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Thermodynamics, Experimental, and Modelling of Aqueous Electrolyte and Amino Acid Solutions

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Thermodynamics, Experimental, and Modelling of Aqueous Electrolyte and Amino Acid Solutions Downloaded from orbit.dtu.dk on: Sep 26, 2021 Thermodynamics, Experimental, and Modelling of Aqueous Electrolyte and Amino Acid Solutions Breil, Martin Peter Publication date: 2001 Document Version Publisher's PDF, also known as Version of record Link back to DTU Orbit Citation (APA): Breil, M. P. (2001). Thermodynamics, Experimental, and Modelling of Aqueous Electrolyte and Amino Acid Solutions. General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. Users may download and print one copy of any publication from the public portal for the purpose of private study or research. You may not further distribute the material or use it for any profit-making activity or commercial gain You may freely distribute the URL identifying the publication in the public portal If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Thermodynamics, Experimental, and Modelling of Aqueous Electrolyte and Amino Acid Solutions Martin P. Breil 2001 IVC-SEP Department of Chemical Engineering Technical University of Denmark DK-2800 Kongens Lyngby, Denmark Preface iii Preface This thesis is submitted as a partial fulfilment of the Ph.D. degree at the Technical University of Denmark. The project, granted by the IVC-SEP, has been carried out from October 1998 to September 2001 at the Department of Chemical Engineering, Technical University of Denmark under the supervision of Jørgen Mollerup. I wish to thank my supervisor for his guidance, his ideas, and his ability to encourage me. I would also like to thank Kaj Thomsen for our many discussions on matters of electrolytes and for letting me borrow articles from his extensive library when necessary. My thanks also extend to the people that I met during my sabbatical at the Kluyver Laboratory for Biotechnology, Delft University of Technology in the Netherlands. Especially, Luuk van der Wielen and Marcel Ottens who made the stay possible, and Susanne Rudolph who was my supervisor. Finally, I wish to thank the staff of the IVC-SEP and of the Kluyver Laboratory for making the past three years so successful. Martin Peter Breil Kongens Lyngby, September 2001 Preface iv Summary v Summary The thesis addresses the thermodynamics involved when describing the properties of solutions of amino acids and dipeptides. Furthermore, it presents the solubility measurements of two dipeptides (glycylglycine and glycyl-L-alanine) in aqueous salt solutions and electrode potential measurements of the same two dipeptides in aqueous NaCl solutions. Chapter 1 is an introduction to the chemistry of amino acids and dipeptides. It presents the principles of the Bjerrum diagram and the isoelectric point of a polyvalent compound. The industrial and medical use of amino acids is briefly touched. Chapter 2 is the main thermodynamic chapter where most of the required properties are presented and defined. The schism of defining the activity coefficient at infinite dilution in a non-binary mixture is pointed out as well as the alternative types of concentration scales. In Chapter 3 the four most common types for experimental methods for determination of solvent or solute activity are described by using the thermodynamic properties of the proceeding chapter. Chapter 4 focuses on the thermodynamics of electrochemistry and is based on the principles of Chapter 2. As an example experimental data obtained on a so-called Harned cell is presented. Chapter 5 presents the results of the experimental work carried out during the sabbatical, namely the solubility of glycylglycine and glycyl-L-alanine in aqueous NaCl, Na2SO4,and (NH4)2SO4 solutions - and electrode potential measurements with ISE's of solutions containing NaCl and the two dipeptides mentioned above. Chapter 6 presents the basis for the so-called McMillan-Mayer framework in relation to statistical thermodynamics and in relation to the usual (Lewis-Randall) framework. In Chapter 7, the osmotic equilibrium and limitations of the van't Hoff equation are examined. In Chapter 8, the continuum concept is described and related to the McMillan-Mayer framework. Different types of electrolyte models are presented: Debye-Hückel, extended UNIQUAC, and HS-MSA. The usually approach to model solubility data is presented. Summary vi In Chapter 9, the modelling results of the extended UNIQUAC model on binary and ternary aqueous solutions containing amino acid are presented. The solubility prediction of the extended UNIQUAC model commented. Furthermore, an analysis of the behaviour of the HS- MSA model in electrolyte solutions is carried out and commented. Chapter 10 is giving an overview of the extent of the database created during this project. Chapter 11 is a conclusion, summarising the results achieved during this project. Three appendices are included: one on Euler's theorem, one on equilibrium, and one on electrostatics. Resumé på dansk vii Resumé på dansk Afhandlingen omhandler den termodynamik, der er involveret, når man skal beskrive egenskaberne af opløsninger af aminosyrer og dipeptider. Ydermere præsenteres opløse- lighedsmålinger af to dipeptider (glycylglycin og glycyl-L-alanin) i vandige salt-opløsninger og målinger af elektrode-potentialer af de samme to dipeptider i vandig NaCl opløsninger. Kapitel 1 er en introduktion til aminosyrer og dipeptiders kemi. Det præsenterer principperne ved Bjerrum-diagrammerne og det isoelektriske punkt af et fler-valent stof. Den industrielle og medicinale brug af aminosyrer er kort berørt. Kapitel 2 er det centrale termodynamiske kapitel, hvor de fleste af de krævede egenskaber er præsenteret og defineret. Skismaet ved definitionen af aktivitetskoefficienten ved uendelig fortynding i en ikke-binær blanding er belyst, ligeledes som alternative koncentrationsskalaer. I Kapitel 3 er de fire mest almindelige typer af eksperimentelle metoder til bestemmelse af aktiviteten af opløsningsmidlet eller det opløste stof beskrevet af hjælp af de termodynamiske egenskaber fra det foregående kapitel. Kapitel 4 fokuserer på termodynamikken i elektrokemien og er baseret på principperne fra Kapitel 2. Som et eksempel er eksperimentelle data fra en såkaldt Harned-celle præsenteret. Kapitel 5 præsenterer resultaterne af det eksperimentelle arbejde, som er udført under det eksterne forskningsophold, nemlig opløseligheden af glycylglycin og glycyl-L-alanin i vandig NaCl, Na2SO4 og (NH4)2SO4 opløsninger - og målinger af elektrode-potentialer med ionselektive elektroder i opløsninger indeholdende NaCl og de to ovennævnte dipeptider. Kapitel 6 præsenterer grundlaget for det såkaldte McMillan-Mayer framework i relation til statistisk termodynamik og i relation til det sædvanlige (Lewis-Randall) framework. I Kapitel 7 forklares den osmotiske ligevægt og begrænsningerne af van't Hoff-ligningen. I Kapitel 8 beskrives kontinuum-konceptet og relateres til McMillan-Mayer framework'et. Forskellige typer af elektrolyt-modeller er præsenterede: Debye-Hückel, udvidet UNIQUAC og HS-MSA. Den sædvanlige måde, hvorpå opløselighedsdata modelleres, er præsenteret. I Kapitel 9 præsenteres modelleringsresultaterne fra den udvidede UNIQUAC-model på binære og ternære vandige opløsninger indeholdende aminosyre. Den udvidede UNIQUAC- Resumé på dansk viii models forudsagte opløseligheder er kommenteret. Ydermere er der udført en analyse af forløbet af HS-MSA-modellen i elektrolyt-opløsninger og kommenteret. Kapitel 10 giver et overblik over omfanget af den database, som er skabt i løbet af projektet. Kapitel 11 er en konklusion, der opsummerer de opnåede resultater. Tre appendices er inkluderede: ét om Euler's theorem, ét om ligevægt og ét om elektrostatik. Table of Contents ix Table of Contents Preface................................................................................................................................... i Summary ............................................................................................................................... iii Resumé på dansk...................................................................................................................v Table of Contents .................................................................................................................. vii 1. Introduction to the Chemistry of Amino Acids................................................................. 1 1.1 Structure of amino acids .................................................................................................................. 1 1.2 Stereochemistry ............................................................................................................................... 2 1.3 The influence of pH ......................................................................................................................... 2 1.4 The isoelectric point......................................................................................................................... 6 1.5 The use of amino acids .................................................................................................................... 9 2. Basic Thermodynamics..................................................................................................... 13 2.1 States...............................................................................................................................................
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