heavy water Stefan Herrig

Thursday, 6 September, 08:30–10:10 BOHEMIA 2PCC7 Flue Gas Condensation Chair: Wolfgang Hater

O 70 District heat and flue gas condensation Folmer Fogh

O 71 Review of experiences on flue gas condensation and the re-use of the condensate Karsten Normann Thomsen

O 72 Challenges in FGC treatment with re-use of the Flue Gas Condensate Roger Lundberg

O 73 Microbial growth in membrane-based plants for rinsing of flue gas condensate Linda Wiig

O 74 Management of flue gas condensate at Skærbækværket Unit 401/402 Folmer Fogh


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Thursday, 6 September, 11:00–12:20 BOHEMIA 2PCC8 Flue Gas Condensation and Water Purification Chair: Karsten Normann Thomsen

O 75 Design of a new plant for flue gas condensation and treatment of condensate based on 23 years of field experience

Anders Fredrikson

O 76 Experiences regarding treatment and reuse of flue gas condensate in waste incineration plant Jani Vuorinen

O 77 TOC composition more important than concentration in IEX demineralisation of different water qualities for the production of steam

Evelyn De Meyer

O 78 Design considerations for UF filtration and demineralization of flue gas condensate for make-up water Thomas Dalsgaard

Thursday, 6 September, 11:00–12:20 BOHEMIA 1PCAS3 Thermodynamic and Transport Properties Chair: Andre Anderko

O 79 A modified flow-through apparatus for high pressure viscosity measurements of salt solutions Ulrike Hoffert

O 80 High-temperature NMR and MD study on self-diffusion coefficients of water and cyclohexane in binary mixture in supercritical states

Ken Yoshida

O 81 Recommended data on thermodynamic properties of hydration for selected oxygen containing compounds Josef Šedlbauer

O 82 Implementation of different COSMO-SAC models in TREND and combination with multi-fluid mixture models

Andreas Jäger

IRS Industrial Requirements and SolutionsPCAS Physical Chemistry of Aqueous SolutionsPCC Power Cycle ChemistrySW SeawaterSWW Seawater WorkshopTPWS Thermodynamic Properties of Water and SteamSS Special SessionKL Keynote Lecture


15

Tuesday, 4 September, 15:10 – 16:30, Poster AreaThe posters correspond to the following topics:P 01 – P 02 Industrial Requirements and Solutions

P 03 Physical Chemistry of Aqueous Solutions

P 04 Power Cycle Chemistry

P 05 Seawater

P 06 – P 08 Thermodynamic Properties of Water and Steam

LIST OF POSTERSP 01 Property libraries for water, steam, humid air, and other working fluids for calculating heat cycles,

turbines, heat pumps, and refrigeration processes Hans-Joachim Kretzschmar

P 02 Steam tables and property libraries for Excel, MATLAB, Mathcad, Dymola, SimulationX, LabVIEW, Engineering Equation Solver, smartphones, tablets, pocket calculators and online use

Hans-Joachim Kretzschmar

P 03 Molecular simulation of volumetric properties and hydration numbers of gas hydrates Andreas Jäger

P 04 Dissolution rates of nickel oxide in the primary circuit conditions of a pressurized water reactor Anais Graff

P 05 Absolute Salinity measurements based on sound velocity and refractive index measurements Hiroshi Uchida

P 06 Transport properties of the TIP4P/2005 model for water and their analysis with a two-state model Frédéric Caupin

P 07 Theoretical calculating the polarization characteristics for ice and water in the wide temperature range Dmitry Putintsev

P 08 Water vapor enhancement factor estimation based on the inter-molecular potentials Shahin Tabandeh

POSTER SESSION


16

Addison D. 13

Anderko A. 8

Arcis H. 11

Ayuba S. 11

Bartos O. 12

Bastkowski F. 9

Bell S. 11

Bellows J. 10

Blahut A. 8

Camoes M. F. 10

Carvalho L. 7

Caupin F. 8, 15

Clegg S. 9

Cook W. 9

Császár A. G. 7

Daal L. 9

Dalsgaard T. 14

De Meyer E. 11, 14

Dickson A. 9

Disci-Zayed D. 11

Dooley B. 7, 9, 10

Dyachenko F. 11

Feistel R. 11

Fernandez-Prini R. 7

Fernicola V. C. 13

Fogh F. 13

Fredrikson A. 14

Giuliano Albo P. A. 12

Goy C. 10

Graff A. 15

Harvey A. 11

Hater W. 7, 13

Hellmann R. 11

Hellmuth O. 11

Henderson H. 9

Herrig S. 13

Herrmann S. 13

Hielscher S. 13

Hirano H. 13

Hoffert U. 14

Holl C. 9

Hrubý J. 12

Imre A. R. 8

Issenmann B. 8

Jäger 13, 14, 15

Kanyile S. 10

Kayukawa Y. 8, 12

Kretzschmar H. J. 15

Kunick M. 9

Lago S. 10

Lavaei A. 9

Le Menn M. 7

Lister D. 9, 10

Lundberg R. 13

Macák J. 12

Mares R. 8

McDougall T. 10, 12

Meier K. 10

Moghul D. 10

Niu L. B. 12

Okita N. 12

Orlov K. 9

Palazhchenko O. 10

Pawlowicz R. 7, 8, 12

Petrova T. 11

Picard S. 7

Powalisz J. 9, 10

Putintsev D. 15

Qiu L. 13

Rathke B. 8

Romeo R. 13

Rziha M. 7

Sawatsubashi T. 10

Sedlar M. 9

Seitz S. 8

Span R. 7

Šedlbauer J. 14

Tabandeh S. 13, 15

Thomsen K. N. 7, 13

Tremaine P. 8

Trusler J. P. M. 7

Uchida H. 7, 15

Ustyuzhanin E. 10

Vidojkovic S. 11

Vinš V. 8

Vuorinen J. 14

Wiig L. 13

Woosley R. 10

Xue Y. 11

Yoshida K. 8, 14

Yuhara D. 11

INDEX OF AUTHORS

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18

SOCIAL PROGRAMME


Sunday, 2 September, 2018, 18:00 – 20:00Hotel Marriott, 1st floor, foyer

All conference participants and ac-companying persons are kindly invited to take part in the opening Ice-Breaker Cocktail. This is the perfect opportu-nity to build up and strengthen your social networks and friendships. Light cocktail refreshment will be served.

Included in the registration fee.

Dinner Cruise on the River VltavaMonday, 3 September, 2018, 19:00 – 22:00 Meeting point: 18:45, Hotel Marriott, 1st floor, foyer

This tour offers the opportunity to ex-plore enchanted Prague from the deck of a boat. The river cruise allows you to discover some of the city’s major monuments and sights, while relaxing over dinner or a drink and listening to music or dancing. During the dinner on the boat which is served buffet-style you can admire the illuminated sights of Prague passing the Charles Bridge, the Castle district (Hradčany), the National Theatre, the Vyšehrad Castle etc.Not included in the registration fee.Transfer from and back to the hotel will be provided.

Conference dinner

Wednesday, 5 September, 2018, 19:00 – 22:00, Letenský zámeček, Letenské sady 341, 170 00 Prague 7Meeting point: 18:45, Hotel Marriott, 1st floor, foyer Letenský zámeček is a unique res-taurant in the heart of Letná park with wonderful views over the historic centre of Prague. More than a century of tradition in restaurateurship is here wedded with contemporary trends in gastronomy and sincere customer care. All this in elegant surroundings which imbue a discreet luxuriousness and against the striking panorama of Prague’s Old Town as a backdrop.Not included in the registration fee.Transfers from and back to the venue will be provided.Dress code: Business attire Group photo will be taken during the dinner.

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20

COMPANY PROFILES

Silver Partner

Sentry Equipment Corporationsentry-equip.com

With accurate monitoring and measuring, plant leadership can glean the critical insights needed to control and optimize processes for improved production efficiency, output and safety. As your partner, we provide reliable sampling and monitoring solutions for all areas of a plant to help you maintain seamless and safe operations.

Since 1924, Sentry® products and services provide proven expertise to power generation with representative steam and water sampling, conditioning and analysis techniques to improve plant efficiency, output and safety. We provide a complete range of solutions no other partner offers, from sample conditioning, to water chemistry cycle services, to parts and consumables.

For oil and gas, chemical and petrochemical industries, we offer a portfolio of representative sampling and monitoring solutions to ensure process samples are safe, repeatable and reliable, every time. Our solutions include liquid, slurry, solid and powder samplers for all areas of the plant, corrosion monitoring and chemical injection solutions for pressur-ized pipelines and vessels, low-emission gas, hydrocarbon liquid and LPG sampling, and heat exchangers.

Sentry sampling and monitoring solutions provide better product and loss control, more efficient operations, and lower operating costs.

Bronze Partner

SIGMA GROUP a. s.sigmagroup.cz

The joint-stock company SIGMA GROUP a. s. is a modern and dynamically motivated engineering company which is the most significant producer of pumping machinery in the Czech Republic.

Today the company concentrates on researching, developing and producing mid-size, heavy and one-off specialized pumps and pumping sets for industrial applications. In this sector the company ranks among the best in the world successfully continuing the tradition of pump production, dating back many years, in central Moravia. Our key customers consist of both domestic and foreign industrial companies working in light and heavy engineering, the nuclear and non-nuclear energy industries, petrochemical industry, oil exploration, mineral mining and processing and water management.

Many years of application, combined with its own research departments, production plants with latest equipment and its extensive service facilities, SIGMA GROUP is able to offer its customers the best and most comprehensive packages involving pumping technology on a turnkey basis.

Further, SIGMA GROUP a. s. is the leader of the Czech Pump Manufacturers’ Association and member of EUROPUMP, the European Association of Pump Manufacturers.


21

Partner

SWAN Analytical Instrumentsswan.ch

SWAN is a Swiss global leading provider of online analytical systems in the water industry. SWAN, a company entirely dedicated to water analysis, develops, produces and sells technologically advanced instruments for the control of water quality. The analytical instruments developed by their highly qualified engineers rank amongst the leading products for safety in operation, user-friendliness and reliability.

The current product portfolio ranges from ultrapure water (like pharmaceutical and semiconductor applications), feedwater, steam and condensate monitoring as well as potable water and industrial water treatment up to swimming pool and sanitary water applications.

SWAN cooperates with independent representatives all over the world including 13 subsidiaries.

SIGMA GROUP a.s. Jana Sigmunda 313 783 49 Lutí[email protected] www.sigma.cz www.facebook.com/sigma.cz

SIGMA GROUP a.s.researching, developing and producing mid-size, heavy and one-off specialized pumps and pumping sets for industrial applications

EnergeticsPumps for conventional and nuclear power stations and heating plants.

- Feeding pumps with a large range of flow

- Condensate pumps in horizontal or vertical arrangements

- Cooling pumps

- Pumps for the pumping and delivery of raw water

- Pumps for fire water

- Pumps for heat distribution systems

- Pumps for turbine oil systems

Water managementThe company produces complete series of highly efficient and reliable centrifugal

pumps of vertical as well as horizontal designs and flow range from tens to seve-

ral thousands litres per second.

AgricultureLarge diagonal and propeller pumps with flow rates up to several thousands litres

per second are currently installed in countries with intensive irrigation of sizeable

areas, for example Egypt, Sudan, Iraq, Syria, Ecuador and India.

Chemical and petrochemical industriesPumpsPumps intended for pumping of a wide range of petroleum products, form a vital

link in the complex and demanding chain of technologies in refineries and crude

oil processing plants.

Mines and metallurgical worksPumps and sets for mines and metallurgical works focused on mine water pum-

ping.

Special applicationsA part of the SIGMA GROUP a.s. production programme is focussed at producti-

on of special pumps and pumping sets intended for environmental protection and

civil defence and protection. This especially involves pumps and mixers for con-

ventional and biological waste water treatment plants, as well as pumping equip-

ment for rescue units to elimination of effects of natural disasters.


23SIGMA GROUP a.s. Jana Sigmunda 313 783 49 Lutín

[email protected] www.sigma.cz www.facebook.com/sigma.cz

SIGMA GROUP a.s.researching, developing and producing mid-size, heavy and one-off specialized pumps and pumping sets for industrial applications

EnergeticsPumps for conventional and nuclear power stations and heating plants.

- Feeding pumps with a large range of flow

- Condensate pumps in horizontal or vertical arrangements

- Cooling pumps

- Pumps for the pumping and delivery of raw water

- Pumps for fire water

- Pumps for heat distribution systems

- Pumps for turbine oil systems

Water managementThe company produces complete series of highly efficient and reliable centrifugal

pumps of vertical as well as horizontal designs and flow range from tens to seve-

ral thousands litres per second.

AgricultureLarge diagonal and propeller pumps with flow rates up to several thousands litres

per second are currently installed in countries with intensive irrigation of sizeable

areas, for example Egypt, Sudan, Iraq, Syria, Ecuador and India.

Chemical and petrochemical industriesPumpsPumps intended for pumping of a wide range of petroleum products, form a vital

link in the complex and demanding chain of technologies in refineries and crude

oil processing plants.

Mines and metallurgical worksPumps and sets for mines and metallurgical works focused on mine water pum-

ping.

Special applicationsA part of the SIGMA GROUP a.s. production programme is focussed at producti-

on of special pumps and pumping sets intended for environmental protection and

civil defence and protection. This especially involves pumps and mixers for con-

ventional and biological waste water treatment plants, as well as pumping equip-

ment for rescue units to elimination of effects of natural disasters.

FLOORPLAN


24

GENERAL INFORMATION

AirportVáclav Havel Airport Prague handles flights from within Europe and from overseas. It is located 30 – 45 minutes by car from the centre of Prague. There are good connections between the airport and the city centre by public transport – buses and taxis.Airport information – nonstop phone lineTel.: +420 220 111 888AFTN: LKPRYDYXSITA: PRGCZ7X, PRVCZ7Xwww.prg.aero

Arrival to Conference Venue Prague Marriott Hotel is easily and comfortably reached by car as well as by public transport. The venue is located in Prague city centre – at walking distance to the metro line B – Náměstí Republiky. From the Vaclav Havel Airport Prague is situated about 10 km from the hotel. Take the nr. 119 bus (the bus stop is lo-cated directly in front of Terminals 1 and 2) to Zličín. Change here and take the Line B underground train in the direction of Černý Most. Alight at Náměstí Republiky. (Journey time: approx. 45 mins. Fare: approx. EUR 1,40*). Walking distance to the venue: 170 m. From the main railway station: The easiest way is to take the trams nr. 26 or 15 towards Divoká Šárka or Kotlářka and alight at Masarykovo nádraží. (Journey time: approx. 3 mins. Fare: approx. EUR 1*).

BadgesName badges will be provided during the onsite registration, and they must be worn when attend-ing the sessions and official meeting programme.

Cash points There is a cash machine in the lobby of the venue.

Certificate of AttendanceCertificates will be emailed to all on-site registered delegates after the conference.

Cloakroom There is a cloakroom located near the registration desk on the 1st floor.

Currency/ExchangeThe Czech currency is called the Czech crown (CZK). Exchange offices are located all around the city centre (exchange offices, banks, post offices).

Doctor / First AidIn urgent matters, dial 112 to get specialized help. No first aid service is available at the Conference venue. For medical assistance of non-urgent character, a local clinic may be helpful. The closest clinic with non-stop ser-vice is located at Vodičkova street (approx. 5 mins by taxi from the Conference venue). Health Centre PragueVodičkova 28, 2nd floorPrague 1+420 – 603 433 833+420 – 603 481 361

EmergencyGeneral emergency 112Police 158Fire department 150Emergency medical service 155

Food and BeveragesCoffee breaks (2× Monday – Wednesday, 1× Thurs-day) and lunches (Monday – Thursday) are included in the Delegate registration fee and will be served within the conference foyer on the 1st floor. Lunches will be served at the hotel restaurant on the ground floor.

Insurance and LiabilityThe Organisers will accept no liability for per-sonal injuries sustained by or for loss or damage to property belonging to Conference participants, accompanying persons either during or as a result of the Conference or during all tours and events. Participants are strongly recommended to seek insurance coverage for health and accident, lost luggage and trip cancellation.

Lost & FoundA lost and found service is available at the registration desk.

Conference SecretariatC-IN Prague Congress Centre 5. kvetna 65140 21 Prague 4Czech RepublicTel.: +420 261 174 301Fax: +420 261 174 307Website: www.c-in.euE-mail: [email protected]

Mobile PhonesParticipants are kindly requested to keep their mobile phones in the off position in the meeting rooms while sessions are being held.


25

Programme ChangesThe organisers cannot assume liability for any changes in the programme due to the external or unforeseen circumstances.

Registration Opening HoursSunday, 2 September 8:30 – 20:00Monday, 3 September 7:30 – 17:30Tuesday, 4 September 8:00 – 17:30Wednesday, 5 September 8:00 – 16:30Thursday, 6 September 8:00 – 14:30

Registration hotline: +420 727 803 209

SafetyPrague is among the most popular destinations in the world. Statistics show that when compared to other major European cities like Paris, Rome or Madrid the rate of crime is much lower in Prague. A night walk around the city is relatively safe but, of course, like in all other big cities with a high culmination of people we recommend handling your personal belongings with utmost care.

ShoppingMost shops in Prague are open from 9:00 to 18:00, Monday through Saturday. Shops in the city centre are usually open from 09:00 – 20:00, Monday through Sunday.

Slide Preview Room Please note that slide preview room will not be available. Make sure that you will bring your presentation on USB directly to the lecture room well before your session will start.

Smoking PolicyPlease note that smoking is not permitted in the venue.

TaxiIn the city centre taxis are easy to hail from the street but we strongly recommend that you use hotel taxis or obtain taxis by phone through the radio taxi service e.g. AAA (+420 14 014), City taxi (+420 257 257 257) or Speed cars (+420 224 234 234).Boarding charge: approximately 40 CZK. Journeys within the city: approximately 28 CZK / 1 km.

TippingService is usually included in the bill in bars and restaurants but tips are welcome. If you consider the service good enough to warrant a tip, suggested level is around 10 %.

Venue Prague Marriott Hotel *****V Celnici 8110 00 Prague 1www.marriott.com+420 222 888 888

WiFi There is a WiFi internet connection available at the venue.Username: Marriott_ConferencePassword: Marriott2018


26

Keynote Lectures 27

IAPWS Gibbs Award Lecture 29

IAPWS Helmholtz Award Lecture 30

Industrial Requirements and Solutions 31

Physical Chemistry of Aqueous Solutions 37

Power Cycle Chemistry 43

Seawater 56

Thermodynamic Properties of Water and Steam 61

Abstract book


27

International metrology and the redefinition of the International System of Units (SI) S. Picard1

1 International Bureau for Weights and Measures, France

At the establishment of the Metre Convention in 1875, the International Bureau for Weights and Measures (BIPM) had the key role maintaining the international prototypes for the Kilogram and the Metre. This arrangement enabled countries having signed the Metre convention to have their national standards calibrated against the international standards, and a metric reference system was in this way established and disseminated. Subsequently, enlarging the common reference system to include unit definitions based on material properties or constants rather than artefacts, as for example tem-perature or electricity, allowed National Metrology Institutes to realize their proper primary standards. The International System of Units (SI) was adopted in 1960 and the BIPM has successively adapted its role to also coordinate and/or realize comparisons of primary standards. The first ‘dematerialized’ definition of a unit based on a fundamental constant is the definition of the Metre. It was adopted in 1983 and is based on the speed of light. Progress in the art of measurement during the last decades has triggered a revision of the SI, expected to be adopted at the General Conference of Weights and Measures in Versailles November 2018. All seven base units of the SI will be defined by fixed physical constants and are therefore inherently stable. The quantities have been chosen so that the revised definitions will not need to be modified to accommodate future improvements in the technologies used to realize them. Metrology, i.e. the science and practice of measurements, is the cornerstone for a developed society. Although most users will not notice the change, the redefinition is important for traceability on a long term basis and a key for future developments associated with high precision. With the target to end poverty and protect the planet set by the United Nations in 2015, metrology infrastructure and an international network are essential factors.

Ideal ideal-gas thermochemical functionsA.G. Császár1,2

1 MTA-ELTE Complex Chemical Systems Research Group, Budapest, Hungary2 Eötvös Loránd University, Institute of Chemistry, Budapest, Hungary

Due to their considerable scientific and engineering interest, temperature-dependent (in the wide range of 0–6000 K) thermochemical properties of molecular systems, such as water, have been reported in databases and information sys-tems [1]. Most useful for practical applications would be real-gas and not ideal-gas thermochemical data but these are available only for a relatively small number of molecules and they are hard to obtain via quantum chemical approaches. Ideal-gas data, forming the majority of data in information systems, are considerably more straightforward to obtain theoretically. The total ideal-gas partition function, the subject of the present lecture, is assumed to be the product of the internal and the translational partition functions.For semirigid molecules, the simplest analytic technique to obtain internal partition functions, namely use of the harmonic oscillator (HO) and rigid rotor (RR) approximations for the vibrational and the rotational motions, respectively, yields rea-sonably accurate results at relatively low temperatures (especially around room temperature). Partition functions have an integrative nature: basically they are a direct sum of weighted energy levels. This provides much room for approximate treatments; for example, an approach more sophisticated than the RRHO approximation uses effective spectroscopic Hamiltonians providing an improved estimate for the partition functions and the related thermochemical data, even up to somewhat elevated temperatures. For water, in particular, the perturbative approach is insufficient and even breaks down at relatively low excitations or, alternatively, at relatively low temperatures. Therefore, to obtain highly accurate, high-temperature partition and thermodynamic functions for the water isotopologues requires the use of sophisticated variational nuclear-motion techniques for the computation of the rovibronic energy levels. These techniques have become available in the fourth age of quantum chemistry [2].Due to the Boltzmann distribution characterizing thermodynamic equilibria, the contribution of energy levels to the par-tition function depends strongly on the thermodynamic temperature T of the system. At the lowest temperatures, where the thermochemical functions depend only on a relatively small number of energy levels, an accuracy considerably higher than that provided by even the most sophisticated modeling studies can be achieved, once energy levels of experimental quality are used. The experimental energy levels can be obtained via the MARVEL (Measured Active Rotational-Vibrational Energy Levels) technique [3],[4] utilizing the theory of spectroscopic networks [5],[6]. At the lowest temperatures, one must also pay attention how the ortho and para nuclear-spin isomers of water are treated. These isomers have been treated explicitly during the present study.As shown for the case of three isotopologues of the diatomic molecule MgH [7], beyond a given temperature, dependent upon the first dissociation threshold of the molecule, unbound states can make a significant contribution to the partition function and the related thermochemical quantities. Studies have begun to consider quasibound states of water [8], here these molecular states are considered for the partition function for the first time, albeit via a simplified model.

KEYNOTE LECTURES


28

In a complete treatment, the contribution of excited electronic states must also be investigated. The effect of the excited electronic states of water has not been considered during the present study, as it deemed to be minuscule even at the high accuracy sought.The most accurate and most complete dataset of bound rovibrational energy levels of the ground electronic state of H216O can be obtained by combining the complete set of variationally computed levels, employing a highly accurate, empirically adjusted potential energy surface (PES), like the PoKaZaTeL PES of H216O [9], with the accurate MARVEL set of empirical levels. Therefore, we replaced the PoKaZaTeL energy levels with MARVEL energies whenever possible and in this way we obtain a hybrid dataset. A similar replacement was done for the case of heavy water [10].For quantification of the approximately two standard deviation uncertainties of the computed thermochemical quantities, it is essential that each energy level has its own uncertainty. The MARVEL energy levels have well determined uncer-tainties, originating from the uncertainties of the measured transitions. The computed PoKaZaTeL list does not have uncertainties but approximate uncertainties can be chosen: up to 20,000 cm-1 a value of 0.2 cm-1, while above 0.5 cm-1.There are four sources of error preventing the determination of “exact” temperature-dependent internal partition func-tions, Qint(T). Traditionally, the largest source of the uncertainty in a partition function, especially at higher temperatures, has been the uncertainty about the number of bound energy levels (uncertainty about the energy level density). A second significant source of error lies in the uncertainty of the energy levels used to determine Qint(T). A third type of (usually less significant) uncertainty is connected with the question of how unbound states and states associated with excited electronic states should be accounted for. A fourth source of uncertainty, left unexplored in computational thermochem-ical studies before the present studies, is connected to the uncertainty of the physical constants entering the relevant thermochemical equations. All these sources of error will be discussed in detail during the presentation.The data of Refs. 9 and 10, with the associated approximately two standard deviation uncertainties, should be considered as the most accurate ideal-gas thermochemical data available for H216O and the deuterated analogs and heavy water. We also note that many of the modeling methods of the present investigation on water can be utilized when determining temperature-dependent thermochemical functions of other molecular systems.[1] R. R. Gamache, C. Roller, E. Lopes, I. E. Gordon, L. S. Rothman, O. L. Polyansky, N. F. Zobov, A. A. Kyuberis, J. Tennyson,

A. G. Császár, T. Furtenbacher, X. Huang, D. W. Schwenke, T. J. Lee, B. J. Drouin, S. A. Tashkun, V. I. Perevalov, R. V. Kochanov, Total Internal Partition Sums for 166 Isotopologues of 51 Molecules Important in Planetary Atmospheres: Application to HITRAN2016 and Beyond, J. Quant. Spectrosc. Rad. Trans. 203 (2017) 70.

[2] A. G. Császár, C. Fábri, T. Szidarovszky, E. Mátyus, T. Furtenbacher, G. Czakó, Fourth Age of Quantum Chemistry: Molecules in Motion, Phys. Chem. Chem. Phys. 14 (2012) 1085.

[3] T. Furtenbacher, A. G. Császár, J. Tennyson, MARVEL: Measured Active Rotational-Vibrational Energy Levels, J. Mol. Spectrosc. 245 (2007) 115.

[4] T. Furtenbacher, A. G. Császár, MARVEL: Measured Active Rotational-Vibrational Energy Levels. II. Algorithmic Improvements, J. Quant. Spectr. Rad. Transfer 113 (2012) 929.

[5] A. G. Császár, T. Furtenbacher, Spectroscopic Networks, J. Mol. Spectrosc. 266 (2011) 99.[6] A. G. Császár, T. Furtenbacher, P. Árendás, Small Molecules – Big Data, J. Phys. Chem. A 120 (2016) 8949.[7] T. Szidarovszky, A. G. Császár, Toward Accurate Thermochemistry of the 24MgH, 25MgH, and 26MgH Molecules at

Elevated Temperatures: Corrections Due to Unbound States, J. Chem. Phys. 142 (2015) 014103.[8] T. Szidarovszky, A. G. Császár, Low-Lying Quasibound Rovibrational States of H216O, Mol. Phys. 111 (2013) 2131.[9] T. Furtenbacher, T. Szidarovszky, J. Hruby, A. A. Kyuberis, N. F. Zobov, O. L. Polyansky, J. Tennyson, A. G. Császár,

Definitive Ideal-Gas Thermochemical Functions of the H216O Molecule, J. Phys. Chem. Ref. Data 45 (2016) 043104.[10] I. Simkó, T. Furtenbacher, J. Hruby, N. F. Zobov, O. L. Polyansky, J. Tennyson, R. R. Gamache, T. Szidarovszky, N. Dénes,

A. G. Császár, Recommended Ideal-Gas Thermochemical Functions for Heavy Water and Its Substituent Isotopologues, J. Phys. Chem. Ref. Data 46 (2017) 023104.

Capture, transport and storage of carbon dioxide – Thermodynamic property models for different tasks in an integrated chain of processesR. Span1, J. P. M. Trusler2

1 Ruhr-Universität Bochum, Thermodynamics, Bochum, Germany2 Imperial College London, Department of Chemical Engineering, London, UK

Carbon capture and storage (CCS) processes offer the possibility of continued exploitation of fossil fuels but with greatly reduced carbon dioxide emissions to the atmosphere. This technology may be beneficial not only in power generation but more generally for decarbonising energy-intensive industrial processes. CCS involved a sequence of processes starting with capture of CO2 from the fossil fuel, either pre- or post-combustion, compression, transportation by pipeline or ship and finally storage in a geological sink such as a deep saline aquifer or a depleted hydrocarbon reservoir. CCS thus involves a complex set of interlinked processes and whole-chain modelling is essential to ensure correct technical design and reliable process economics. In order to model CCS operations reliably, it is essential to have a detailed understanding of


29

the thermodynamic and transport properties of fluids involved. CO2 forms mixtures with a wide range of other substances as it passes through the CCS chain including, for example, solvents, combustion impurities, and brines. In addition to this broad component slate, wide ranges of temperature and pressure are involved and, for these reasons, modelling of thermodynamic and transport properties presents significant challenges. For example, it can be observed that none of the currently-available thermodynamic models are suitable for application with acceptable uncertainty throughout the entire chain; therefore, different models are typically applied to various stages in the CCS chain. For example, multi-fluid Helmholtz equations of state are highly accurate for many of the non-aqueous mixtures involved, while cubic equations of state coupled with excess-Gibbs-energy models may be more suitable for aqueous streams, especially those containing electrolytes. In this contribution, we focus on thermodynamic-property models including multi-fluid Helmholtz equations of state, cubic equations of state and models for aqueous solutions containing electrolytes. The strengths and limitations of these different approaches will be reviewed and avenues for further development will be identified.

IAPWS GIBBS AWARD LECTURE

Molecular Conformation of Long Chain n-Alkanes (LCA’s): from gas phase to bulk water through the interface: the Gibbs and the Instantaneous InterfacesR. Fernandez-Prini1, E. Murina2, C. Pastorino3

1 Instituto de Química Física de los Materiales, Medio Ambiente y Energía, Argentina2 Comisión Nacional de Energía Atómica (CNEA), Argentina3 FCEN-UBA, Argentina

Recently the role of bulk water in the molecular conformation of LCA’s has been a matter of discussion, we think it is important to study the changes of molecular conformation that follow the ingress of the alkanes into water through the interface water-vapour. We present results for several LCA’s up to eicosane (C-20) and how their most stable molecular conformations change as the distance from the interface changes. We have studied these for the Gibbs interface and for C-20 also using the instantaneous interface. The results will be discussed.


30

IAPWS HELMHOLTZ AWARD LECTURE

Thermodynamic and transport properties of dilute aqueous electrolytes under nuclear reactor primary coolant conditions by flow ac conductivity methodsH. Arcis1

1 University of Guelph, Department of Chemistry, Guelph, Canada

Accurate thermodynamic properties of water and steam have always been of significant interest for the electric power industry. Current and proposed industrial designs have generated a strong push to extend our understanding of aqueous solutions up to extreme temperatures and pressures. The physical properties of water undergo severe variations from room temperature up to conditions approaching the critical point (tc = 373.946 °C and pc = 22.064 MPa), and such drastic changes impact the chemical speciation in solution. This talk will focus on the thermodynamic and transport properties of dilute aqueous electrolytes under primary coolant conditions in Canadian Deuterium Uranium (CANDU) nuclear reactors and in Pressurized Water (PWR) nuclear reactors.The method used to study these hydrothermal systems is a state-of-the-art flow AC conductivity technique [1], which was originally designed by R.H. Wood and his co-workers at the University of Delaware and which is able to operate up to supercritical conditions (400 °C, 28 MPa).Two examples studied at the University of Guelph with this technique will be presented. First, the contribution of the D2O isotope effect to ionic movement will be discussed [2], with special emphasis on the impact of proton hopping on ionic mobility for D3O+/H3O+ and OD-/OH- as the temperature increases from 25 to 300 °C. Second, recent results [3-5] from a comprehensive study to develop a quantitative understanding of aqueous boron chemistry up to 350 °C will be presented. Such results are particularly important to improve mass transport models used to simulate the chemistry in fuel crud deposit crevices under boron “hideout” conditions.The novelty of this work lies in the direct measurement of transport and thermodynamic constants under extreme condi-tions. Such results offer new insights for the understanding of ionic hydration and ion-ion interactions, and therefore are critical to the development of our basic understanding of hydrothermal systems.[1] Arcis, H.; Zimmerman, G.H.; Tremaine, P.R.; Ion-Pair Formation in Aqueous Strontium Chloride and Strontium Hydroxide

Solutions under Hydrothermal Conditions. Phys. Chem. Chem. Phys. 2014, 16, 17688–17704[2] Plumridge, J.; Arcis, H.; Tremaine, P.R.; Limiting Conductivities of Univalent Cations and the Chloride Ion in H2O and

D2O under Hydrothermal Conditions. J. Solution Chem. 2015, 44, 1062–1089[3] Arcis, H.; Ferguson, J.P.; Zimmerman, G.H.; Tremaine, P.R.; The Limiting Conductivity of the Borate Ion and its Ion-Pair

Formation Constants with Sodium and Potassium under Hydrothermal Conditions. PCCP 2016, 18, 24081−24094[4] Arcis, H.; Ferguson, J.P.; Applegarth, L.M.S.G.A.; Zimmerman, G.H.; Tremaine, P.R.; Ionization of Boric Acid in Water from

298 K to 623 K by AC Conductivity and Raman Spectroscopy. J. Chem. Thermodyn. 2017, 187−198[5] Ferguson, J.P.; Arcis, H.; Zimmerman, G.H.; Tremaine, P.R.; Ion-Pair Formation Constants of Lithium Borate and Lithium

Hydroxide under Pressurized Water Nuclear Reactor Coolant Conditions. Ind. Eng. Chem. Res. 2017, 56, 8121−8132


31

INDUSTRIAL REQUIREMENTS AND SOLUTIONS

IRS1: COMPUTATIONAL FLUID DYNAMICS AND CALCULATIONS

4 September 2018, 08:30 – 10:10 BOHEMIA 1

O 21Numerical modeling of three-dimensional cavitating flow of air-saturated water around hydrofoilM. Sedlar1, T. Kratky2, M. Komarek2

1 SIGMA Research and Development Institute, Department of Hydraulic Research, Lutín, Czechia2 Centre of Hydraulic Research, Department of Hydraulic Research, Lutín, Czechia

This work deals with the numerical investigation of unsteady cavitating flow around the straight NACA2412 hydrofoil at the incidence angle of 8 deg and the Reynolds number of 1.56 x 106. The hydrofoil with the span/chord ratio of 1.25 corresponds to the experiments carried out in the cavitation tunnel operated in the SIGMA Research and Development Institute. The numerical simulations play the main part in this study; nevertheless the experimental work is also presented as an impor-tant background for validation of the results. A comprehensive CFD analysis has been carried out with Scale-Resolving Simulations (SRS) including the SAS-SST, LES-WALE and DES models. The main attention is focused on the prediction of interactions between the re-entrant flow and cavitation structures as well as the pressure excited by cavitation. The monitored pressure fluctuations during the cavity cycles as well as the intervals between the dominant pressure pulses are discussed in detail. The simulations show, that the physical models based on the incompressible constant property liquid (water) overpredict the sharp high-pressure peaks during the collapses of the bubble clouds as well as the speed of pressure pulse propagation. The real properties of water including estimated content of undissolved air are therefore considered to affect the compressibility of the mixture and its speed of sound. Comparisons with experimental data prove that the amount of air in the water has a significant influence on accuracy of predicting pressure pulses generated due to the cavitation instabilities on blades of hydrodynamic machines (Fig. 1).Keywords: cavitation; vortex structures; 3D effects; NACA2412; CFD, SRS, real water properties, dissolved airFig. 1 Maximum value of sharp high-pressure peaks during collapses of the bubble clouds. Comparison of CFD analysis with experimental data

O 22The localised thinning of pipe walls by disturbed flowsD. Lister1, N. Kippers1, S. Raval1, P. Garland2, S. Shulder3, M. Caravaggio4

1 University of New Brunswick, Chemical Engineering, Fredericton, Canada2 University of New Brunswick, Mechanical Engineering, Fredericton, Canada3 Electric Power Research Institute, P64 Boiler and Turbine Steam and Cycle Chemistry, Charlotte, USA4 Electric Power Research Institute, Major Component Reliability, Charlotte, USA

The effects of local turbulence on flow-accelerated corrosion (FAC) have been re-examined using computational fluid dynamics (CFD) in the light of new information from laboratory experiments. On-line FAC probes were exposed in high-temperature loops to flowing water under power plant feedwater conditions. The probes were carbon steel tubes of millimetre-scale bore and the wall-thinning rate was monitored continuously by measuring the electrical resistance along the length (resistance increases as the wall thins). Departure from fully-devel-oped flow was induced by making probes with inserted stainless steel nozzles or by bending probes to an angle between


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20° and 60°. An experiment lasted several weeks, after which the probe was removed from the loop, sectioned along its length (in the plane of the bend for a bent probe) and its inner surface examined with laser-Raman microscopy and scanning-electron microscopy (SEM). Optical microscopy complemented low-magnification SEM and X-radiography in providing high-resolution images for determining the bore profile. Computational fluid dynamic (CFD) analysis of an experiment provided fluid shear stress at the wall directly and mass transfer indirectly via an analogy with the equivalent heat transfer parameter. The corrosion was similar to that seen in industrial pipe. The nozzle probes experienced aggravated FAC downstream of the nozzle, peaking at a position close to the mass transfer and shear stress peaks computed for the initial, undamaged bore. Applying CFD to the bore profile as it developed with exposure, however, showed that the fluid peaks broadened and moved with increasing exposure, finally appearing downstream of the actual damage peak. Similar examinations and analyses of the bent probes indicated that the fluid parameter peaks corresponded to aggravated FAC on the intrados at the start of the bend and on the extrados at the end of the bend and were also modified as geometry changed with increased exposure.

O 23Water hammer analyses using characteristic methodA. Lavaei1, A. Lohrasbi11 College of Engineering- Boroujerd Branch- Islamic Azad University- Iran, Department of Civil Engineering, Borojerd, Islamic Republic

of Iran

Rapid changes in the velocity of fluid in closed conduits generate large pressure, which are transmitted through the sys-tem with the speed of sound. When the fluid medium is a liquid the pressure surges and related phenomena are described as “water hammer”. Water hammer is caused by normal operation of the system, such as valve opening or closure, pump starts and stoppages, and by abnormal condition, such as power failure. The more rapid the closure of the valve, the more rapid is the change in momentum, and hence, greater is the additional pressure developed. The likely effects of water hammer must be taken into account in the structural design of pipelines and in the design of operating procedures for pumps, valves, etc. The physical phenomena of water hammer and the mathematical model which provides the basis for design computations are described. Most water hammer analysis involves computer solution by the method of charac-teristics. In this paper water hammer is modeled with this method and effect of valve opening and closure will be surveyed with a program that is used for this purpose and with a numerical example.

O 24Hybrid calculations of the thermodynamic properties of substancesV. Ochkov1,2, K. Orlov1,2, E. Dzhuraeva1, V. Kuznetsov1, S. Gurke3

1 National Research University “Moscow Power Engineering Institute”, Theoretical basis of heat engineering, Moscow, Russian Federation2 Joint Institute for High Temperatures, Russian Academy of Science, Moscow, Russian Federation3 Elsevier Reference Solutions, Knovel, New York, USA

Modern mathematical programs for engineering and scientific calculations (Mathcad, Maple, Mathematica etc) allow to carry out calculations using units of measurement of physical quantities, as well as numerical and symbolic calculation methods for solving various equations of thermodynamics.These modern tools with their combined (hybrid) use allow to refrain from setting the numerical values of the parameters of the substance (temperature and pressure) in the standard state.The parameters of the substance in the standard state remain symbolic, and not a numerical value during the calculation.This approach makes it possible to conduct, without problems, calculations of binary thermodynamic cycles, cycles, where various substances like water and steam, as well as various refrigerants, are used as working bodies.The authors give an example in the report of a hybrid calculation of the thermodynamic parameters of a substance when it is compressed (see the picture). The standard parameters of this substance remain symbolic values of T0 and p0 when calculating thermodynamic quantities such as specific enthalpy entropy, temperature and pressure.The authors of the report raise the question of the dimensionality of certain physicochemical constants used in the calculation of the thermodynamic properties of substances (in particular, aqueous solutions) and certain heat-energy processes.


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O 25The IAPWS Guideline on the Fast Calculation of Steam and Water Properties with the Spline-Based Table Look-Up Method (SBTL)M. Kunick1, H.J. Kretzschmar1, R. Berry2, R. Martineau2, F. di Mare3, P. Post3, U. Gampe4

1 Zittau/Görlitz University of Applied Sciences, Dept. of Technical Thermodynamics, Zittau, Germany2 Idaho National Laboratory, Nuclear Science & Technology, Idaho Falls, USA3 Ruhr-Universität Bochum, Chair of Thermal Turbomachines and Aeroengines, Bochum, Germany4 Technische Universität Dresden, Chair of Thermal Power Machinery and Plants, Dresden, Germany

Numerical simulations of transient processes with heat-cycle calculation software, computational fluid dynamics (CFD), or thermohydraulic codes, are widely used in power engineering. During these simulations, the thermophysical properties of the utilized working fluids need to be calculated extremely often. The calculation of these properties from multiparam-eter equations is very time-consuming and leads to inacceptable computing times. Therefore, property calculations are often simplified through the use of the ideal-gas equation or a cubic equation of state. Depending on the range of state, these simplifications cause inaccuracies in the results of the process simulation.To provide more suitable property calculation algorithms for computationally intensive process simulations, the Spline-Based Table Look-up Method (SBTL) was developed in a project of IAPWS. This method applies spline-interpolation tech-niques and specialized variable transformations to reproduce the results of an underlying formulation, e.g., the industrial formulation for water and steam IAPWS-IF97, with high accuracy and low computing time. The corresponding IAPWS Guideline contains a detailed description of the SBTL method as well as SBTL functions of specific volume and internal energy (v,u), as required in CFD, and of pressure and enthalpy (p,h), as used in heat-cycle calculations, for water and steam. Fast and numerically consistent inverse functions of (p,v) and (u,s), as well as of (p,T), (p,s), and (h,s) are also provided. The maximum deviations of the SBTL functions from the underlying IAPWS formulations are less than 10 – 100 ppm. With regard to IAPWS-IF97, computations from the (v,u) spline functions are more than 130 times faster.The applicability of the SBTL method was verified in various process simulations. The results of these simulations show negligible differences to those obtained with the direct application of IAPWS-IF97, but the overall computing times are reduced significantly.


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IRS2: NON-EQUILIBRIUM WET STEAM FLOW AND ENGINEERING REQUIREMENTS


O 55Cluster distribution and nucleation in steam over a broad temperature rangeJ. Hrubý1, V. Vinš1, M. Čenský1, F. Moučka2, N. Ivo2

1 Institute of Thermomechanics of the Academy of Sciences CR, Thermodynamics, Prague, Czechia2 J. E. Purkinje University, Faculty of Science, Ústí nad Labem, Czechia

Homogeneous nucleation of water droplets in steam and various gaseous environments occurs in steam turbines, rapid moist air flows and in prospective technologies for carbon capture and storage. Homogeneous nucleation of water droplets near room temperature appears to be relatively well predicted by the classical nucleation theory (CNT, [1]). Recently, Hrubý et al. [2] combined experimental nucleation rate data for water in various carrier gases with nucleation in technically pure steam studied in supersonic nozzles and turbines, providing an unprecedented temperature range of 250 K of the data showing a strongly temperature-dependent deviation from CNT. In the present study we include the effect of non-ideality of the gas phase which has been recently studied by molecular simulations using polarizable force fields [3] which, unlike simpler models, provides quantitatively correct predictions of thermophysical properties for both liquid and gas phases. Besides considering the thermodynamic effect of non-ideal gas phase on the critical cluster we also compare cluster distributions corresponding to the CNT with distributions of small clusters found in molecular simulations and discuss possible semi-empirical corrections of CNT.[1] H. Vehkamäki: Classical Nucleation Theory in Multicomponent Systems, Springer-Verlag, Berlin Heidelberg, 2006 [2] J. Hrubý, M. Duška, T. Němec, M. Kolovratník: Nucleation rates of droplets in supersaturated steam and water vapour

– carrier gas mixtures between 200 K and 450 K. Proc. Inst. Mech. Eng. A: J. Power Energy, in press. [3] M. Rouha, I. Nezbeda, J. Hrubý, F. Moučka: Higher virial coefficients of water. J Molec Liquids, in press, available online,

https://doi.org/10.1016/j.molliq.2017.11.105

O 56A formation of the coarse droplets from the liquid films in steam turbineO. Bartos1

1 Czech Technical University in Prague, Energy Engineering, Prague, Czechia

The paper introduces first results from a new steam/air wind tunnel built for the study of the coarse water droplets in the steam turbines. The purpose of the tunnel is a study of the water droplets formation from liquid films at high speed flow. The atomization of liquid is a widely studied problem for the liquid sprays and in the field of aerosol research. A similar phenomenon is found in steam turbines but mostly with undesirable effects, the coarse droplets have a negative effect on the reliability and efficiency of the turbines. The turbine blades are eroded by and also break the coarse droplets. The new wind tunnel is equipped with the classical pressure and temperature measurement for the determination of the initial condition in the settling chamber and measurement of the static pressure along the nozzle with known profile. The meas-urement with the photogrammetric method and light scattering is used for the determination of the size determination function of the droplets. The liquid film is produced on the standard symmetrical airfoil by the aqueous solution pumping. A different aqueous solution are studied.

O 57Non-condensable gas effects on geothermal plantsN. Yamaguchi1, N. Okita2

1 Fuji Electric Co.- Ltd, Thermal & Geothermal Power Plant Engineering Dept., Kawasaki, Japan2 Toshiba Energy Systems & Solutions Corporation, Plant Engineering Dept., Yokohama, Japan

There are some special aspects for considering and specifying on planning geothermal power plants and main compo-nents such as steam turbine and condenser.First of all, calculation method and notational convention for the thermophysical properties restrictedly cover geothermal steam which contains non-condensable gases, and the following current approaches seem to be dominant within the geothermal industry;• Simply use the IF97 formulation to calculate temperature, enthalpy, etc. from the pressure of geothermal fluid for very

low gas mixtures


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• Use the IF97 formulation to calculate the fluid temperature from the H2O partial pressure of the geothermal fluid, and calculate enthalpy assuming that H2O and gases are in thermal equilibrium.

• Secondly, measurement of the steam quality (wetness) at the turbine inlet is essential to verify the turbine efficiency. However, the following existing methods are inadequate.

• Calorimeter: less accurate• Chemical tracer method: expensive, not suitable for frequent use due to possible steam contamination by tracer

chemicalsThirdly, design of “Steam scrubbing”, a method to remove impurities by combination of water spraying and moisture sepa-ration is still rather experimental. Better understanding for mechanism of impurities removal by water droplets is needed.Presentation would concentrate on non-condensable gas effect in order to design steam turbines and auxiliary equipment more adequately.We evaluate the effect of mixture of CO2 with H2O as main non-condensable gas of geothermal fluid on the thermophysical properties such as enthalpy in planning. Comparisons among existing equations of states (EOSs) with mixture rules will be discussed in detail for more accurate and realistic design method.Finally, we would suggest and require methods and/or process for evaluating EOSs, which can be utilized properly within industrial fields of geothermal system considering the above aspects and fundamental solutions from thermophysical point of view.

O 58Acid dew of low sulfur flue gas causes corrosion on GTCC-HRSGH. Shimada1, N. Okita2

1 Toshiba Energy Systems & Solutions Corporation, Thermal & Hydro Power Systems & Services Div., Yokohama, Japan2 Toshiba Energy Systems & Solutions Corporation, Plant Engineering Dept., Yokohama, Japan

In power plants design, we should consider sulfuric acid dew point causing corrosion when we decrease the flue gas outlet temperature for achieving higher efficiency. In Japan, Otsuka equation has been applied to coal-fired and oil-fired plants since 1960’s. In these days, gas turbine combined cycle (GTCC) plants have been applied for lower CO2 and emissions and higher effi-ciency compared to conventional coal-fired power plants which emit considerable amount of CO2, SOx and NOx. However, Otsuka equation cannot be utilized to GTCC because the equation does not cover such low sulfur fuel like natural gas or LNG. Same situation seems to happen in Germany and many countries. For such low sulfur conditions for GTCC in design of heat recovery steam generator (HRSG), each HRSG manufacturer uses individual equation or method for preventing HRSG tubes from sulfuric acid corrosion.Recently in Japan, we sometimes experience corrosion and SCC on HRSG tubes with intensive damage which might be caused by the following mechanism.• SO2 + ½ O2⇔SO3 (inside HRSG)• SO3 raises dew point temperature of exhaust gas⇒Condensation• SO3 + H2O = H2SO4⇒Corrosion• 4NO2 + 2H2O + O2 = 4HNO3⇒SCC• SCC occurs⇒Water leakage from the tube⇒Intensive corrosionThis mechanism has not been verified because it is difficult to get actual data on sites which is affected by additives and/or SCRs and to reaffirm the conditions as low as actual flue gas in sulfur concentration.We need to establish an empirical dew equation on low sulfur content flue gas by the following collaborative approaches with institutions or manufacturers.1) Investigate the existing methods and select the best some candidates2) Create or modify the best method including verification of the candidates by actual plant or laboratory dataTheoretical approaches also would be helpful to understand the mechanism of reducing vapor pressure with chemical reactions and to simulate the micro-actions over the time in actual conditions.


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Poster Session

4 September 2018, 15:10 – 16:30 Poster Area

P 01Property libraries for water, steam, humid air, and other working fluids for calculating heat cycles, turbines, heat pumps, and refrigeration processesH.J. Kretzschmar1, M. Kunick1, S. Herrmann1

1 Zittau/Goerlitz University of Applied Sciences, Technical Thermodynamics, Zittau, Germany

The program libraries for calculating the thermophysical properties for water and steam, for mixtures with water and steam, and for other working fluids are designed for practical use by engineers who calculate heat cycles, steam or gas turbine, boiler, heat pump, or other thermal or refrigeration processes. Thermodynamic and transport properties, thermo-dynamic derivatives and inverse functions can be calculated.The following property libraries are presented here:LibIF97 for water and steamLibIF97-META for metastable steamLibICE for iceLibSeaWa for seawaterLibHuGas for humid combustion-gas mixtures also at high pressuresLibHuAir for humid air also at high pressures and with high water contentLibAmWa for ammonia/water mixtures in absorption processes and the Kalina processLibWaLi for water/lithium bromide mixtures in absorption processesLibIdGasMix for 25 ideal gases and their mixturesLibRealAir for real dry airLibCO2 for carbon dioxide including dry ice,LibNH3 for ammoniaLibPropane for propaneLibButane_Iso and LibButane_n for iso-butane and n-butaneLibD4, LibD5, LibD6, LibMDM, LibMD2M, LibMD3M, LibMD4M, and LibMM for siloxanes used in ORC processesLibCH3OH for methanol, LibC2H5OH for ethanolLibH2 for hydrogen, LibN2 for nitrogen, LibHe for helium andLibSecRef for liquid coolants.In addition, property libraries for a number of refrigerants and hydrocarbons are available.These libraries contain the most accurate algorithms currently available for calculating thermodynamic and transport properties.For extremely fast property computations in CFD or non-stationary process simulations, the Spline-based Table Look-up Method (SBTL) property libraries are available.The property libraries can be used in user-specific programs written in Fortran, C++, C#, Java, Pascal (Delphi), Python, Visual Basic, or other programming languages under the operating systems Windows, Unix/Linux, or Mac OS.Student versions of certain property libraries are available.

P 02Steam tables and property libraries for Excel, MATLAB, Mathcad, Dymola, SimulationX, LabVIEW, Engineering Equation Solver, smartphones, tablets, pocket calculators and online useH.J. Kretzschmar1, M. Kunick1, S. Herrmann1

1 Zittau/Goerlitz University of Applied Sciences, Technical Thermodynamics, Zittau, Germany

The software developed for calculating the thermodynamic and transport properties for water and steam, mixtures with water and steam, and other working fluids have been designed for very convenient use by engineers who routinely calcu-late heat cycles, steam or gas turbines, boilers, heat pumps, or other thermal or refrigeration processes.


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The following software solutions will be presented:Add-In FluidEXLGraphics for Excel®Add-On FluidLAB for MATLAB®Add-On FluidMAT for Mathcad®Add-On FluidDYM for Dymola® (Modelica) and SimulationX®Add-On FluidVIEW for LabVIEW™ andAdd-On FluidEES for the Engineering Equation Solver® (EES).The program FluidDIA was developed for calculating and plotting large-sized and camera-ready thermodynamic charts.Steam tables are available for iPhone, iPad and iPod touch, and for Android smartphones and tablets.The software for using steam tables and property software on Texas Instruments®, Hewlett Packard®, and Casio® pocket calculators is of particular interest for students.Thermodynamic and transport properties of several working fluids can be online calculated using the Fluid Property Calculator at our website www.thermodynamics-zittau.de.

PHYSICAL CHEMISTRY OF AQUEOUS SOLUTIONS

PCAS1: AQUEOUS SOLUTION CHEMISTRY


O 11Uranyl sulfate complexation under hydrothermal conditions by quantitative Raman spectroscopy and density functional theory calculationsC. Alcorn1, J. Cox1, L. Applegarth1, P. Tremaine1

1 University of Guelph, Chemistry, Guelph, Canada

Quantitative first and second formation constants of aqueous uranyl sulfate complexes were obtained from Raman spectra of solutions contained in quartz capillary cells at 25 MPa, at temperatures ranging from 25 –375 °C. Temperature-dependent values of the O=U=O vibrational frequencies of UO2

2+(aq), UO2SO40(aq) and UO2(SO4)2

2-(aq) were derived from the high temperature spectra. Temperature-independent Raman scattering coefficients of UO2

2+(aq) were calculated directly from uranyl triflate spectra from 25 – 300 °C, while those of UO2SO4

0(aq) and UO2(SO4)22-(aq) were derived from

spectroscopic data at 25 °C using concentrations calculated using the formation constants and Specific Ion Interaction Theory (SIT) activity coefficient model reported by Tian and Rao (J. Chem. Thermodyn., 2009, 41, 569 – 574). Chemical structures and vibrational frequencies predicted from Density Functional Theory (Gaussian 09) were employed to in-terpret the Raman spectra. Values of log K1 and log β2 were determined, using several activity coefficient models, with a precision of ± 0.03 and ± 0.10 respectively at 25 °C, and ± 0.14 and ± 0.19, respectively at 375 °C. The formation constants consistent with the activity coefficients used in the EPRI chemical modeling code MULTEQ are suitable for describing uranium releases in fuel-failure scenarios in Generation IV Super-Critical Water-cooled nuclear Reactor (SCWR) coolant circuits.

O 12Modeling phase equilibria and solution chemistry in complex aqueous systems containing rare earth elementsG. Das1, M. Lencka1, A. Eslamimanesh1, P. Wang1, A. Anderko1, R. Riman2, A. Navrotsky3

1 OLI Systems Inc., Properties and Materials, Cedar Knolls, USA2 Rutgers- The State University of New Jersey, Department of Materials Science and Engineering, Piscataway, USA3 University of California Davis, Peter A. Rock Thermochemistry Laboratory and NEAT ORU, Davis, USA

Rare earth elements (REEs) are increasingly important in a variety of technological applications including magnets in electrical and electronic devices, battery alloys, phosphors, high-performance metal alloys, automobile and petroleum refining catalysts, polishing powders, glass additives and ceramics. For the rational development and optimization of REE recovery and recycling processes, the knowledge of thermodynamic properties, aqueous solution chemistry and phase equilibria is of utmost importance. In this study, a comprehensive model has been developed for calculating phase


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equilibria in binary and multicomponent aqueous systems containing rare earth chlorides, sulfates, carbonates and phosphates. The computational framework is based on the previously developed Mixed-Solvent Electrolyte (MSE) model. The model simultaneously reproduces solid-liquid equilibria, vapor-liquid equilibria, and caloric properties. The model has been shown to capture complex phase behavior of salt solutions, including the formation of multiple congruently or incongruently melting hydrated solid phases and double salts in multicomponent mixtures. Phase equilibria have been accurately reproduced for binary rare earth salt – water systems and for ternary mixtures that additionally include acids and common salts. Solid-liquid phase diagrams have been generated to provide a convenient summary of the solubility of stable and metastable hydrated solid phases. Analysis of the stability of solid hydrates reveals systematic trends within the rare earth series and can be used to fill the gaps in the experimental database. Furthermore, implications of solution thermodynamics for REE separation have been investigated. This includes the recovery of rare-earth elements in the form of sparingly soluble double sodium - rare earth – sulfate salts and the formation of carbonate phases.

O 13Unimolecular pyrolysis of dimethyl ether: Elementary fragmentation into methane and formaldehyde evidenced by gas 1H NMRK. Yoshida1, Y. Tsujino2, M. Nakahara2

1 Tokushima University, Department of Applied Chemistry, Tokushima, Japan2 Kyoto University, Institute for Chemical Research, Uji, Japan

Pyrolysis plays key roles in refining crude oils and biomass into lower-molecules for useful fuels through degradations and hydrogenations. Long before the time that no convenient fossil fuels exist on Earth comes up, we are to endeavor to find sustainable and green methods for quickly converting the natural products like cellulose into gaseous fuels as methanol, formic acid, methane, hydrogen, etc. A study of the pyrolysis of ether bonds (C-O-C) is essential for these innovations because ether or glycosidic bonds are involved in biomass. We pay attention to the simplest ether molecule, dimethyl ether, CH3OCH3 (C2H6O, DME), a fuel gas that can be synthesized from methanol. For the efficient pyrolysis or combustion of DME, the kinetic control is required and the reaction mechanisms to be clarified. The thermal DME decomposition has long been believed to be due to the radical mechanism, and the typical products in literature have been CH4, H2, and CO. To directly detect the initial fragments, we have applied gas-phase 1H NMR spectroscopy and quenching method for a tube reactor containing DME as low as 1.0 and 5.0 mM perfectly in the dark at 400–500 °C. We have found that CH3OCH3 is initially fragmented into CH4 and HCHO with no H2 detected. Formaldehyde is reactive at high temperatures and is subjected to the consecutive thermal oxidation-reduction (so-called disproportionations) reactions, expressed as HCHO + HCHO → CH3OH + CO and HCHO + CH3OH → CH4 + H2O + CO. These two are extremely sensitive to the concentration due to the bimolecular nature and are much faster than the initial fragmentation of DME at practical reactant concentrations; note that presently we lowered the DME concentration on purpose to detect the initial step. When the background light is not completely shut out as in the case of combustion processes, the HCHO is almost totally consumed in the unimolecular photodecomposition HCHO → H2 + CO, and the disproportionations of HCHO do not occur.

O 14Nucleation rates of carbon dioxide gas-hydratesJ. Castellanos Muñoz1, J. Kiefer1, B. Rathke1

1 Technische Thermodynamik, Universität Bremen, Bremen, Germany

The formation of gas hydrates is one of the challenges in plant operation under conditions of elevated pressures, humidity and low temperatures. Furthermore, applications like the sequestration of carbon-dioxide, the basic understanding of pro-cesses in oil industry and natural gas processing are the most prominent applications, which urgently require a profound knowledge of the physico-chemical aspects of the underlying mechanisms.Unfortunately, basic research on the kinetics of hydrate formation taking into account the different aspects of equilibrium thermodynamics and the kinetics of phase transitions is scarce. This contribution summarizes different experimental ap-proaches to determine the formation of gas hydrates. Advantages and disadvantages of these techniques are explicated and discussed in the light of investigations on nucleation.Against this background, we have been characterized onset-conditions of the formation of gas hydrates from carbon-di-oxide saturated water and have been determined characteristic times and nucleation rates for different degrees of super-saturation. Such specific type of experiments should contribute to the understanding of the basics of hydrate formation.For this purpose a set of experiments has been performed using a high pressure apparatus suitable up to pressures of p = 700 bar. The set-up consists of two independent parts, which allow for a preparation of binary mixtures under defined conditions and rapid kinetic studies of phase transitions induced by fast pressure changes, respectively. This concept allows for an independent control of temperature and pressure without a change of the composition of a sample.Results indicate a strong variation of induction times or even nucleation rates of hydrate formation at different degrees of supersaturation and are discussed in terms of classical nucleation theories.


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PCAS2: ELETROCHEMISTRY AND CORROSION


O 53In-situ electrochemical impedance measurements of corroding steel in supercritical waterJ. Macák1, R. Novotný2, A. Krausová1, V. Bystrianský1, L. Tůma1, M. Novák1

1 University of Chemistry and Technology, Power Engineering Dpt., Prague 6, Czechia2 Joint Research Centre, Directorate G - Nuclear Safety & Security, Petten, Netherlands

To increase the efficiency of heat to work transformation in power cycles, admission steam enthalpy has to be increased. This trend peaks currently in advanced ultra-supercritical technology, which offers efficiency as high as 50 % at steam pressure of 32MPa and temperature of 650 °C. The knowledge gained in the fossil technology can partly be used in the super-critical-water-cooled reactor (SCWR) concept, one of the six designs selected by the Generation IV International Forum (GIF). Most of the SCWR concepts employs temperatures between 280 °C and 530 – 625 °C at the reactor core inlet and outlet respectively. Consequently, the SCWR concept will contend with enormous changes in physical and chemical properties of the cooling water around the critical point (374 °C).Most of the chemistry-material challenges are still to be resolved. The majority of the corrosion studies is based on an exposure of the studied material in scw and a subsequent analysis. In the presented paper, we aimed at getting in-situ information on charge transfer/corrosion properties of subcritical and supercritical water (SCW) from electrochemical measurements. In-situ electrochemical impedance spectroscopy (EIS) measurements were performed with 316L steel sample. The experimental set-up included a supercritical autoclave connected to a recirculation water loop. The experiment consisted of gradual heating up to 500 °C (at the constant pressure of 25 MPa), than constant temperature of 500 °C was maintained for over 2000 hours. After the isothermal stage temperature was increased gradually to 600 °C and then slow cooling occured. The series of EIS measurements was performed sequentially – during all the stages of the experiment.The experiment confirmed feasibility of EIS measurements in a broad temperature range (Fig. 1). The EIS data were ana-lysed and the impedance parameters were interpreted using their relation to the significant changes of physico-chemical properties of water around the critical point.


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O 54Corrosion behavior of STBA24 steel and its weldment in the simulated boiler water added chloride ions and formic acidL.B. Niu1, S. Kosaka2

1 Faculty of Engineering- Shinshu University, Department of Mechanical Systems Engineering, Nagano City, Japan2 Graduate School of Shinshu University, Mechanical Systems Engineering Division, Nagano City, Japan

In thermal power plants, corrosive species such as chloride ions (Cl-) will be mixed into the boiler water in the case of inad-equate water treatment and so on. On other hand, in order to suppress corrosion of boiler materials, there is a tendency to add organic amines into boiler feed water. However, at high temperatures the organic amines produce organic acids such as formic acid (HCOOH) by decomposition. In this work, the combined effect of Cl- and HCOOH on corrosion behavior of STBA24 steel and its weldment was investigated. Anodic polarizations and open circuit potential (OCP) measurements were conducted on the base metal (BM) and its weldment (WM) of STBA24 steel. The test waters were prepared by the addition in combination of 100 ppm Cl- and 50 ppm HCOOH to the simulated boiler water.In anodic polarization tests, BM and WM specimens exhibited passive states in the test waters. Pitting potentials of the specimens were higher in the water added not only 100 ppm Cl- but also 50 ppm HCOOH than those in the water added only 100 ppm Cl-. It suggests that pit initiation was inhibited by the presence of HCOOH in the water containing 100 ppm Cl-. In OCP measurements, the specimens in the water added 100 ppm Cl- and 50 ppm HCOOH showed nobler potentials after the start of measurements. However, the OCP dropped after several tens of hours.By the surface observations after OCP measurements, it was confirmed that the film formed on the specimen in the water added Cl- and HCOOH was thicker than that formed in the water added only Cl-. It is considered that the suppression of pit initiation and the rise of OCP at the early stage of measurements were in virtue of the formation of the thicker film. On other hand, it is also considered that the OCP drops were due to deterioration in denseness of the thicker film.There was no large difference in the corrosion behavior between BM and WM specimens, even though a better corrosion resistance exhibited on the weld metal regions.

PCAS3: THERMODYNAMIC AND TRANSPORT PROPERTIES


O 79A modified flow-through apparatus for high pressure viscosity measurements of salt solutionsU. Hoffert1, H. Milsch1

1 Helmholtz-Zentrum Potsdam Deutsches GeoForschungsZentrum GFZ, Geothermal Energy Systems, Potsdam, Germany

For the sustainable operation of a geothermal system, it is important to know the flow characteristics of the geothermal fluid as exactly as possible. Viscosity, here, is the determining thermophysical parameter. In sedimentary basins, as prom-inent targets for geothermal energy exploitation, fluids are mostly highly saline and mainly consist of sodium chloride and calcium chloride. To obtain systematic knowledge about the viscosity of sodium chloride and calcium chloride solutions and mixtures of both salts, a laboratory study was conducted. For geothermal applications, salt solutions with different concentrations need to be measured at pressure and temperature conditions up to 200 °C and 500 bar. Therefore, a flow-through apparatus originally designed for rock-physical measurements was converted into a capillary viscometer. So far, measurements up to 125 bar and 90 °C were conducted. Viscosity data of the salt solutions were obtained relative as deviation from pure water, used as the calibration agent for each temperature and pressure step. In this contribution, the general concept and the modifications of this apparatus will be outlined. Also, the results obtained so far will be presented and compared to exiting literature values, whenever available.


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O 80High-temperature NMR and MD study on self-diffusion coefficients of water and cyclohexane in binary mixture in supercritical statesK. Yoshida1, M. Nakahara2

1 Tokushima University, Department of Applied Chemistry, Tokushima, Japan2 Kyoto University, Institute for Chemical Research, Uji, Japan

The unique high ability of sub- and supercritical water can make a progress in green chemistry and provide us clues as to the reduction or removement of a variety of serious troubles in power cycle chemistry. To get an insight into the mi-croscopic-level mechanism of unique phenomena in water, we have investigated the self-diffusion in water, cyclohexane and benzene as pure solvents in sub- and supercritical states by means of the high-temperature NMR spectroscopy in combination with molecular dynamics (MD) simulation [1]. In the present study, we examine the self-diffusion coefficients of water and cyclohexane in their binary mixture in sub- and supercritical states. The characteristic of the diffusion processes of water and hydrophobic cyclohexane have been analyzed in detail in view of the microscopic solvation shell structure and dynamics. The self-diffusion coefficients of water (Dw) and cyclohexane (Dch) in their binary mixture are determined using the proton pulsed-field-gradient spin echo method by using the high-temperature NMR apparatus in sub- and supercritical states at 250 – 400 °C. The relative diffusivity ratio Dw/Dch is examined as a measure of the dynamic effects of the hydrogen-bonding interaction on water diffusion. The ratio Dw/Dch decreases at the higher water mole fraction and the higher density, as an indication of the larger effect of the hydrogen-bonding interaction on the self-diffusion of water. The anomalous increase in Dw/Dch with increasing temperature is observed at the higher water mole fraction xw above ~0.5. We have explained this tendency by considering the difference in the activation energy. In other words, this is because the hydrogen-bonding interactions, which hinder the diffusion of water at the lower temperatures, are more overwhelmed by the kinetic effects at higher temperatures.

[1] K. Yoshida, N. Matubayasi, M. Nakahara, J. Chem. Phys. 129, 214501 (2008); Id. J. Mol. Liq. 147, 96 (2009).

O 81Recommended data on thermodynamic properties of hydration for selected oxygen containing compoundsJ. Šedlbauer1, V. Majer1, M. Slavík1

1 Technical University of Liberec, Department of Chemistry, Liberec, Czechia

Database of thermodynamic properties of hydration was established for selected oxygen containing organic solutes at reference conditions of 298.15 K and 0.1 MPa and, where available, at high temperatures and pressures up to the near-crit-ical region of water. The aim is to obtain representative values of hydration properties for solutes covering different molecular structures retrieved from the best available literature data for aqueous and pure solutes. The database can be used as a standard for testing and establishment of new physico-chemical models and methods of molecular simulation as well as for developing semi-theoretical prediction schemes of interest for chemical engineering, power cycle chemistry, environmental chemistry and geochemistry.

O 82Implementation of different COSMO-SAC models in TREND and combination with multi-fluid mixture modelsE. Mickoleit1, A. Jäger1, C. Breitkopf1

1 Technische Universität Dresden, Chair of Technical Thermodynamics, Dresden, Germany

Since the development of the conductor-like screening model (COSMO) for real solvents [1], various modifications of the model have been published. One of the modifications that has proven to yield good predictions for phase equilibria of mixtures is the COSMO segment activity coefficient model (COSMO-SAC) [2]. In this work, three modifications of this model [3–5] have been implemented into the thermophysical property software TREND [6], where the model of Mullins et al. [3] is a slightly modified open-source implementation of [2]. In the model of Hsieh et al. [4], the hydrogen-bonding interactions have been differentiated and the electrostatic interactions have been modified. Finally in the model of Hsieh et al. [5], dispersive interactions have been taken into account.The different models for COSMO-SAC in combination with the assumption of ideal gas for the vapor phase have been used to calculate phase equilibria of mixtures in order to demonstrate the capabilities of the model. Furthermore, COSMO-SAC has been combined with the multi-fluid model (see paper “A theoretically based departure function for multi-fluid mixture models applied to mixtures containing water”) and has been applied to mixtures with water, where water has been modeled using the IAPWS-95 [7].

[1] A. Klamt, J. Phys. Chem. 99 (1995) 2224.


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[2] S.-T. Lin, S.I. Sandler, Ind. Eng. Chem. Res. 41 (2002) 899.[3] E. Mullins, R. Oldland, Y.A. Liu, S. Wang, S.I. Sandler, C.-C. Chen, M. Zwolak, K.C. Seavey, Ind. Eng. Chem. Res. 45 (2006)

4389.[4] C.-M. Hsieh, S.I. Sandler, S.-T. Lin, Fluid Phase Equilib. 297 (2010) 90.[5] C.-M. Hsieh, S.-T. Lin, J. Vrabec, Fluid Phase Equilib. 367 (2014) 109.[6] R. Span, T. Eckermann, S. Herrig, S. Hielscher, A. Jäger, M. Thol, TREND. Thermodynamic Reference and Engineering

Data 3.0, Lehrstuhl fuer Thermodynamik, Ruhr-Universitaet Bochum, Bochum, Germany, 2016.[7] W. Wagner, A. Pruß, J. Phys. Chem. Ref. Data 31 (2002) 387.

Poster Session


P 03Molecular simulation of volumetric properties and hydration numbers of gas hydratesT. Lorenz1, A. Jäger1, N. Kamphausen1, C. Breitkopf1

1 Technische Universität Dresden, Chair of Technical Thermodynamics, Dresden, Germany

During the last years, gas hydrate models for components of mixtures that are relevant for carbon capture and storage processes have been developed and combined with the best available equations of state for fluid phases and solid phases in equilibrium with hydrate. In a first step, models for gas hydrates in the binary systems of water + CO2, CH4, C2H6, CO, N2, O2, Ar, and C3H8 have been developed [1–3]. The components CO2, CH4, C2H6, and CO form cubic crystal structure sI hydrates in binary mixtures with water and the components N2, O2, Ar, and C3H8 form cubic crystal structure sII hydrates. Recently, the gas hydrate model has been extended in order to model mixed hydrates of the aforementioned components [4]. So far, it is only possible to combine hydrate formers that form the same crystal structure with this model. In order to model sII hydrate formers in sI and vice versa, properties of these hydrate formers in the other structure are needed. For example, modeling CH4 in sII requires the lattice parameter of CH4 in sII as a pure hydrate, which is experimentally difficult to obtain. However, molecular simulations of gas hydrates are a viable option to obtain these properties.Therefore, in this work molecular simulations of the composition, the lattice parameter, and the bulk modulus of gas hy-drates have been performed. Methane hydrates have been simulated in structure sI and the results have been compared to available experimental data. The simulations are in good agreement with the experimental findings. Subsequently, properties for methane hydrates in structure sII have been calculated and analyzed.

[1] V. Vinš, A. Jäger, R. Span, J. Hrubý, Fluid Phase Equilib. 427 (2016) 268.[2] V. Vinš, A. Jäger, J. Hrubý, R. Span, Fluid Phase Equilib. 435 (2017) 104.[3] A. Jäger, V. Vinš, R. Span, J. Hrubý, Fluid Phase Equilib. 429 (2016) 55.[4] S. Hielscher, V. Vinš, A. Jäger, J. Hrubý, C. Breitkopf, R. Span, Fluid Phase Equilib. 459 (2018) 170.


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POWER CYCLE CHEMISTRY

PCC1: TECHNICAL GUIDANCE DOCUMENTS (TGD)


O 01Field-tests on the route towards a corrosion product sampling and analysis TGD covering flexible plantsK.N. Thomsen1

1 COWI a/s, Bioenergy and Thermal Power, Aalborg, Denmark

The IAPWS TGD on corrosion products (CP) sampling and analysis from 2013 covers the design of proper sampling sys-tems and the process getting from the representative sample to the validated result. The users have received the TGD very well, and it is now widely used for monitoring CP formation and transport. Following the classical understanding, the TGD specifies sampling conditions at high and stable load. In many cases, these conditions seldom occur, since flexible (cyclic) operation is the demand of the electricity market.This paper describes a series of field-test performed to widen the scope of the TGD to flexible plants. This purpose is not trivial, since the guidance must address the increased CP transport taking place under the transient conditions of start/stop and frequent load changes. The guidance of the revised TGD must explain how such transient CP transport phe-nomena are monitored, assessed and related to the general water chemistry conditions. The field-tests have focused on (proxy) methods for on-line measurement and simple, easy-to-use filtration methods as means for tracking the transient CP transport. Along with this, mathematical models describing the distribution of corrosion product levels and particle size in samples are established. These physical properties are interrelated and may explain why many previous tests of particle-based methods for on-line measurement of CPs have concluded that there is only a rough qualitative correlation between measured values and CP levels in grab samples.The decay of CP levels following transient conditions is modelled as an exponential decay towards as steady-state level. The peak level of CPs is related to the water chemistry applied and to the procedures used for start, stop and preservation and may thus be optimized. This is summarized in the IAPWS Chart for CP Decay explaining the relation between optimal water chemistry and short waiting time during start-up for proper water chemistry conditions.

PCC2: CYCLE CHEMISTRY


O 15The status of cycle chemistry worldwide for fossil and combined cycle plantsB. Dooley1

1 Structural Integrity Associates, Inc., Southport, United Kingdom

Although much research work has been conducted over the last 25 years which has led to consolidation of the cycle chemistry for fossil and combined cycle plants, the suite of cycle chemistry damage has changed very little over the same time period. This presentation will delineate the author’s thoughts on why this has occurred and provide analysis and case studies. Specific results on Repeat Cycle Chemistry Situations (RCCS) from over 200 plants worldwide will also be provided. There have been few new areas of cycle chemistry control within the last 25 years with maybe only the introduction of film forming substances in the 1980s. But the generating industry is very slow in adopting new tech-nology. The IAPWS Technical Guidance Documents have provided a new approach for all plants worldwide which allows customization to each and every plant, has introduced new guidance and achievable limits, and in some areas (such as instrumentation, corrosion products, and steam purity) have become the international standards. The IAPWS TGD will be covered in a separate session at ICPWS.


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O 16An electrochemical investigation of the effect of impurity concentration on the corrosion of boiler steelsW. Cook1, D. Addison2

1 University of New Brunswick, Chemical Engineering, Fredericton, Canada2 Thermal Chemistry Limited, Chemistry, Hamilton, New Zealand

Operational specifications for impurities within the feed-water and boiler drum have been developed and used with great success over the past several decades to minimize degradation mechanisms on boiler steel. For example, the IAPWS Technical Guidance Document – Volatile Treatments for the Steam-Water Circuits of Fossil and Combined Cycle/HRSG Power Plants specifies ranges and limits on parameters such as pH and conductivity after cation exchange (CACE) as an indication of proper dosing of the alkalizing amine and for identification of anionic impurities within the system, respective-ly. Other guidance documents may also specify action limits for chloride and/or sulfate impurities in the Economizer Inlet as a measure to protect the boiler drum and tubes from degradation mechanisms such as under-deposit corrosion (UDC) and wastage. While decades of operational experience have validated these limits and the overall approach, a detailed scientific confirmation of the threshold for chloride and/or sulphate induced corrosion within the boiler systems, including the effects of combined concentrations of these impurities, has never been fully examined.This experimental program aims to provide a detailed map of the corrosion rates of typical boiler steel with increasing concentrations of chloride, sulfate and combinations of the two anions under simulated HP boiler conditions (350oC and 17MPa). A flow-through test rig has been assembled at the UNB that includes reservoirs of simulated boiler water with varying concentrations of the impurity ions of interests. Samples of boiler steel have been fabricated into a working elec-trode for an electrochemical cell where the corrosion potential and corrosion rate of the steel is monitored using standard electrochemical techniques such as linear polarization resistance and impedance spectroscopy. Preliminary results are presented identifying the threshold concentrations for the onset of corrosion of the boiler steel.

O 17Alkalizing treatment with lithium hydroxide – practical examples in CCGTs and industrial plantsC. Holl1, H. Woizick2

1 HYDRO-ENGINEERING, Main office, Muelheim an der Ruhr, Germany2 RheinEnergie, Köln-Merkenich, Köln, Germany

For optimum operation of drum and shell boilers alkaline boiler water conditions are necessary. The choice of solid al-kalizing agents to control the boiler water corrosion is limited by the design of the boiler and the water substances. As conventional, non-organic conditioning agent sodium hydroxide and trisodium phosphate are mainly used. The use of lithium hydroxide is less well known and unfortunately a rarely used alternative. This alkalizing agent has several signifi-cant advantages, especially in harmful boiler constructions, for example in boiling surfaces with low tube gradients and / or other plant designs which are difficult to control in regard to flow conditions as for example flow accelerated corrosion (FAC).CCGT – plants at RheinEnergie (Cologne) as well as some by HYDRO-ENGINEERING maintained industrial power plants are operating successfully with LiOH partial for many years. Some problems and consequential damages during operation with other alkalizing or without solid alkalizing agents could be extensively minimized.The insights gained during changing treatment to lithium hydroxide dosing and the many years of experience gained with this treatment are presented. The results of the detected iron and hydrogen contents show the positive effects.

O 18Operation and maintenance of process and cooling water systems in a renewable worldL. Venhuis1, B. Maarten1, L. Daal11 Bluexprt, Operations, Arnhem, Netherlands

Through rapid urbanization and economic growth, there is an increasing demand on availability and quality of both energy and water resources. Simultaneously there is a global trend to adopt renewable energy resources and increased stress on water availability. Here, cycling mode of generation assets play a key role. In particular HRSG’s consume little water and are much more flexible in operation to accommodate the new renewable energy world. The most efficient means of cooling is once-through cooling, however developments in cooling water availability and more stringent environmental legislation make it increasingly challenging to adopt this cooling method and the trend is to adopt hybrid or air cooling as an alternative. On the process water side chemical conditioning strategies of the water/steam cycle has become more challenging over the years.Up until a few years ago developments in the power sector where reasonably predictable. Since the past decade the introduction and use of renewable energy has significantly changed the energy generation landscape. It creates both


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opportunities and challenges for power plant operators. It has forced for example operators to determine if a (newly built) HRSG unit needs to be mothballed and if so for how long. Such choices have great impact on water chemistry control of the boiler and approach for maintenance of the cooling water system. Another recognized risk with high impact is the loss of expertise within generation assets and suppliers due to retirement and/or multiple roles and tasks for operators and chemists. This paper describes the present situation in the Netherlands with its current developments and provides an outlook with respect to process and cooling water application. The associated risks, challenges and opportunities for power plant operators going ahead will be particularly highlighted.

O 19The future of chemistry for AGL in a changing electricity marketH. Henderson1

1 AGL Energy, Group Operations, Docklands- Victoria, Australia

AGL Energy is the largest power generator in Australia, the company has grown by acquisition from 160 mw to over 10 000 mw in 8 years. This has presented numerous cycle chemistry challenges across four thermal power generation sites.This paper discusses and highlights the common challenges in cycle chemistry across the AGL fleet and demonstrates the future direction AGL chemistry is moving towards in a changing electricity market. There are significant renewable developments ins Australia and several large thermal sites are expected to close within the next 10 years. All traditionally baseloaded units in Australia can be expected to be cycling within the next 10 years.This paper will include discussion of data analytics, predictive inspection techniques, film-forming substances and the power station chemists role in a renewable electricity market. With a specific emphasis on the projects AGL has initiated to address the risks created by flexible operation and an aging fleet.

O 20Intelligent chemistry alarmsD. Hubbard1, J. Powalisz2

1 American Electric Power, Corporate Chemistry, Columbus, USA2 Sentry Equipment Corp, Corporate Development, Oconomowoc, USA

This paper discusses the development and application of intelligent chemistry alarms for power plant cycle chemistry.Today it is standard practice to use online analyzers to monitor and control cycle chemistry in steam power plants. This data can be used to indicate when a parameter is outside of normal limits and provide an alarm to alert operations staff.Unfortunately interpreting these alarms can be problematic. Problems include evaluating whether the alarm was caused by a faulty instrument or an actual parameter excursion. It is also common to have to diagnose and confirm a problem using multiple analyzer parameters. This diagnosis may require advanced chemistry support which may not always be available.An “intelligent alarm system” has been co-developed by EPRI and Doug Hubbard of AEP (Logic) along with Sentry Equipment Corp providing the hardware, software and user interface. This system uses data from existing analyzers and it’s logic filter’s out nuisance alarms caused by analyzer issues, uses multiple analyzers to indicate when actual chemistry “events” are happening and provides actionable guidance to operators to identify and act on the problem.This concept addresses fundamental human performance dynamics associated with interpreting on-line chemistry analyzers, the systems used to monitor these analyzers and actions/inaction taken in response to alarms created by these systems.Several methods to implement this system are discussed; from a stand-alone black box to customized software modules.The details of these systems and an example will be presented.


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PCC3: FLOW-ACCELERATED CORROSION AND CORROSION PRODUCTS


O 26Toward a resolution of the amines vs. hydrogen cation exchanged conductivity questionJ. Bellows1

1 James Bellows and Associates, Maitland- FL, USA

Amines have been used in power cycles for over half a century. In those cycles, they decompose to carboxylic acids which raise cation conductivity. There has been much discussion on whether the high pH compensates for the high cation conductivity. Some modeling of the chemistry in the PWR cycle has shown that as pH increases, the conductivity in the first moisture also increases. The increase depends upon the pH control agent. Considerations are developed for research to help further advance understanding of the effects of amines in the steam cycle on steam turbines.Note (not part of abstract): A Copyright license to publish will be given to the conference. All other copyright will be retained by the author.

O 27Distribution of organic anions in the secondary side and their influence on Monel 400 steam generator tubing at Pickering Nuclear Generating Station Unit 4D. Moghul1, A.M. McKay2

1 Ontario Power Generation Inc., Pickering Nuclear Generating Station - Pickering Chemistry Technical, Pickering, Canada2 Ontario Power Generation Inc., Consultant: Secondary Side Chemistry Expert, Pickering, Canada

Morpholine is used at Pickering Nuclear Generating Station to maintain the secondary side pH within an alkaline range to minimize corrosion product transport. Morpholine decomposes to ethanolamine, acetate, glycolate, formate, and ammonia under operating conditions. Hideout return (HOR) studies and enhanced sampling was performed to assess the decomposition of morpholine to organic anions and their distribution in the secondary side. The relative amounts of acetate, glycolate, and formate depend on the presence of SG sludge and copper deposits, and oxygen ingress. Unit 4 Steam Generator (SG) concentrations of acetate, glycolate, and formate have increased after each planned main-tenance outage since the morpholine specification was increased to 10 – 20 mg/kg in 2009. SG concentrations of acetate, formate, and glycolate peaked at 1200 mg/kg, 102 mg/kg, and 340 mg/kg respectively prior to the 2016 outage. High concentrations of these organics are associated with SG deposit loading, presence of copper containing deposits, and likely incomplete removal during outages / start-up.Acetate is a final decomposition product of morpholine and is relatively volatile resulting in persistent concentrations in the secondary side. HOR studies show that formate and glycolate return to bulk SG water during the cooldown period (i.e., SG heat flux removed), with the formate concentration increasing up to ten fold during this period for Unit 4. This suggests that the glycolate and formate are adsorbed to SG oxides to a higher degree than acetate. High concentrations of glyco-late indicate the preferential decomposition under oxidizing conditions that may be found in the condensate system or due to SG oxides. It appears that glycolate and formate likely had a greater role than acetate, under oxidizing conditions, in contributing to the Unit 4 Monel 400 SG tubing degradation identified during the 2016 outage.

O 28UNB’s CANDU-6 primary heat transport system code: implications of corrosion product transport on heat transfer degradation and activity fieldsO. Palazhchenko1, W. Cook1, D. Lister2, D. Taylor3

1 University of New Brunswick, Centre for Nuclear Energy Research, Fredericton, Canada2 University of New Brunswick, Chemical Engineering, Fredericton, Canada3 New Brunswick Power, Reactor Safety, Maces Bay, Canada

Over the past two decades, a comprehensive computer code has been developed at UNB with the intention of mechanis-tically predicting flow-accelerated corrosion of the outlet feeder pipes and corrosion product and activity transport in the


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CANDU primary heat transport (PHT) system. The model has recently been enhanced by the addition of a comprehensive steam generator heat-transfer and fouling component. A detailed numerical approach to the thermal-hydraulics in the boilers has increased the accuracy of oxide growth predictions that are key for determining areas of radioactivity accu-mulation. The code expansion has also enabled modelling of reactor inlet header temperature (RIHT) rise, which eventually may require a de-rating in station power to remain within nuclear safety margins.The model accounts for boiler degradation mechanisms and station events such as primary and secondary side fouling, chemical and mechanical cleaning, pressure changes and leakage or bypass flow in the divider plate. Variation in heat transfer with position in the boiler allows for calculation of bulk PHT coolant temperature that influences the tempera-ture-dependent corrosion product (magnetite) solubility. In turn, this affects the rate of oxide growth on the boiler tube surfaces. The codes make extensive use of the IAPWS formulations for H2O and D2O, which are central to the iterative heat transfer computations.For this work, oxide deposition within a set of steam generator tubes, grouped into bundles based on U-bend arc lengths, is simulated. The work highlights which sets of tubes should be targeted for cleaning and corrosion product removal. A detailed map of oxide deposit distribution, validated against station data, also pinpoints regions where active corrosion products will accumulate. As the CANDU fleet continues to age and undergo maintenance and refurbishment, such pre-dictive modelling is of great importance.

PCC4: FLOW-ACCELERATED CORROSION


O 32Flow-accelerated corrosion – theory and practice: The latest understanding of the fac mechanismD. Lister1, B. Dooley2

1 University of New Brunswick, Chemical Engineering, Fredericton, Canada2 Structural Integrity Associates, Inc., Southport, United Kingdom

In outlining the underlying mechanisms of FAC, the presentation will discuss the resilience of the indigenous oxide film on the metal as the controlling factor. It is shown how the film is affected by fluid dynamics, mass transfer and chemistry and describes how mass transfer has become generally accepted as the sole basis for mathematical models, including those underlying many commercial codes. The limitations of the approach are pointed out.

O 33Flow-accelerated corrosion – theory and practice: The experience in fossil and combined cycle plantsB. Dooley1, D. Lister2

1 Structural Integrity Associates, Inc., Southport, United Kingdom2 University of New Brunswick, Chemical Engineering, Fredericton, Canada

Part 2 will provide the latest information on FAC in fossil and combined cycle/HRSG plants worldwide. The results from assessments at over 200 plants will be presented to detail the common features in location and cycle chemistry control. In many of these plants air-cooled condensers (ACC) are becoming more common, and FAC is the most common damage mechanism in these systems. The detailed mechanisms of single- and two-phase FAC will be outlined and how they can be overcome by the optimum choice of the cycle chemistry.

O 34Analytical method for iron tracing in boiler feedwater using filter concentration methodT. Sawatsubashi1, A. Ureshino1, A. Nozaki1, H. Akamine2, S. Tsubakizaki31 Mitsubishi Heavy Industries, Chemical Research Department- Research & Innovation Center, Nagasaki, Japan2 Mitsubishi Hitachi Power Systems, Plant Engineering Department- Plant Engineering Division, Nagasaki, Japan3 Mitsubishi Hitachi Power Systems, Nagasaki Power Systems Service Department- Power Systems Service Headquarters, Nagasaki,

Japan

Boilers that use an oxygen treatment (OT) for water treatment have the risk where the growth of powder-like scale con-sisting of eluted iron in feedwater equipment causes heat transfer inhibition and leads to problems such as tube leakage. For this reason, it is necessary to control the iron concentration of boiler feedwater to 2 μg/L or less to maintain stable


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boiler operation. This time, we developed a double filter concentration method that simultaneously uses a membrane filter and an iminodiacetate type chelate filter as a method to analyze minute amounts of iron easily and inexpensively. This method is adopted in the JISB8224 Boiler Feed Water and Boiler Water Testing Methods revised and published in March 2016.

O 35Integrated corrosion products sampling and case studyJ. Powalisz1

1 Sentry Equipment Corp, Corporate Development, Oconomowoc, USA

Corrosion of metal surfaces in the water/steam cycle of power plants can affect safety, equipment reliability, efficiency and plant capacity. Besides the obvious effects of metal degeneration at the point of attack, the products of corrosion can migrate through the system and collect on the turbine blades, causing a loss in turbine efficiency and capacity. They can also collect on heat transfer surfaces, leading to further loss of efficiency and under-deposit corrosion. Additionally, they can accumulate in “sludge traps” in piping, valves and vessels. This contributes to further corrosion, increased pressure drops, and equipment malfunction.Collecting these corrosion products and analyzing them can be useful in identifying the sources, determine the rate, iden-tifying the type and cause of corrosion, and track the path of corrosion products as they move through the system and settle in low velocity/flow locations. The products of concern are generally iron or copper, but other metals and chemical compounds may be present in the sample. There are several methods by which to capture corrosion products and analyze them, however, arguably the most useful method is the integrated corrosion products sampling method which captures corrosion products and simultaneously records volumetric flow so that the concentration of particulate and ionic corrosion species can be determined.This data is particularly useful in determining base corrosion levels, effectiveness of cycle chemistry before and after changes and unit operating mode corrosion variations.This paper covers the basics of integrated corrosion products sampling, sampling system design, operation and a case study.

O 36Corrosion product transport monitoring using corrosion product sampler, particle counter, and particle monitor in the water and steam circuitS. Kanyile1, S. Marais2

1 Eskom, Medupi Chemical Services, Lephalale, South Africa2 Eskom, Production Engineering Integration, Johannesburg, South Africa

Cycle chemistry is concerned with maintaining optimum protection of internal surfaces of water and steam touched plant components from corrosion (and deposition), under all operating conditions. Central to cycle chemistry control is corrosion product transport monitoring. Generated from flow accelerated corrosion and other corrosion mechanisms, corrosion products are a measure of the efficacy of the chemical treatment regime applied. The conventional method for corrosion product monitoring involves sample collection by a suitable method, sample processing in the laboratory, and later computation of the final corrosion product concentration. Cycle chemistry control requires timeous monitoring and response, and the conventional method is time consuming and often leads to a delayed response in terms of cycle chemistry optimization. A study was conducted in Eskom to compare a number of online corrosion product monitoring techniques with the aim of improving corrosion product transport monitoring, and interpretation thereof, in the water and steam cycle. The study evaluated the use of corrosion product sampling, particle counters and particle monitors. This paper presents the results and makes recommendations about the application of these monitoring techniques for cycle chemistry optimization.


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PCC5: FILM FORMING SUBSTANCES


O 41Fate and distribution of film forming and alkalizing amines in steam-water cyclesY. Xue1, A.M. Brunner2, D. Vughs2, W. Hater3, H. Huiting4, M. Vanoppen1, A. Verliefde1

1 Ghent University, Department of applied analytical and physical chemistry, Ghent, Belgium2 KWR Watercycle Research Institute, Chemical laboratory, Nieuwegein, Netherlands3 Kurita Europe GmbH, Water department, Duesseldorf, Germany4 KWR Watercycle Research Institute, Industry- Wastewater and Reuse team, Nieuwegein, Netherlands

Boiler water treatment and conditioning are employed in most industrial plants to control corrosion. The plant studied here switched its treatment program in 2013. The former program was based on hydrazine, Na3PO4 and ammonia. Due to boiler tube failures, a program based on film forming amines (FFA) and alkalizing amines (AA) was implemented instead. After the transition no further boiler tube failures occurred. Moreover, considerable water and energy savings could be realised.Although FFA based treatment has been used successfully for years, more studies are needed for a comprehensive understanding of the exact mechanisms behind the corrosion protection in steam-water cycles. The ISPT Joint Industrial Project ‘Steam and Condensate Quality Water Process Technology’ addresses this need.Within the ISPT framework, the goal of the study is to get detailed insight into the distribution of FFA and AA and their major breakdown products in the steam-water cycle of the plant mentioned above. Therefore, lab-scale flow-through boiler experiments were combined with a sampling campaign in the full-scale steam-water cycle.Lab-scale boiler experiments were performed to study the thermal stability and potential breakdown products of the FFA and AA. The lab-scale boiler was operated at conditions mimicking the plant’s superheater conditions. Samples prior and after thermal exposure were collected for analysis. An extended sampling campaign was run in the plant, whereby several sampling points were selected to analyze the distribution of relevant components of the treatment chemicals and breakdown products in the system.The water samples were submitted to regular monitoring scheme. Furthermore, several specialized analytical methods were used, such as liquid chromatography-mass spectrometry, ion chromatography and gas chromatography-mass spectrometry.Based on the obtained results a first attempt to model the behavior of the components in the steam-water cycle will be presented.

O 42The effect of boiler conditions on the thermolysis of film forming aminesE. De Meyer1, W. Hater2, A. Verliefde1

1 Ghent University, Applied Analytical and Physical Chemistry, Ghent, Belgium2 Kurita Europe GmbH, Technical Director Water, Ludwigshafen, Germany

The protection mechanism by which film forming amines (FFA) protect metal surfaces is a continuous process of adsorp-tion and desorption, the question is what the thermal stability of the desorbed FFA is. In addition, the thermal stability of the absorbed FFA is unknown. In this research the potential formation of FFA degradation products was investigated under boiler conditions at lab-scale. Thermolytic degradation was assessed by analysing the concentration and composition of organic acids, short-chain amines and potential neutral components formed as well as the residual FFA in the condensate. The formation of organic acids could be a negative side effect of the FFA use, as these acidic compounds lower pH at the metal surface. The effect of the residence time was investigated to establish the kinetics. The outcome of this research helps to better understand the behaviour of FFA in the water-steam cycles and gives indications for optimisation of their application.


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O 43Distribution ratios of polyamines present in Helamin chemical between boiling water and saturated steamT. Petrova1, I. Burakov1

1 MPEI, TOT-TWT, Moscow, Russian Federation

The test data on the effect of pressure on distribution ratio of polyamines between boiling water and saturated steam during treatment of boiler water with different grades of Helamin are presented. The tests were performed at two pres-sures: 0.2 and 7.0 MPa. The test results showed different pattern of pressure effect on distribution ratios of polyamines for different Helamin grades. For the BRW-150 grade, pressure increase resulted in decrease in polyamine distribution ratio; for the 906H grade, pressure did not virtually have any effect on the distribution ratio, and for the 90H Turbo grade, increase in pressure made polyamine distribution ratio higher. In addition, polyamine distribution ratio was influenced by composition of other chemicals present in boiling water.

O 44AVT vs FFAP treatment: comparison of key indicesT. Petrova1, F. Dyachenko1

1 MPEI, Theoretical Bases of Heat Engineering, Moscow, Russian Federation

The TGD8-16 issued by IAPWS in 2016 stays that “It is extremely important that the key objectives and performance indicators are identified and monitored prior to and during the application of a FFA/FFAP” and that “the best way of determining the baseline is through measurement of the key indices for the cycle chemistry, especially total iron (and total copper and/or aluminum if the plant contains these metallurgies) under the conditions of the chemistry before the application of the FFA/FFAP treatment.”This presentation consists of comparison of water chemistry before and after FFAP application for different power plants. The impact of FFAP on CACE of the steam. The iron concentrations before and after the application of FFAP. What other benefits and risks were noted during FFAP application.

O 45Adsorption of oleyl propylenediamine on metal surfacesT. Petrick1, J. Jasper2, D. Disci-Zayed2, W. Hater2

1 Kurita Europe GmbH, Technical Sales, Ludwigshafen, Germany2 Kurita Europe GmbH, Technical Water, Ludwigshafen, Germany

Operation of water/steam cycle is threatened by corrosion unless proper conditioning measures are taken. As an alterna-tive for traditional cycle chemistry film forming amines (FFAs) is getting increasingly important.FFAs inhibit corrosion by being adsorbed on the metal surface as a thin film. Efficiency of FFA is reported for various applications in power plants, which operate continuously or under wet/dry lay-up conditions.Oleyl Propylenediamine (OLDA) is an effective film former. This contribution presents the results of an extensive study on adsorption characteristics of OLDA on metal surfaces: stainless steel, carbon steel, copper and aluminum alloys. Tests were carried out with different OLDA concentrations and at different temperatures.Adsorption of OLDA is accelerated with temperature and follows first order kinetics. Moreover, surface coverage of OLDA was determined being greatly influenced by the metal used. Selected findings are compared to data obtained with other FFA.

O 46Thermal decomposition of film forming amines in the power generating cycleS. Vidojkovic1,2, H. Spanjers1, M. Mijajlovic3

1 TU Delft, Faculty of Civil Engineering and Geosciences - Watermanagement Department, Delft, Netherlands2 University of Belgrade, Institute of Chemistry, Technology, and Metallurgy, Belgrade, Serbia3 University of Nis, Faculty of Mechanical Engineering, Nis, Serbia

Film forming amines (FFA) have been used as organic feedwater additives in the power industry for several decades. However, the utilization of FFA is still accompanied by a huge lack of data related to their decomposition in power water/steam cycle conditions and the impact of decomposition on power plant operation. In this paper the state-of-the-art for thermolysis of film forming amines in the water/steam cycle of thermal power plants is presented. A comprehensive criti-cal review and a thorough analysis of research findings have been performed. Attention is primarily given to the commonly used filming amines: octadecylamine (ODA), oleylamine (OLA), oleil propylendiamine (OLDA). The results both obtained in industrial steam generators and laboratory high temperature conditions were analyzed. The possible mechanism of ther-mal decomposition of film forming amines was explained, the decomposition products were discussed, the deposition


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rate was considered and the most important parameters influencing thermal decomposition were identified. All obtained results are consistent in regard to organic acids which have been found in extremely low and harmless concentrations. On the basis of the published data it may be also stated that the decomposition products of film forming amines were: ammonia, acetic acid, hydrogen, carbon monoxide and methane. The results indicate that advanced fundamental scien-tific background information and additional research, allowing for a complexity of multicomponent solutions, are needed to improve the understanding of the thermolysis of film forming amines in order to facilitate their application in the power industry and provide their safe and effective application in industrial facilities using the high temperature water.

PCC6: CYCLE CHEMISTRY IN VARIOUS PLANTS


O 63Sulphate adsorption on magnetite under steam generator chemistry conditionsL. Qiu1, G. Burton1, S. Rosseau1, J. Qian1

1 Canadian Nuclear Laboratories, Reactor Chemistry & Corrosion, Chalk River, Canada

Magnetite is a major corrosion product of carbon steel that forms deposits in the steam generators in water cooled nuclear reactors. Sulphate is present as an impurity in the steam generator feedwater that accumulates in the magnetite deposits within the steam generators and leads to formation of acidic crevices, which can affect corrosion and stress corrosion cracking of steam generator tubing. Reliable adsorption data are required to understand material degradation of steam generator tubing. Sulphate adsorption onto magnetite has been studied at temperatures from 25 to 300 °C as a function of pH, and chloride and sulphate concentrations. The results show that adsorption decreases with increasing pH and ionic strength, and adsorption followed Langmuir adsorption isotherm. Overall, sulphate adsorption onto magnet-ite is endothermic and the enthalpy of adsorption depends on the pH and ionic strength of solutions. Sulphate adsorption onto magnetite likely can lessen steam generator tube degradation in acidic conditions.

O 64Makeup water treatment systems in nuclear power plantsH. Hirano1

1 Former Central Research Institute of Electric Power Industry, Materials Science Research Laboratory, Yokosuka-shi, Japan

IntroductionThe manufacturing process of the makeup water in the nuclear power plants and the fossil power plants is fundamentally the same. However, as for the nuclear power plants, the concentration management of the impurities being contained in the makeup water which affects the water qualities of the reactor coolant is very important issue. The impurities of reactor coolant affect the long-term integrity of nuclear power plants.PWR Makeup Water Treatment SystemSchematic makeup water system of PWR is shown in Figure 1. As shown in Fig.1, the makeup water made after various processes from the raw water is sent to the secondary system pure water tank and to the primary cooling system makeup water tank through a degasifier.

The makeup water of a primary cooling system is supplied to the chemical volume control system (CVCS). Primary coolant system makeup water mainly aims at the dilution of boric acid which is used to control reactor core reactivity. Because


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primary coolant makeup water is supplied to CVCS, water quality is usually managed like the reactor primary coolant appropriately.On the other hand, the main purpose of the makeup water of secondary system is to provide an effluent water that meets both the quality and quantity of water to the condenser. The condensate water is supplied to feedwater and then to steam generator (SG).BWR Makeup Water Treatment System The makeup water is supplied to the main condenser via the demineralized water storage tank and the condensate storage tank. Since the condensate is supplied to a reactor cooling system, it is necessary to carry out water chemical management appropriately from a viewpoint of the long-term integrity of BWR power plants. The qualities of BWR makeup water shall meet tight specification for feed water and reactor coolant. In this paper, the normal operation values for the makeup waters of PWR and BWR are provided linked with PWR and BWR water cycle treatments, respectively.

O 65Geothermal steam turbine deposition mechanismsD. Addison1

1 Thermal Chemistry Limited, None, Hamilton, New Zealand

Geothermal steam turbines prone to forming significant turbine mineral deposits resulting in operational and maintenance problems under various steam purity & quality conditions and certain operating conditions.The mechanisms related to how deposits form within geothermal steam turbines are discussed in relation to both va-porous and mechanical transport of impurities in steam. Saturated and Superheated steam conditions and their impact on deposition within a geothermal turbine are discussed. The formation and behavior of the liquid films that form within geothermal steam turbines is outlined and the impact on these liquid films by reheating due to heat transfer across a turbine disk or shaft is discussed.

O 66The application of an environmental friendly scale-Inhibitor to mitigate deposit formation in the Soultz geothermal power plantR. Guillaume1, J. Mouchot2, J. Scheiber3, W. Hater4

1 ES Geothermie, Etudes et développement, Strassbourg, France2 ES Geothermie, Geochemistry, Strassbourg, France3 Bestec GmbH, Geochemie, Landau, Germany4 Kurita Europe GmbH, Technical Water, Duesseldorf, Germany

The formation of mineral scale is one of the phenomena that may take place when geothermal waters are pumped to the surface and used for production of electricity or heating and thereby can significantly deteriorate the function of a geo-thermal plant. In the area of the upper Rhine valley deposits found in heat exchangers consist of mainly barium sulfate and heavy metal sulfides, predominantly lead sulfide. In order to mitigate scale formation and necessity of frequent shutdown and cleaning of heat exchangers in the Soultz geothermal plant applies the dosage of a scale Inhibitor. This contribution presents the work done in order to reduce the environmental impact of the inhibitor dosage as well as to improve the antiscale performance especially with regard to the prevention of lead sulfide scale. Laboratory studies and the data of field application are shown.

PCC7: FLUE GAS CONDENSATION


O 70District heat and flue gas condensationF. Fogh1

1 Ørsted Bioenergy & Thermal Power, Chemistry, Fredericia, Denmark

In the Nordic countries district heat is the household heat source of choice in many areas. District heat is the grown up version of an ordinary central heating system.


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The district heat distribution in the Nordic countries with technical details comprising temperatures, water quality, net-work sizes … will be presented. A variety of heat sources are available and in use ranging from steam extraction in big power plants to small boilers with and without power generation and recently heat pumps have entered the scene. Flue gas condensation can efficiently squeeze out heat from wet fuels – what is the thermodynamics behind and what is the technology and equipment needed? Flue gas condensation yields a condensate that needs to be managed. This will be covered in supplementary presentations.

O 71Review of experiences on flue gas condensation and the re-use of the condensateK.N. Thomsen1, R. Lundberg2

1 COWI a/s, Bioenergy and Thermal Power, Aalborg, Denmark2 RL Aquaconsult, Chemistry, Västerås, Sweden

This presentation gives an introduction to the water treatment used in the Nordic countries for flue gas condensate to meet the environmental demands and possible reuse of the condensate. During the last decade, the concept of the con-densate has changed from wastewater that needed treatment ahead of discharge to a valuable resource for production of make-up water for district heating nets and water-steam circuits. The initial treatment of the water for discharge or reuse produces a condensate with neutral pH, trace contents of heavy metals, and low levels of suspended solids. For reuse this condensate is typically treated by a series of membrane techniques that produce water with purity corresponding to the intended use, e.g. as make-up water for combined heat-and-power plants. From the first Swedish experiences 15 years ago with demineralization of the condensate to the now widespread use in the Nordic countries, valuable experiences concerning the design and operation of the flue condensate rinsing plants have crystallized. However, there are still ob-stacles and challenges operating the plants, and these are briefly summarized here.

O 72Challenges in FGC treatment with re-use of the Flue Gas CondensateK.N. Thomsen2, R. Lundberg3

1 COWI a/s, Bioenergy and Thermal Power, Aalborg, Denmark2 RL Aquaconsult, Chemistry, Västerås, Sweden

The first flue gas condensate treatment plant using membrane techniques was installed in 1999 in Sweden. During the first years of operation of this kind of plants, a number of teething problems were encountered that are now mainly solved. Dissolved gases in the flue gas condensate caused problems: Ammonia from the SCNR process and carbon dioxide from the combustion. The strategies for removal of these gases from the condensate are exemplified, showing that the treatment of the concentrate (excess) streams from the membrane processes often causes the problems. Other causes of operational problems are also briefly mentioned.

O 73Microbial growth in membrane-based plants for rinsing of flue gas condensateL. Wiig1

1 lindawiig, Energy- process and environmental engineering, Rosersberg, Sweden

Growth of microbes in the condensate from flue gas condensation is frequently hampering the subsequent treatment of the water by membrane-based techniques. When the heat production is optimized by humidification of the combustion air by means of condensate, a raw condensate is produced with a temperature range that is about optimal for bacteria and they are often introduced through the humidification of combustion air. However, operational problems have also been encountered with plant designs without this obvious source of infection. The Swedish research foundation Energiforsk has financed the research project presented here. Based on several case studies, the report summarizes the experiences with bacterial growth in flue gas condensate, the obstacle for further treatment, and the abatement that has been tested. Bacterial analysis may be used to identify the type of bacteria and select the best method for combating.


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O 74Management of flue gas condensate at Skærbækværket Unit 401/402F. Fogh1

1 Ørsted Bioenergy & Thermal Power, Chemistry, Fredericia, Denmark

The Danish energy supplier, Ørsted, has recently commissioned two new wood chips-fired CHP-plants in Skærbæk in Jutland. These plants are designed with flue gas condensation as an integral part of the heat production for district heating, and the flue gas condensate is treated for reuse as make-up water for the district heating net and the boilers at the site including an USC once-through unit. This presentation summarized the experiences gained during the commissioning phase of the two new boilers on the treatment of the flue gas condensate.

PCC8: FLUE GAS CONDENSATION AND WATER PURIFICATION


O 75Design of a new plant for flue gas condensation and treatment of condensate based on 23 years of field experienceA. Fredrikson1

1 Tekniska Verken i Linköping AB, Department of Process and Chemistry, Linköping, Sweden

This presentation addresses the experiences of 23 years of operation of flue gas condensate treatment at Igelsta CHP in Södertälje, Sweden. Furthermore, we explain our considerations for the construction of a new flue gas condensation plant at an existing boiler. In 1994, we built our first flue gas condensation plant. After partial reconstruction in 2001 to meet environmental condi-tions, the treatment consisted of sand filtration, activated carbon filtration and reverse osmosis (RO). In 2009, we built Igelsta CHP, a recycled-wood-fired 240 MW boiler with extra 60 MW heat production by flue gas condensation. The FGC treatment is based on UF, RO and ammonia gas transfer membranes. Our experience reaches from the necessity of leak free textile filters in the flue gas filtratrion across the benefits of robust and simple solutions to the difficulty foreseeing the long-term economically most advantageous options. In 2019 a new flue gas condensation is commissioned at an existing waste-fired boiler. Here we briefly describe our ambition to use the technology that over the years has proved to be most robust.

O 76Experiences regarding treatment and reuse of flue gas condensate in waste incineration plantJ. Vuorinen1

1 Vesi-Ihminen, Problem solving and consulting, Helsinki, Finland

The presentation introduces the treatment scheme and reuse of flue gas condensate in waste incineration plant in Vantaa, Finland. The presentation goes through the key technology, commissioning and operation experiences of the process where condensate is treated to be used as make-up water for the power plant. Use of condensate cuts down the sewage and reduces the purchase of potable water. Main treatment steps before raw water tank include continuous sand filtration and RO. UF and chemical precipitation are used to treat and concentrate the wash water from sand filtration. Heavy metal selective ion exchangers are placed in flue gas condensate RO concentrate stream to guarentee the quality of sewage. During the first four years of operation, the challenges of reuse have not caused problems in condensate treatment pro-cess but in the make-up process. Most severe disturbances have been heavy alum- and silica-based scaling in make-up RO and problems created by carbon dioxide in EDI plant. Both of these problems originate from poor pH control in flue gas condensate treatment. In addition to process and technology details, some economical aspects, waste water permission and monitoring requirements are also presented.


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O 77TOC composition more important than concentration in IEX demineralisation of different water qualities for the production of steamE. De Meyer1, B. Peeters2, M. Vanoppen1, K. Verbeken3, A. Verliefde1

1 Ghent University, Applied Analytical and Physical Chemistry, Ghent, Belgium2 Monsanto Europe N.V., Environmental Department, Antwerp, Belgium3 Ghent University, Department of Materials- Textiles and Chemical Engineering, Ghent, Belgium

Fresh water becomes a limited resource in the industry. In order to help chemical industries to use other water sources and to close their water cycle for the production of steam, a well-founded insight on the challenges and possibilities of switching from one specific water quality to another is needed. A case study for Monsanto Europe N.V. was carried out, but the main findings hold for many more applications. Besides demineralisation by Ion Exchange (IEX), both the Total Organic Carbon (TOC) concentration, composition and the for-mation of organic acids under boiler conditions were investigated for two different water qualities (Antwerp tap water and wastewater after Reverse Osmosis (RO) treatment). The comparison included the effect of TOC composition on its removal by IEX and the potential corrosiveness of TOC compounds. Despite tap water showed a more efficient and higher TOC removal compared to RO permeate, tap water led to more organic acid formation under boiler conditions.

O 78Design considerations for UF filtration and demineralization of flue gas condensate for make-up waterT. Dalsgaard1, J. Kastensson2, A. Svensson3, J. Hilden1

1 Silhorko-Eurowater A/S, Technical Water, Skanderborg, Denmark2 Mercatus Engineering AB, Technical Dept., Vimmerby, Sweden3 Mercatus Engineering AB, Project Dept., Vimmerby, Sweden

The use of ultrafiltration and other membrane based technologies has been proven to be effective for treating flue gas condensates of waste and bio-fuel incinerated boilers. The use membranes combined with total flue gas cleaning and con-densation process allows minimizing the liquid waste streams. Using demineralized flue gas condensate, it is also possible to replace fresh water as a source for boiler or district heating make-up water. This paper describes design considerations and practical experiences for ultrafiltration plants used in Scandinavian power plants used as pretreatment for further desalination by reverse osmosis. Multiple fuels used and different techniques of treatment prior to condensing stage of flue gases mean wide fluctuation of the condensate quality and flow between the plants and season. Design practices for different plants operated in fluctuating conditions from the last decade are shown. Double pass reverse osmosis removes very much dissolved salts from the flue gas condensate. Most of the cases still require further treatment with membrane degassing and ion exchange. Design considerations for membrane degassers and electrodeionization system (EDI) are also shown.


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Poster Session


P 04Dissolution rates of nickel oxide in the primary circuit conditions of a pressurized water reactorA. Graff1, M. Bachet1, P. Bénézeth2

1 EDF Research and Development, Materials and Mechanics of Components, Moret sur loing, France2 CNRS, Geoscience Environnement Toulouse, Toulouse, France

The primary circuit of a pressurized water reactor (PWR) is subject to corrosion due to the formation of different oxides, called corrosion products. Some particles of these oxides are released in the primary fluid and may be activated when they pass through the core of the reactor. The radiation dose rates can be strongly influenced by their deposition on the whole primary circuit. Nickel comes from steam generator tubing and is one of the major studied corrosion product because of its activation into 58cobalt. Precise knowledge of the dissolution rates of nickel and how it changes with temperature and solution chemistry would be then valuable to understand its transport from steam generator tubes to the core and to control the contamination. Dissolution rates of nickel oxide were measured in hydrochloric acid and in boric acid media up to 100°C and pH 6. Two types of experiments were conducted: room temperature experiments by the stationary pH method and high temperatures experiments in mixed flow reactor. Results showed that boric acid is an inhibitor of the dissolution rates of NiO. Furthermore, this phenomenon is enhanced by the temperature and the concentration of boron. The formation of a surface complex was postulated to explain this effect. A 2pK monosite with a diffuse layer model was used to calculate the associated surface complexation constant Kbin order to determine the surface speciation of NiO in the chemical conditions of our trials. Then, a kinetic equation was used to model the experimental dissolution rates in boric acid medium. According to those results, the inhibitor effect is believed to be related to the concentration’s decrease of the protonated surface sites. Nevertheless, further investigations, as sorption experiments in boron medium, are needed to improve this kinetic model.

SEAWATER

SW1: EFFECTS OF SEAWATER SALT COMPOSITION


O 02The absolute salinity of seawater, its real components and its measurandsP.A. Giuliano Albo1, M. Le Menn2, S. Lago1, F. Sparasci31 INRiM, Thermodynamics, Turin, Italy2 SHOM, French Hydrographic and Oceanographic Service, Brest, France3 Laboratoire Commun de Métrologie LNE-CNAM, Termometry, La Plain Saint-Denis, France

Salinity is an essential quantity to calculate many of physical properties of oceans, but it is also a quantity hardly defin-able considering the complexity of the middle in its bio-geo-chemical composition and the imperfections of the existing measurement techniques. The TEOS-10 gives several definitions to the notion of absolute salinity, usable in function of the properties to study, but they are based on the concept of a constant elemental composition of seawater, so that, if its major inorganic components are well known, its real composition vary in time and space and its determination is still a challenge. Most of salinity calculations are based on conductivity measurements. This communication reviews other techniques which are used or could be used to assess the absolute salinity of seawater, and question about the mesurand of these techniques and the possibility to redefine the concept of salinity from physical properties.


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O 03Composition changes in sea salt and their effect on conductivity/salinity/density relationships in seawaterR. Pawlowicz1, N. Simantris1

1 University of British Columbia, Dept. of Earth- Ocean- and Atmospheric Sciences, Vancouver, Canada

Changes in the relative chemical composition of sea salt can lead to differences between the density of sewaters com-puted using salinity/conductivity/density relationships for Standard Seawater, which are codified in the TEOS-10 standard, and the actual density. Measurements of differences between actual and computed densities (the so-called “density anomaly”) can therefore provide information about the scale and location of composition changes in the ocean, and hence information about chemical mechanisms and the general circulation. Previous theoretical work has quantified the effects on density anomaly of biological production and remineralization processes, which involve relative changes in elements of the carbonate system and the macronutrients. Here we quantify the relationship between changes in the relative chemi-cal composition and the density anomaly of processes occurring in or near hydrothermal vents, which modify magnesium, sulfates, and silicic acid, and in regions where double-diffusive processes are important, which may lead to fractionation.

O 04A modified algorithm for estimating Absolute SalinityH. Uchida1

1 Japan Agency for Marine-Earth Science and Technology, Research and Development Center for Global Change, Yokosuka, Japan

In 2010, the International Thermodynamic Equation of Seawater 2010 (TEOS-10) was adopted as the replacement for the International Equation of State of Seawater 1980 (EOS-80). In TEOS-10, Absolute Salinity is introduced instead of using Practical Salinity. Density of seawater is defined as a function of Absolute Salinity rather than conductivity, and an algorithm for estimating Absolute Salinity from Practical Salinity measurement was provided along with TEOS-10. The algorithm exploits the correlation between the Absolute Salinity anomaly and the silicate concentration, making use of the global atlas of silicate concentrations. However, the algorithm provided along with TEOS-10 have a latitude-dependent error (an order of ±0.01 g/kg) and an error (an order of +0.01 g/kg) caused by the effect of river water in the surface layer (< 100 m) of the Arctic Ocean. To evaluate the algorithm for estimating Absolute Salinity, Absolute Salinities for a total of 7126 samples were measured by vibrating tube densitometers, and Practical Salinity, silicate, nitrate, total alkalinity, and dissolved inorganic carbon were also measured for the global ocean (Fig. 1). A simple modified algorithm for estimating Absolute Salinity for the global ocean is proposed by using this dataset. Estimation error is largely reduced for the mod-ified algorithm, especially for the surface later of the Arctic Ocean. Standard deviation of difference between estimated and measured Absolute Salinity is 4.4 and 3.2 g/kg for the TEOS-10 algorithm and the modified algorithm, respectively.


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SW2: TEOS-10 APPLICATIONS


O 29A thermodynamic potential of seawater as a function of potential enthalpyT. McDougall11 University of New South Wales, School of Mathematics and Statistics, Sydney, Australia

A thermodynamic potential is found for seawater as a function of potential enthalpy, Absolute Salinity and pressure. This thermodynamic potential is simply a linear combination of enthalpy and entropy. From this thermodynamic potential, all the thermophysical properties of seawater can be derived, just as all these thermophysical properties can be found from the Gibbs function (which is a function of in situ temperature, Absolute Salinity and pressure). We have been unable to find a thermodynamic potential for seawater in terms of potential temperature and it is probably impossible to do so.

O 30Salinity/density anomalies in the deep North Pacific – Evidence of a hydrothermal vent signal?R. Woosley1

1 MIT Center for Global Change Science, Department of Earth, Atmospheric & Planetary Sciences, Cambridge, USA

Positive salinity anomalies caused by deviations in the concentrations of minor components of seawater are well known to occur. Most deviations are caused by increases of dissolved inorganic carbon (DIC) and nutrients in deep water as a result of remineralization of organic matter. As a result, the largest anomalies would be expected in the deep North Pacific where DIC and nutrients are highest. Measurements from Line P, P18, and 9° N indicate otherwise. Salinity and density measure-ments from these locations are lower than expected based on their DIC and nutrient concentrations. Could precipitation reactions at hydrothermal vents induce a deficit in sulfate concentrations and lower the salinity anomaly? Deep currents and hydrothermal vent locations hint at such a possibility.

O 31Comparability of Seawater pH values – definition and measurandM.F. Camoes1, C.M.R. Oliveira1, R.B. Silva1

1 University of Lisbon, CQE- Faculdade de Ciências, Lisboa, Portugal

Accurate measurements of pH values are key for reliable expression of the acidity of solutions, function of the chemical potential of hydrogen ions, H+. Firm observation of the quantity’s conceptual definition and a clear account of the related measurand, are mandatory to overcome claimed problems associated with lack of comparability of seawater pH values, in space, time and laboratory.The concept of pH is very well defined and routinely used in dilute aqueous solutions. In 1985 a Pure & Applied Chemistry publication addressed the issue of a multistandard approach vs. that based on the definition of a single standard, and came out with a compromise which recognized the advantages of both. This proved to be not satisfactory and a metrolog-ically well founded basis for Measurement of pH. Definition, Standards, and Procedures was reached and recommended in 2002. In high ionic strength matrices, namely seawater, despite great progress has taken place at both the fundamental and the practical levels, pH measurements are still lacking harmonization, which urges for the sake of valid pH values.“Several scales, all masquerading under the name pH, are in common use. Many investigators are thinking and computing in terms of one definition and measuring a different quantity”. (R. Bates, 1948)


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SW3: PHYSICAL PROPERTIES OF SEAWATER


O 51Comparison between TEOS-10 estimated density and experimental density measured in IAPSO standard seawater by a single sinker hydrostatic balanceP.A. Giuliano Albo1, S. Lago1, R. Romeo1, A. Malengo2

1 INRiM, Thermodynamics, Turin, Italy2 INRiM, Department of Innovation and Metrology Services, Turin, Italy

IAPSO Standard Seawater (ISSW) is used by oceanographic laboratories all over the world as reference for salinity thanks to its stability in terms of conductivity. On the other side, oceans water density is, mainly, calculated by equations of state linking measurements of conductivity, depth and temperature (CDT) to their correspondent thermodynamic state varia-bles, namely salinity, pressure and temperature. Since numerical models of the oceans dynamics depend on the reliability of the properties calculated by equations of state, in this work, density measurements of IAPSO Standard Seawater have been carried out in the temperature range of (15 and 35) °C, at atmospheric pressure. The adopted instrument is a single sinker hydrostatic balance modified to work with corrosive fluids like seawater. Furthermore, density measurements in double distilled water have been used to characterize the apparatus and to correct ISSW density measurement, when possible. A comparison with density values predicted by TEOS-10 has revealed that experimental values differ by up to 45 ppm, at 35 °C.

O 52Absolute density measurements for sea-water by a hydrostatic weighing methodY. Kayukawa1, H. Uchida2

1 National Institute of Advanced Industrial Science and Technology AIST, National Metrology Institute of Japan NMIJ, Tsukuba, Japan2 Japan Agency of Marine-Earth Science and Technology, Research and Development R&D Center for Global Change RCGC, Yokosuka,

Japan

Thermodynamic equation of state for seawater plays an important role in ocean monitoring and long-term climate predic-tion. The latest version of the sea-water equation is called TEOS-10, and most of input data of sea-water density used to formulate the equation are not absolute, it has been pointed out that there exists a relative uncertainty of about 5 ppm in calculating density. As a critical evaluation of TEOS-10, absolute density measurements for standard sea-water sample were conducted in this study. Figure 1 illustrates a schematic diagram of a hydrostatic weighing apparatus. By using the present apparatus, sea-water density was measured by means of a buoyancy force acting on a sinker. The sinker is made of silicon single crystal and its mass (100.241706 g +/- 0.000 0008 8 g) and density (2.329 085 09 g · cm-3 +/- 0.000 000 38 · cm-3) were calibrated with small uncertainty. Required sample amount of sea-water is 200 cm3. The sample is filled in a quartz glass cell which is immersed in a water-bath so that the sample temperature is controlled at (20.000 +/- 0.000 3 C). Validity of the hydrostatic weighing measurements were confirmed by measuring an organic liquid (n-tridecane) and pure water (purified by Milli-Q). The density of n-tridecane is calibrated by a hydrostatic weighing with an 1-kg silicon sphere. The measurement results showed a good agreement with reference values within 0.9 ppm for n-tridecane and 1.2 ppm for pure water, where an expanded uncertainty of the present measurement is 1.3 ppm in density. In the present study, a set of absolute density measurements were conducted for standard sea water reference material (Pre18RM for O2 and CO2 concentration measurements) and standard sea water (IAPSO P series). Density deviation of the present measurements f rom TEOS-10 are discussed.


60

Poster Session


P 05Absolute Salinity measurements based on sound velocity and refractive index measurementsH. Uchida1, Y. Kayukawa2

1 Japan Agency for Marine-Earth Science and Technology, Research and Development Center for Global Change, Yokosuka, Japan2 National Institute of Advanced Industrial Science and Technology, National Metrology Institute of Japan, Tsukuba, Japan

In the International Thermodynamic Equation of Seawater 2010 (TEOS-10), Absolute Salinity is introduced instead of using Practical Salinity. Absolute Salinity can be estimated from density measurement by a vibrating tube densitometer. However, the densitometer can be used only in a laboratory. To measure Absolute Salinity in the ocean, sound velocity and refractive index sensors are commercially available. Although measurement resolution of Absolute Salinity (0.001 g/kg) for these commercially available sensors is an order magnitude lower than that of the Practical Salinity based on conductivity measurement (0.0002 g/kg), a high-resolution Absolute Salinity sensor based on refractive index measure-ment (0.0001 g/kg) is being developed. In this study, we present results of in situ measurements of Absolute Salinity by sound velocity sensors calibrated with bottle sampled density measurements. We will also present preliminary results of Absolute Salinity measurements by the developing refractive index salinometer.


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THERMODYNAMIC PROPERTIES OF WATER AND STEAM

TPWS1: METASTABLE WATER


O 05Measurements of density for supercooled ordinary water, heavy water, and seawater at high pressuresA. Blahut1, M. Duška1, J. Hykl1, P. Peukert1, V. Vinš1, M. Čenský1, J. Hrubý1

1 Institute of Thermomechanics of the CAS- v. v. i., Thermodynamics, Prague, Czechia

An apparatus tailored to accurate density measurements of supercooled liquids up to pressure of 200 MPa has been recently developed at the Institute of Thermomechanics of the Czech Academy of Sciences. The measurement principle is based on an optical evaluation of volume changes of supercooled liquid enclosed in fused silica capillaries. The apparatus allows for accurate measurements of density relative to density at the reference temperature (e.g., 298.15 K) and given pressure.An overview of the apparatus, measurement and calibration procedures are presented together with new results for the density of supercooled ordinary water, heavy water, and standard seawater. The new data in temperature range from 253.15 to 298.15 K and pressures up to 100 MPa are compared with respective IAPWS thermodynamic property formula-tions and relevant literature experimental data.

O 06Measurements of the surface tension of the supercooled ordinary water substance down to -32 °CR. Mares1, J. Kalová2

1 University of West Bohemia, Power System Engineering, Pilsen, Czechia2 University of South Bohemia- Faculty of Science, Department of Mathematics and Biomathematics, České Budějovice, Czechia

The capillary elevation method with capillaries of very small inner diameters operates with a very small volume of liquid which enables measurements below freezing point. The smaller the inner diameter of the capillary, the higher the column of the liquid in the capillary, and the more accurate measurements can be achieved. But the smaller the diameter is, the longer time is necessary to reach the steady (stabilized) state of the liquid column in the capillary. In very thin capillaries the relaxation time takes several tens of minutes. The diameter of the capillary in our last measurements was 0.097 mm. With this capillary the surface tension of supercooled ordinary water substance was measured in the temperature range from -20 °C down to -32 °C. In this way, the temperature range of the measured data in previous years can be extended to lower temperatures. The course of these data is almost linear. The line connecting new experimental data points is very close to the points representing experimental data down to -25 °C gained by the authors in 2013. New experimental data are compared with the data by Hacker P. T., Technical Note 2510, National Advisory Committee for Aeronautics, Washington (1951) measured down to 23 °C, with the data by Floriano M. A. and Angell C. A., J. Phys. Chem., 94, 4199 (1990) measured down to -27 °C and with the data calculated from the extrapolated international IAPWS equation (1994), http://www.iapws.org/. With the quartz glass capillary of the diameter 0.097 mm the experimental data of the surface tension of the supercooled ordinary water substance have been extended down to 32 °C.

O 07Seven years of measurement of the surface tension of supercooled water and aqueous mixtures at IT CASV. Vinš1, J. Hykl1, J. Hrubý1, J. Hošek1, M. Fransen2, B. Šmíd1, Z. Nikl11 Institute of Thermomechanics of the CAS, Thermodynamics, Prague, Czechia2 Shell- Amsterdam, Flow Assurance, Amsterdam, Netherlands

The contribution presents an overview of more than half a decade research focused on the experimental investigation of the surface tension of water and aqueous mixtures under the metastable supercooled conditions. The surface tension of supercooled water was successfully measured with two different measuring techniques. In the first case, a modified capillary rise technique allowed for measurements down to -26 °C [1,2]. The second method, similar to that employed by Hacker [3], whose data showed a potential anomaly at temperatures below -8 °C [4], used a horizontal capillary tube [5]. The data obtained with both methods agree with each other and can be correlated with the IAPWS standard [6]


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extrapolated below 0.01 °C. The data were recently used by Pátek et al. [7] in the new correlation for the surface tension valid from -26 °C up to the critical point, which is being revised as a potential replacement of the current IAPWS standard. In 2017, the experimental apparatus was further modified for the measurements of aqueous mixtures using a capillary rise method [8]. The setup was tested on the measurements of aqueous mixtures with lower alcohols [8] and sodium chloride. Currently, new data for the surface tension of supercooled seawater are being measured. The preliminary data show promising agreement with the correlation by Nayar et al. [9] within the stable region from 0 °C to 30 °C. The new data might be considered in the development of the IAPWS standard for the surface tension of seawater extended also in the supercooled region.References1. Hrubý et al., J. Phys. Chem. Lett. 5 (2014) 425 2. Vinš et al., J. Phys. Chem. B 119 (2015) 5567 3. Hacker, NACA TN 2510 (1951) 4. Kalová and Mareš, Int. J. Thermophys. 33 (2012) 992 5. Vinš at al., J. Chem. Eng. Data 62 (2017) 3823 6. IAPWS R1-76(2014) 7. Pátek et al., J. Chem. Eng. Data 61 (2016) 928 8. Vinš et al., EPJ Web Conf. (2018) 9. Nayar et al., J. Phys. Chem. Ref. Data 43 (2014) 043103

O 08Viscosity of supercooled water under pressure and two-state interpretation of water anomaliesB. Issenmann1, L.P. Singh1, A. Dehaoui1, R. Berthelard1, F. Caupin1

1 Institut Lumière Matière, Département de physique, Villeurbanne, France

Among the numerous anomalies of water, the effect of pressure on its transport coefficients is particularly striking. Around room temperature, an increase in pressure from ambient results in a decrease of viscosity and rotational correlation time, while the translational diffusion coefficient increases. At high enough pressure, the pressure dependence is reversed and water behaves as a normal liquid. The pressure anomalies for translational and rotational diffusion have been followed deep in the supercooled region. However, up to now, viscosity data for supercooled water under pressure was not available. We report for the first time such data, obtained with a Poiseuille flow experiment performed up to 300 MPa and down to 20°C below the melting line [1]. Our data reveal a large intensification of the viscosity anomaly upon cooling: pressurization at 244 K reduces the viscosity of water by nearly a factor of 2. The location of the viscosity minimum follows that of the translational diffusion coefficient maximum. We discuss experimental data on dynamic properties in the framework of two-state models for water. Combining a mod-ified version of a previous dynamic model [2] with an existing, quantitative model for thermodynamics [3], we obtain an accurate description of dynamic properties of stable and supercooled water under pressure. We discuss the possible connection with a putative phase transition between two distinct liquid forms of supercooled water [4]. Motivated by analogies between solutes and pressure and recent experiments on water-glycerol mixtures [5] we also present measurements of the viscosity of supercooled water-glycerol mixtures rich in water.

[1] L. P. Singh, B. Issenmann, F. Caupin. Proc. Natl. Acad. Sci. USA 114, 4312 (2017)[2] H. Tanaka. J. Chem. Phys. 112, 799–809 (2000).[3] V. Holten and M.A. Anisimov. Sci. Rep. 2, 713 (2012)[4] P. Gallo et al. Chem. Rev. 116, 7463-7500 (2016)[5] Y. Suzuki and O. Mishima. J. Chem. Phys. 141, 094505 (2014)

O 09Equation of state of water at negative pressure and relations between lines of thermodynamic anomaliesF. Caupin1, V. Holten1, C. Qiu2, E. Guillerm1, M. Wilke3, M. Frenz2

1 Université Claude Bernard Lyon 1, Institut Lumière Matière, Villeurbanne, France2 University of Bern, Institute of Applied Physics, Bern, Switzerland3 Deutsches GeoForschungsZentrum and Universität Potsdam, Erd- und Umweltwissenschaften, Potsdam, Germany

The most prominent anomaly of water is its density maximum near 4 °C at ambient pressure. Although the locus of density maxima has been followed at positive pressure down into the supercooled region, experimental data at negative pressure are scarce. Negative pressure is a metastable state where the liquid density is reduced. Following up a pioneering work by the group of Angell [1], we have used micrometric inclusions of water in quartz to bring water to the largest negative pressure to date [2-5].


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Using Brillouin spectroscopy, we have measured sound velocity for a series of temperatures and densities. These data were interpolated and integrated to determine an experimental equation of state for water down to -137 MPa [4,5]. We find a line of density maxima whose temperature increases up to 18 °C with decreasing pressure. We also find lines of minima and maxima in sound velocity and compressibility. We discuss the thermodynamic rules relating these lines and prescribing their order.Our results shed light on the origin of the anomalies of water [6]. In particular, the existence of a line of isothermal com-pressibility maxima along isobars is a necessary condition for the second critical point scenario [7] and the singularity-free interpretation [8].

[1] Zheng, Q.; Durben, D. J.; Wolf, G. H.; Angell, C. A. Science 1991, 254, 829−832.[2] Azouzi, M. E. M.; Ramboz, C.; Lenain, J.-F.; Caupin, F. Nat. Phys. 2012, 9, 38−41.[3] Pallares, G. et al. Proc. Natl. Acad. Sci. U. S. A. 2014, 111, 7936−7941.[4] Pallares, G.; Gonzalez, M. A.; Abascal, J. L. F.; Valeriani, C.; Caupin, F. Phys. Chem. Chem. Phys. 2016, 18, 5896−5900.[5] Holten, V; Qiu, C.; Guillerm, C; Wilke, M.; Rička,J; Frenz, M.; Caupin, F. J. Phys. Chem. Lett. 2017, 8, 5519-5522.[6] Gallo, P. et al. Chem. Rev. 2016, 116, 7463−7500.[7] Poole, P. H.; Sciortino, F.; Essmann, U.; Stanley, H. E. Nature 1992, 360, 324−328.[8] Sastry, S.; Debenedetti, P. G.; Sciortino, F.; Stanley, H. E. Phys. Rev. E 1996, 53, 6144−6154.

O 10Application of quintic and quasi-quintic equation of states to describe some pecularities of metastable waterA.R. Imre1, A. Groniewsky2, G. Györke2

1 MTA Centre for Energy Research, Department of Thermohydraulics, Budapest, Hungary2 Budapest University of Technology and Economics, Department of Energy Engineering, Budapest, Hungary

Although the properties of stable liquid water can be extended smoothly to the slightly metastable liquid states, the deeply metastable territories are still quite unknown. Experiments trying to reach the tensile strength of water (i.e. the deepest, most often negative pressure at a given temperature where water still exist in liquid state) are providing confusing results. High-quality experiments can be divided into two groups, depending on the way to obtain metastability. With ultrasonic method the measured tensile strength at temperatures close to ambient one is around -30 MPa, while for inclusion method it is around or below -100 MPa. The difference could be explained by assuming the effect of an already vanished, long-suspected low-temperature critical point, i.e. the existence of a second Widom-region which observable only under negative pressures. Enhanced compressibility in this region can cause extremely high nucleation probability, cavitating the water still far from the liquid-vapour stability line. A quantic, van der Waals-like equation of states is proposed, which can qualitatively describe the anomaly. The anomalous region can be passed by approaching the deeply metastable region on isochoric paths (like in the inclusion method), while processes with metastable liquid following adiabatic paths (like in the ultrasonic method) might hit it, causing prompt cavitation and providing false tensile strengths.

TPWS2: SOUND SPEED, MISCELLANEOUS


O 37Speed of sound measurements in subcooled waterS. Lago1, P.A. Giuliano Albo1, G. Cavuoto2

1 INRIM, Thermodynamics, Turin, Italy2 Politecnico di Torino, Dipartimento di elettronica e telecomunicazioni, Turin, Italy

Besides being a very common and extremely important substance for the known form of life, water, with its own prop-erties, has a remarkable influence on the physical and chemical processes for a great number of different technical and scientific applications. The current research on the thermodynamic properties of pure water has been mostly focused on properties like density, heat capacity, vapour pressure or osmotic coefficients at atmospheric pressure; but, in order to improve the equation of state of the IAPWS-95 Formulation [1] in the subcooled water region, accurate experimental data of speed of sound, with a very low relative uncertainty, are needed. Nowadays only very few sound velocity results in metastable water have been obtained [2-5] and they are, in some cases, not enough accurate. In this context, at INRiM accurate experimental speed of sound measurements in high-purity subcooled water have been carried out in wide range of temperature (between 263 K and 293 K) and for pressures up to 300 MPa. The results will be useful to verify experi-mentally and eventually restate the dedicated equation of state in the IAPWS-95 formulation, so that it can also be valid in the metastable region.

[1] Wagner, Prus, J. Phys. Chem. Ref. Data 31, 387 (2002).


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[2] Lin and Trusler, J of Chem. Physics 136, 094511 (2012).[3] Hidalgo Baltasar, Taravillo, Baonza, Sanz, and Guignon, J. Chem. Eng. Data 56, 4800 (2011).[4] Vance and Brown, J. Acoust. Soc. Am. 127, 174 (2010).[5] Petitet, Tufeu, and Le Neindre, Int. J. Thermophys. 4, 35 (1983).

O 38Speed-of-sound measurements and derived thermodynamic properties of liquid waterK. Meier1, A. El Hawary1

1 Helmut-Schmidt-University/University of the Federal Armed Forces Hamburg, Institute for Thermodynamics, Hamburg, Germany

New measurements of the speed of sound in liquid water have been carried out with a double-path-length pulse-echo technique. The new data cover the temperature range between 0.5 °C and 95 °C along 11 isotherms with pressures up to 100 MPa. The measurement uncertainties (at the 0.95 confidence level) amount to 2.1 mK for temperature, 70 ppm for pressure, and 70 ppm for speed of sound. The path length in the acoustic sensor has been calibrated against the most accurate literature data for the speed of sound in liquid water at ambient pressure. From the speed-of-sound data set other thermodynamic properties of water, such as isobaric and isochoric heat capacities, were derived by the method of thermodynamic integration. The experimental results and derived properties are compared with IAPWS-95 formulation and literature data.

O 39Densities of the liquid and the gas: some modern models and numerical data in the critical region of H2OE. Ustyuzhanin1

1 National Research University “MPEI” Moscow- Russia- Krasnokazarmennaya 14 111250, Thermophysics, Moscow, Russian Federation

An analysis of some literary sources is made in the report. They contain tabulated data on the liquid density (ρl) and the gas density (ρg) on the saturation line of H2O. We have considered also a work of Alexandrov et al (1998) and a work of Anisimov et al (1990). It is shown that the accurate calculated ρl,ρg,T - data are based on scaling models of Anisimov et al (1990). Among them there is a form, ρg(τ,D,C), which is associated with ρg, where τ = (Tc - T)/Tc is a relative temperature, D = (a,β,Tc …) are critical characteristics, (a, β) are critical indexes, C are adjustable coefficients. This model meets the scale theory of critical phenomena (ST), works in the interval, τ = 0.002 - 0.012, and reflects the density data accumulated before 1990. We have considered a model, fd(τ,D,C), which is intended to describe the mean diameter, fd = (rl,+ rg)(2ρc) - 1 - 1. The model, fd(τ,D,C), is adapted to H2O (Anisimov, 1990) and has contained: 1) a scaling component with (1 - a) index and a linear component. Another type of fd(τ,D,C) is developed in this work and referred to as a combined scaling model [1]. Its struc-ture contains several components, among them: 1) component with 2β index, 2) a component with (1 - a) index. A similar combined scaling models have been developed for other properties (the order parameter, ρl, ρg ). A nonlinear methodology is proposed to calculate characteristics, D = (a,β,Tc, ρc… ), and adjustable coefficients, C. This statistical procedure uses input (ρl,ρg,T) data (IF 97) in a wide temperature range. There are got numerical estimates of parameters those are related to the functions mentioned. We have calculate (ρg,ρl,T) values in the interval 10 -5 < τ < 0.01. A behavior of fd as well as its components are investigated. We have compared our (ρg,ρl,T) data with results those are related to (IF – 95) in 10 -5 < τ < 0.01.

Reference1. Vorob’yev V. S., Ustyuzhanin E. E., Rykov V. A. 2016, J. Phys.: Conf. Ser., 774, 012017


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O 40Temperature of supercooled water droplets evaporating in vacuumC. Goy1, M. Potenza2, S. Dedera3, M. Tomut4, E. Guillerm5, A. Kalinin1,4, K.O. Voss4, A. Schottelius1, N. Petridis4, A. Prosvetov4, G. Tejeda6, J.M. Fernandez6, C. Trautmann4,7, U.A. Glasmacher3, F. Caupin5, R.E. Grisenti1,41 J. W. Goethe-Universität Frankfurt, Institut für Kernphysik, Frankfurt, Germany2 Universita degli Studi di Milano, Dipartimento di Fisica "Aldo Pontremoli", Milano, Italy3 Institute of Earth Sciences, Institute of Earth Sciences, Heidelberg, Germany4 GSI Helmholtzzentrum für Schwerionenforschung, Materials Research Department, Darmstadt, Germany5 Université Claude Bernard Lyon 1, Institut Lumière Matière, Villeurbanne, France6 Instituto de Estructura de la Materia, Laboratory of Molecular Fluid Dynamics, Madrid, Spain7 Technische Universität Darmstadt, Material- und Geowissenschaften, Darmstadt, Germany

In order to achieve a large degree of supercooling with a liquid, it is better to use small samples, short experimental timescales, and to reduce the effects of walls. The three conditions are met for micron-sized water droplets evaporating in vacuum. However, it is not possible to have a thermometer inside such objects, and accurate knowledge of the instanta-neous temperature of the droplets is a challenge. Here we show how Raman light scattering from the evaporating droplets allows determining their size as a function of time with a precision better than 0.2 %. This can be used with a Knudsen evaporative model to calculate the temperature. We find that water can remain liquid down to 230.6 +/- 0.6 K [1]. Raman spectra of water in the OH stretch region are found to exhibit a gradual blue-shift upon cooling.

[1] Claudia Goy et al. “Shrinking of Rapidly Evaporating Water Microdroplets Reveals their Extreme Supercooling”, Phys. Rev. Lett. 120, 015501 (2018)

TPWS3: MOLECULAR THEORY AND SIMULATION


O 47Cross second virial coefficient and dilute gas transport properties of (water vapor + carbon dioxide) mixtures from ab initio intermolecular potentialsR. Hellmann1

1 Universität Rostock, Institut für Chemie, Rostock, Germany

The cross second virial coefficient and the dilute gas shear viscosity, thermal conductivity, and binary diffusion coeffi-cient for mixtures of water vapor and carbon dioxide have been determined at temperatures from (250 to 2000) K using state-of-the-art computational approaches. The required intermolecular potential energy surface (PES) for the H2O–CO2 interaction has been newly developed utilizing high-level quantum-chemical ab initio methods, while existing ab initio PESs have been employed for the H2O–H2O [1] and CO2–CO2 [2] interactions. The cross second virial coefficient and the dilute gas transport properties have been computed from the PESs by means of the Mayer-sampling Monte Carlo technique [3] and the kinetic theory of polyatomic gas mixtures [4], respectively. Particularly for the dilute gas transport properties, experimental data are extremely scarce and of lower accuracy than the new ab initio calculated values.

[1] R. Bukowski et al., J. Chem. Phys. 128, 094313 (2008).[2] R. Hellmann, Chem. Phys. Lett. 613, 133 (2014).[3] J. K. Singh and D. A. Kofke, Phys. Rev. Lett. 92, 220601 (2004).[4] R. Hellmann et al., J. Chem. Phys. 144, 134301 (2016) and references therein.


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O 48Ab initio calculation of the second and third virial coefficients for H2O and D2OA. Harvey1, G. Garberoglio2, P. Jankowski3, K. Szalewicz4

1 National Institute of Standards and Technology, Applied Chemicals and Materials Division, Boulder, USA2 Fondazione Bruno Kessler, European Centre for Theoretical Studies in Nuclear Physics and Related Areas, Villazzano, Italy3 Nicolaus Copernicus University, Faculty of Chemistry, Torun, Poland4 University of Delaware, Department of Physics and Astronomy, Newark, USA

The virial expansion yields a rigorous representation of gas-phase thermodynamics, but for water the second virial co-efficient is only known from experiment over a moderate temperature range. There is even less knowledge of the third coefficient.It is possible to calculate virial coefficients rigorously from the intermolecular potential. We use two state-of-the-art potentials, both of which account for molecular flexibility and can be used for H2O and D2O. In addition, we use one rigid and one flexible three-body potential. The path-integral Monte Carlo method is used to account for quantum effects in both rigid and flexible models. Our second virial coefficients match available data but cover a larger temperature range; our third virial coefficients agree with some data but suggest a possible systematic error in the data at low temperatures. The effect of flexibility is significant. Quantum effects are large near room temperature, and remain significant up to roughly 700 K.

O 49Isothermal-isometric molecular dynamics approach for prediction of three-phase equilibrium conditions of methane hydrate systemD. Yuhara1, P.E. Brumby1, D.T. Wu2, A.K. Sum3, K. Yasuoka1

1 Keio University, Department of Mechanical Engineering, Yokohama-shi, Japan2 Colorado School of Mines, Chemistry Department, Golden Colorado, USA3 Colorado School of Mines, Hydrate Energy Innovation Lab Chemical & Biological Engineering Department, Golden Colorado, USA

Clathrate hydrates are ice-like solid crystalline compounds of water which, together with guest molecules, form under high pressure and low temperature conditions. Clathrate hydrates have been studied for their scientific interest as well as actual and anticipated industrial applications. To realize these applications of clathrate hydrates, broad understanding of the three-phase hydrate-water-vapor equilibrium is of great importance. Although experimental measurements of hy-drate phase equilibrium conditions are difficult and expensive, molecular simulations offer a convenient and inexpensive route with which to estimate them.In this study, isothermal-isometric (NVT) Molecular Dynamics (MD) simulations were applied to predict three-phase equi-librium conditions of the solid methane hydrate, liquid water and vapor methane co-existence system. In NVT simulations, the growth or dissociation of the hydrate phase can lead to significant changes in pressure as the system reaches the equilibrium conditions. We found that the estimated equilibrium pressures were higher than those reported in previous studies using isothermal-isobaric (NPT) MD simulations. The differences between our results and previous simulation results are attributable to long computational time, large system size and the pressure calculation method employed. The first two contribute to avoiding misleading of equilibrium conditions due to insufficient sampling and finite size effects, respectively. Moreover, we calculated the pressure in the vapor methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system. This fact clearly highlights the difficulties in the pressure calculation and control for multiphase systems due to differences in compressibility of each phase and the effects of interfacial tension. The use of NVT MD simulations is a useful approach for the prediction of equilibrium conditions of multiphase systems.

O 50Evaluating the methodology of classical nucleation theory using large scale molecular dynamics simulationS. Ayuba1, K. Nomura2, D. Suh1, K. Yasuoka1

1 Keio University, Mechanical engineering, Hiyoshi- Kouhoku-ku- Yokohama- Kanagawa, Japan2 RIKEN, Advanced Institute for Computational Science, Tonan-cho- Chuo-ku- Kobe- Hyogo, Japan

There is a gap of nucleation rate between the classical nucleation theory (CNT) and experiment, because the first stage of nucleation is a molecular level. In order to investigate the first stage of nucleation, molecular dynamic (MD) simulation is effective. Many studies of homogeneous droplet nucleation using MD have been performed1, but the range of nuclea-tion rate calculated from MD is orderly greater than those measured from experiment, because of the difference of the observable range due to the supersaturation ratio. Recently, Diemand et al. performed a large-scale MD simulation of homogeneous droplet nucleation and directly compared the nucleation rate with experiment2.


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In this study, we carried out large-scale MD simulations of homogeneous droplet nucleation using carrier gas thermostat. Furthermore, in addition to the nucleation rate analysis, we acquired the critical cluster size and cluster formation free en-ergy using kinetic analysis3, and compared with those from CNT to evaluate the validity of the methodology of theoretical nucleation rate calculation.We used the Lennard-Jones particle for argon and observed the droplet nucleation at 80 K. Our simulation results covered supersaturation ratios from 3.78 to 6.87. When we measured the nucleation rate from MD, JMD, using threshold method, the results of JMD are 8 to 13 orders of magnitude larger than the theoretical nucleation rate prediction of CNT. If we input values obtained from MD in the theoretical equation and compared with JMD, the agreement with JMD was within an order of magnitude. Thus, we found that the theoretical equation is reasonable.

1. K. Yasuoka and M. Matsumoto, J. Chem. Phys., 109, 8451 (1998).2. J. Diemand, R. Angélil, K. K. Tanaka, and H. Tanaka, J. Chem. Phys., 139, 074309 (2013).3. H. Matsubara, T. Koishi, T. Ebisuzaki, and K. Yasuoka, J. Chem. Phys., 127, 214507 (2007).

TPWS4: MODELS AND FORMULATIONS


O 59A theoretically based departure function for multi-fluid mixture models applied to mixtures containing waterA. Jäger1, I.H. Bell2, C. Breitkopf1

1 Technische Universität Dresden, Chair of Technical Thermodynamics, Dresden, Germany2 National Institute of Standards and Technology NIST, Thermophysical Properties of Fluids Group, Boulder, USA

The state-of-the-art in accurate mixture modeling are multi-fluid models formulated in the reduced Helmholtz energy, see, e.g. [1]. The model consists of an ideal part and a residual part. The residual part is again split in two parts: a sum over all residual reduced Helmholtz energies of the pure fluids times the respective mole fractions and the so-called departure function. Omitting the departure function, the model contains four adjustable parameters, namely βv, βT, γv, and γT, which can be fitted to experimental data or which can be set to some specific values in order to obtain predictive standard mixing rules. So far, the departure function cannot be used in a predictive manner, because its structure is not known a priori but has to be determined in the fitting procedure by mainly trial and error. The multi-fluid model is also used when modeling mixtures with the reference equation of state for water, the IAPWS-95 [2]. When the parameters are fitted to data, the multi-fluid model is capable of representing phase equilibria very accurately. However, when using standard mixing rules, the model can be quite inaccurate and sometimes predict entirely wrong behavior.In this work, we propose a new theoretically based departure function for multi-fluid models. The new formulation makes use of the well-established idea of combining equations of state with excess Gibbs energy models, see, e.g. [3]. The multi-fluid model was combined with the UNIFAC [4] model with different existing and adjusted parametrizations. Results for binary mixtures with water are shown. The new model is demonstrated to be superior to standard mixing rules for the calculation of phase equilibria of the considered mixtures.

[1] O. Kunz, W. Wagner, J. Chem. Eng. Data 57 (2012) 3032.[2] W. Wagner, A. Pruß, J. Phys. Chem. Ref. Data 31 (2002) 387.[3] M.-J. Huron, J. Vidal, Fluid Phase Equilib. 3 (1979) 255.[4] A. Fredenslund, R.L. Jones, J.M. Prausnitz, AIChE J. 21 (1975) 1086.

O 60A new model for mixed hydrates consistent with multiparameter equations of stateS. Hielscher1, A. Jäger2, V. Vinš3, C. Breitkopf2, J. Hrubý3, R. Span1

1 Ruhr-Universität Bochum, Thermodynamics, Bochum, Germany2 TU Dresden, Institute of Power Engineering- Faculty of Mechanical Science and Engineering, Dresden, Germany3 Institute of Thermomechanics of the CAS, Department D 2 - Thermodynamics, Prague 8, Czechia

In this work, the model for pure hydrates (water + one hydrate forming substance) that was developed by our group [1–3] has been extended to systems with more than one hydrate forming substance in the mixture (mixed hydrates). The refined model can represent high pressure three-phase equilibrium data for which guest molecules are known to double occupy cavities. It is intended for modeling of mixed hydrates in carbon capture and storage (CCS)-relevant mixtures. For the newly developed mixed hydrate model, a simple mixing rule for the volume is used, which does not contain any


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adjustable parameters. The new model is consistent with accurate multiparameter equations of state for fluid phases of the corresponding mixtures.Comparisons of the new model to experimental data for mixed hydrates are presented for several multicomponent mix-tures containing substances that are relevant for the intended application. The influence of double occupied cavities on calculated phase equilibria as well as the improvements for calculated three-phase hydrate formation temperatures at pressures, where double cage occupancy occurs, are shown for argon, nitrogen, oxygen, and air.It has been observed that pure guest components forming a certain structure may form another hydrate modification when present in a mixture [4,5]. With the refined algorithms for the stability analysis, it will be shown which hydrate struc-ture is found to be more stable at the given conditions. The results are compared to experimental results.

[1] V. Vinš, A. Jäger, R. Span, J. Hrubý, Fluid Phase Equilib. 427 (2016) 268–281.[2] V. Vinš, A. Jäger, J. Hrubý, R. Span, Fluid Phase Equilib. 435 (2017) 104–117.[3] A. Jäger, V. Vinš, R. Span, J. Hrubý, Fluid Phase Equilib. 429 (2016) 55–66.[4] J. Shu, X. Chen, I.-M. Chou, W. Yang, J. Hu, R.J. Hemley, H. Mao, Geosci. Front. 2 (2011) 93–100.[5] P. Babu, T. Yang, H.P. Veluswamy, R. Kumar, P. Linga, J. Chem. Thermodyn. 61 (2013) 58–63.

O 61Development of viscosity formulations for working fluids using a structure-optimization methodS. Herrmann1, H.J. Kretzschmar1, E. Vogel2, K. Meier3

1 Zittau/Goerlitz University of Applied Sciences, Department of Technical Thermodynamics, Zittau, Germany2 University of Rostock, Institute of Chemistry, Rostock, Germany3 Helmut-Schmidt-University/University of the Federal Armed Forces Hamburg, Institute for Thermodynamics, Hamburg, Germany

The precise knowledge of thermophysical properties of fluids is required for a more accurate design of steam turbines, pumps, condensers, heat exchangers, and other components of energy and process technology. Furthermore, algorithms have to be adequately provided for the use in engineering calculations. Requirements for property calculations are low uncertainty and high computing speed, which are important in process simulations and online process monitoring in the energy and process industry. Hence, new viscosity formulations for industrially important fluids such as ethane (2015), propane (2016), normal butane (2018), and isobutane (2018) were developed using the structure-optimization method of Setzmann and Wagner (1989).The concept of the new viscosity formulations for normal butane and isobutane incorporates four contributions: the vis-cosity in the limit of zero density, the initial-density dependence, the residual contribution, which describes the high-density region, and a contribution, which describes the behavior in the near-critical region. The viscosity in the limit of zero-density is based on experimental data, which were extrapolated to zero density by the authors. It is characterized by a physically correct extrapolation behavior up to 10000 K. The initial density dependence benefitted from the Rainwater-Friend theory for the second viscosity virial coefficient. An approach for the thermodynamic scaling and double polynomials in inverse reduced temperature and reduced density were used for the residual contribution. The critical-enhancement contribution, which was partly pretreated, is modelled by Gaussian bell-shaped terms and is included into the complete formulation. As a result, the formulations for the four alkanes provide a precise representation of the viscosity in the whole fluid region. The new formulations were compared with the primary data sets employed in their development.


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O 62Review of the humidity formulations for dew point temperatures above 100 °CS. Tabandeh1, V. Fernicola1

1 INRIM Istituto Nazionale di Ricerca Metrologica, dep. of STALT, Turin, Italy

Although humidity measurements above 100 °C are required by the industry and humidity sensors are specified for these conditions, humidity calibration procedures are not still well developed and a clear calculation strategy is not available. This work tries to give a better picture of different conversion formulations and estimates the difference among them. Initially, several water vapor saturation formulations (e.g., Wexler, Sonntag, Hardy) were compared against the Wagner equation and differences reported.The enhancement factor is one of the most important aspect of these conversions and its importance is even more evident for high humidity at high pressures, e.g. the correction due to the enhancement factor is approximately 2 % at Tdp = 130 °C and P = 0.6 MPa. It is estimated that the enhancement factor at high humidity is mainly governed by the non-ideality of the water vapor; on the contrary, the major influencing contribution at low humidity comes from the inter-molecular potentials between the water molecules and the carrying gas. In this work, it was calculated based on TEOS-10 set of equations and compared with the extrapolation of the Greenspan equation. Typically, the enhancement factor adopted for air is also implemented for nitrogen without any correction or uncertainty assessment. This work also proposes a correction to the enhancement factor in air using the second and third virial coefficients of air and nitrogen in a wide range of temperature and pressure.

TPWS5: HEAVY WATER


O 67Deuterium oxide density in stable and metastable states at pressure up to 400 MPaR. Romeo1, P.A. Giuliano Albo1, S. Lago1

1 INRIM, Thermodynamics, Turin, Italy

In this work, experimental densities of deuterium oxide (D2O) are presented. The measurements have been carried out through a pseudo-isochoric method in a wide range of temperature and pressure, covering both liquid stable and meta-stable regions. The measurements have been performed by a high-pressure cell already used to measure ordinary water up to the maximum working pressure of 400 MPa. The cell has been used like a pycnometer, and filled with a variable mass of heavy water. The measuring cycle, performed at constant mass, consists of pressure measurements by changing the temperature, when the thermodynamic equilibrium is reached. The density is calculated according to its definition, from the ratio between the mass of D2O and the volume of the cell. The mass has been determined weighing the cell by means of an analytical balance and using the double substitution method. The volume of the cell has been measured by the gravimetric method at a reference temperature and pressure. This value has been corrected using the thermal expansion and compressibility coefficients of the measurement cell that have been experimentally determined. Heavy water density has been measured for temperature down to 250 K and pressure up to 400 MPa, thus both stable and supercooled states. All terms contributing to the uncertainty in determining the volume and the mass have been considered, obtaining that the expanded relative uncertainty of D2O density is around 0.07 %. Besides, the experimental results are compared with the last formulation of the heavy water equation of state.

O 68Vapour pressure measurements over liquid heavy water in the temperature range from 260 K to 285 KG. Beltramino1, L. Rosso1, R. Cuccaro1, D. Smorgon1, V. Fernicola1

1 INRIM, Stalt, Torino, Italy

The thermodynamic properties of heavy water (D2O) are of interest in the industrial field as well as the scientific domain, both on the application side and for the understanding of isotopic effects in aqueous solutions.In contrast with ordinary water (H2O), comparatively few saturation vapor pressure measurement data of D2O are reported in the literature in the temperature range in which heavy water is at its supercooled state, sometimes with limited or


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unknown measurement uncertainty. Furthermore, it should be noted that the temperature at the triple point of heavy water (276.97 K) is presently known with an associated uncertainty about ten times higher than that of the ordinary water.An experimental apparatus has been set up at the Istituto Nazionale di Ricerca Metrologica (INRIM) in the attempt to achieve accurate measurements of the vapour – liquid equilibrium along the saturation line of heavy water over the tem-perature range from approximately 260 K to 285 K.Two different sample cells, kept in a thermostatic bath at a constant temperature with millikelvin stability, are connected to a high-accuracy manometer with measurement full scale of 1330 Pa, in order to cover the whole vapour pressure measurement range. A comparison between the experimental measurements performed in this work and the available literature data has been carried out along with the recent D2O vapor pressure formulation. Measurement results are discussed and uncertainty sources are estimated.

O 69A new reference equation of state for heavy waterS. Herrig1, M. Thol1, R. Span1, A. Harvey2, E.W. Lemmon2

1 Ruhr-University Bochum, Thermodynamics, Bochum, Germany2 National Institute of Standards and Technology, Applied Chemicals and Materials Division, Boulder, USA

In this work, a new fundamental equation of state for thermodynamic properties of heavy water was developed. Since its discovery in the early 1930’s, heavy water has been of significant industrial interest especially for nuclear power-pro-duction. Aside from this application, it is scientifically important as a source of information about the isotopic impacts on thermophysical properties. The current reference equation of state for heavy water was published by Hill et al. (1982) and became a standard of the International Association for the Properties of Steam (IAPS) in 1984. In comparison to modern formulations for other fluids, this equation has an unnecessary complex functional form, which frequently leads to nu-merical problems. Due to both advances in the development of equations of state and modern computer technology it is now possible to develop an equation with a reduced number of parameters without loss of accuracy. The new formulation is an empirical multiparameter equation of state explicit in the reduced Helmholtz energy with density and temperature as independent variables. Compared to the formulation by Hill et al. (1982), the new equation of state contains less than half the number of terms. It describes the whole fluid region for temperatures and pressures up to T = 825 K and p = 1200 MPa. The accuracy of the equation was validated by comparisons to the available data including recently published measure-ments on speed of sound, second virial coefficient, and density of the metastable subcooled-liquid. Based on evaluations of properties at extreme conditions of temperature and pressure, the extrapolation behavior of the equation was found to be reasonable. The new formulation is adopted as a standard of the International Association for the Properties of Water and Steam (IAPWS) and prepared for publication by Herrig et al. (2018).

Poster Session


P 06Transport properties of the TIP4P/2005 model for water and their analysis with a two-state modelP. Montero de Hijes1, L. Joly2, E. Sanz1, C. Valeriani1, F. Caupin2

1Universidad Complutense de Madrid, Facultad de Ciencias Quimicas, Madrid, Spain2Université Claude Bernard Lyon 1, Institut Lumière Matière, Villeurbanne, FranceDynamic properties of water exhibit an anomalous pressure dependence: below ambient temperature, the shear viscosity η first decreases with pressure, whereas the self-diffusion coefficient D first increases. Simulations usually focus on the calculation of D because it is computationally easier to obtain. We have calculated both D and η for the TIP4P/2005 model of water over a broad region of the phase diagram, covering stable, supercooled and stretched states. This set of data allows us to test the Stokes-Einstein relation Dη/T = cst. A recent work [1] has shown that experimental data for the dynamic properties of stable and supercooled water at positive pressure is described within uncertainty by the dynamic extension of a thermodynamic two-state model [2]. A thermodynamic two-state model is available for TIP4P/2005 [3]. We discuss here how it can be extended to describe D and η.

[1] L. P. Singh, B. Issenmann, F. Caupin. Pressure dependence of viscosity in supercooled water and a unified approach for thermodynamic and dynamic anomalies of water. Proc. Natl. Acad. Sci. USA 2017, 114, 4312.

[2] V. Holten, J.V. Sengers, M.A. Anisimov. Equation of state for supercooled water at pressures up to 400 MPa. J Phys Chem Ref Data 2014, 43, 043101.


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[3] J.W. Biddle, R.S. Singh, E.M. Sparano, F. Ricci, M.A. González, C. Valeriani, J.L.F. Abascal, P.G. Debenedetti, M.A. Anisimov, F. Caupin. Two-structure thermodynamics for the TIP4P/2005 model of water covering supercooled and deeply stretched regions. J. Chem. Phys. 2017, 146, 034502.

P 07Theoretical calculating the polarization characteristics for ice and water in the wide temperature rangeD. Putintsev1, N. Putintsev2

1 Institute for Systems Analysis- FRC CSC RAS, Discrete methods, Moscow, Russian Federation2 Murmansk State Technical University, Department of Continuum Mechanics and Offshore Oil and Gas Industry, Murmansk, Russian

Federation

At the present time, there is no generally accepted theory of the polarization of matter, which would allow us to find the values of εS, ε∞, α, р, PM, Ptot

M def, F, etc. in a real substance depending on environmental conditions. In the work, we use a modified Onsager-Kirkwood-Fröhlich theory, which makes it possible to calculate the polarization characteristics without using the static permittivity εS.In the paper, it is assumed that the dielectric is an isotropic medium consisting of molecules that do not interact with each other and are located in molecular electric fields. This method allows us to use the average cosine of the angle between the strength of local electric fields and the dipole moments of molecules in the medium as the average measure of the local orientation of the dipoles, that is, put <cos θ > = L(χF). This approach also makes it possible to equate the value of the energy of the interaction of dipoles with molecular fields to the value of the internal interaction energy Uinterac if the energy of the interaction of the dipoles with external fields used for the experimental determination of the value of εS is much less than Uinterac.The theoretical calculation of the static permittivity of water in various aggregate states (ice Ih in the range of 123 K - Tmelt, supercooled water in the range of 238 K - Tmelt, water at the saturation line from the melting point to the precritical region) is performed. The calculated values of the dipole moment agree with the modern quantum mechanical calculations, and the results of calculating the values of εS are in practical agreement with experiment in the wide range of 123.15 K-573.15 K. At high temperatures (Т>573.15 К), the discrepancy between the values found by us and the reference values of εS in-creases. This discrepancy may be due to the fact that the results are calculated in the isotropy approximation of the medium and take into account only the first and second order hyperpolarizabilities.


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P 08Water vapor enhancement factor estimation based on the inter-molecular potentialsS. Tabandeh1, V. Fernicola1

1 INRIM Istituto Nazionale di Ricerca Metrologica, dep. of STALT, Turin, Italy

The saturation water pressure plays a crucial role in the estimation of humidity-related quantities or to convert between humidity parameters (e.g. dew point temperature, relative humidity, mole fraction) in any carrier gas. In order to carry our accurate calculations, it is necessary to take into account the non-idealities of the resulting gas mixture using the so-called enhancement factor.The enhancement factor estimation is typically based on complex experiments however, because of that, either there is a lack of experimental data or the information is incomplete in many cases. Water vapor enhancement factor is not reported in the literature for many gases or it does not cover the full range of the interest.In the first part of this work, the enhancement factor was estimated using the properties of water in the condensed phase (e.g. molar volume and isothermal compressibility), the Henry’s law constant and the virial coefficients (i.e. second and third virial and cross-virial coefficients) as suggested by Hyland and Wexler (1973b).In a second approach, the enhancement factor estimation was carried out for mixtures where there is a limited informa-tion on the cross-virial coefficients, but adequate information on the excess parameters (e.g. excess enthalpy). A third approach was attempted, when no information is provided in the literature, relying on the numerical integration of the intermolecular potentials based on Lennard-Jones or Stockmayer potential models.The paper will report the water vapor enhancement factor estimation based on the above methods for air, nitrogen, hydrogen, oxygen, ammonia and sulfur hexafluoride. The agreement between different methods for nitrogen was within 1 part in 104 at Tdp=0 °C and P=0.1 MPa.


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INDEX OF AUTHORS

Addison D. 44, 52

Akamine H. 47

Alcorn C. 37

Anderko A. 37

Applegarth L. 37

Arcis H. 30

Ayuba S. 66

Bachet M. 56

Bartos O. 34

Bell I. H. 67

Bellows J. 46

Beltramino G. 69

Bénézeth P. 56

Berry R. 33

Berthelard R. 62

Blahut A. 61

Breitkopf C. 41–42, 67

Brumby P. E. 66

Brunner A. M. 49

Burakov I. 50

Burton G. 51

Bystrianský V. 39

Camoes M. F. 58

Caravaggio M. 31

Castellanos Muñoz J. 38

Caupin F. 62, 65, 70

Cavuoto G. 63

Čenský M. 34, 61

Cook W. 44, 46

Cox J. 37

Császár A. G. 27

Cuccaro R. 69

Daal L. 44

Dalsgaard T. 55

Das G. 37

Dedera S. 65

Dehaoui A. 62

De Meyer E. 49, 55

di Mare F. 33

Disci-Zayed D. 50

Dooley B. 43, 47

Duška M. 61

Dyachenko F. 50

Dzhuraeva E. 32

El Hawary A. 64

Eslamimanesh A. 37

Fernandez J. M. 65

Fernandez-Prini R. 29

Fernicola V. 69, 72

Fogh F. 52, 54

Fransen M. 61

Fredrikson A. 54

Frenz M. 62

Gampe U. 33

Garberoglio G. 66

Garland P. 31

Giuliano Albo P. A. 56, 59, 63, 69

Glasmacher U. A. 65

Goy C. 65

Graff A. 56

Grisenti R. E. 65

Groniewsky A. 63

Guillaume R. 52

Guillerm E. 62, 65

Gurke S. 32

Györke G. 63

Harvey A. 66, 70

Hater W. 49–50, 52

Hellmann R. 65

Henderson H. 45

Herrig S. 70

Herrmann S. 36, 68

Hielscher S. 67

Hilden J. 55

Hirano H. 51

Hoffert U. 40

Holl C. 44

Holten V. 62

Hošek J. 61

Hrubý J. 34, 61, 67

Hubbard D. 45

Huiting H. 49

Hykl J. 61

Imre A. R. 63

Issenmann B. 62

Ivo N. 34

Jäger A. 41–42, 67

Jankowski P. 66

Jasper J. 50

Joly L. 70

Kalinin A. 65

Kalová J. 61

Kamphausen N. 42

Kanyile S. 48

Kastensson J. 55

Kayukawa Y. 59–60

Kiefer J. 38

Kippers N. 31

Komarek M. 31

Kosaka S. 40

Kratky T. 31

Krausová A. 39

Kretzschmar H. J. 33, 36, 68

Kunick M. 33, 36

Kuznetsov V. 32

Lago S. 56, 59, 63, 69

Lavaei A. 32

Le Menn M. 56

Lemmon E. W. 70

Lencka M. 37

Lister D. 31, 46–47

Lohrasbi A. 32

Lorenz T. 42

Lundberg R. 53


74

Maarten B. 44

Macák J. 39

Majer V. 41

Malengo A. 59

Marais S. 48

Mares R. 61

Martineau R. 33

McDougall T. 58

McKay A. M. 46

Meier K. 64, 68

Mickoleit E. 41

Mijajlovic M. 50

Milsch H. 40

Moghul D. 46

Montero de Hijes P. 70

Mouchot J. 52

Moučka F. 34

Murina E. 29

Nakahara M. 38, 41

Navrotsky A. 37

Nikl Z. 61

Niu L. B. 40

Nomura K. 66

Novák M. 39

Novotný R. 39

Nozaki A. 47

Ochkov V. 32

Okita N. 34–35

Oliveira M. R. 58

Orlov K. 32

Palazhchenko O. 46

Pastorino C. 29

Pawlowicz R. 57

Peeters B. 55

Petrick T. 50

Petridis N. 65

Petrova T. 50

Peukert P. 61

Picard S. 27

Post P. 33

Potenza M. 65

Powalisz J. 45, 48

Prosvetov A. 65

Putintsev D. 71

Putintsev N. 71

Qian J. 51

Qiu C. 62

Qiu L. 51

Rathke B. 38

Raval S. 31

Riman R. 37

Romeo R. 59, 69

Rosseau S. 51

Rosso L. 69

Sanz E. 70

Sawatsubashi T. 47

Scheiber J. 52

Schottelius A. 65

Sedlar M. 31

Šedlbauer J. 41

Shimada H. 35

Shulder S. 31

Silva R. B. 58

Simantris N. 57

Singh L. P. 62

Slavík M. 41

Šmíd B. 61

Smorgon D. 69

Spanjers H. 50

Span R. 28, 67, 70

Sparasci F. 56

Suh D. 66

Sum A. K. 66

Svensson A. 55

Szalewicz K. 66

Tabandeh S. 69, 72

Taylor D. 46

Tejeda G. 65

Thol M. 70

Thomsen K. N. 43, 53

Tomut M. 65

Trautmann C. 65

Tremaine P. 37

Trusler J. P. M. 28

Tsubakizaki S. 47

Tsujino Y. 38

Tůma L. 39

Uchida H. 57, 59–60

Ureshino A. 47

Ustyuzhanin E. 64

Valeriani C. 70

Vanoppen M. 49, 55

Venhuis L. 44

Verbeken K. 55

Verliefde A. 49, 55

Vidojkovic S. 50

Vinš V. 34, 61, 67

Vogel E. 68

Voss K. O. 65

Vughs D. 49

Vuorinen J. 54

Wang P. 37

Wiig L. 53

Wilke M. 62

Woizick H. 44

Woosley R. 58

Wu D. T. 66

Xue Y. 49

Yamaguchi N. 34

Yasuoka K. 66

Yoshida K. 38, 41

Yuhara D. 66


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NOTES


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NOTES

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