MIT-D15 DEUTERIUM CONCENTRATION BY CHEMICALLY-REFLUXED AMMONIA-HYDROGEN EXCHANGE SUPPLEMENTARY REPORTS by M. Benedict, E.A. Mason, E.R. Chow, J.S. Baron June 1969 FOR E.I. DUPONT DE NEMOURS & COMPANY UNDER U.S. ATOMIC ENERGY COMMISSION SUBCONTRACT AX-210280 Department of Nuclear Engineering Massachusetts Institute of Technology Cambridge, Massachusetts 02139 (MITNE-103) AECL PROPRIETARY DOCUMENT Notice: This document contains information obtained from Atomic Energy of Canada Limited, designated AECL PROPRIETARY. Documents so designated are made available to the USAEC pursuant to the Memorandum of Understanding executed June 7, 1960, for distribution restricted to the USAEC or its contractors. No other distribution is to be made without permission of AECL which may be secured by requesting specific clearance from the Scientific Representative, USAEC, Chalk River Liaison Office, Chalk River, Ontario. MIT-Dl5 DEUTERIUM CONCENTRATION BY CHEMICALLY-REFLUXED AMMONIA-HYDROGEN EXCHANGE SUPPLEMENTARY REPORTS by M. Benedict, E.A. Mason, E.R. Chow, J.S. Baron June 1969 for E.I. duPont de Nemours & Company under U.S. Atomic Energy Commission Subcontract AX-210280 (MIT DSR-70672) Department of Nuclear Engineering Massachusetts Institute of Technology Cambridge, Massachusetts 02139 (MITNE-103) Table of Contents Page Introductory Note I-1 Supplement A Liquid-Vapor Equilibrium in the System NH 3-H 2-N2 1. Introduction A-1 2. Results 2.1 Liquid Phase A-1 2.2 Vapor Phase A-2 3. Sources of Data A-3 4. Procedure for Correlating Data 4.1 Henry's Law Constants A-4 4.2 Ammonia Content of Vapor A-5 5. Bibliography A-19 Supplement B Enthalpies of Hydrogen, Nitrogen, and Ammonia to 14000 F and from 0 to 200 Atmospheres 1. General Information A. Introduction B-1 B. Manner of Reporting B-1 C. Use of Graphs B-2 II Hydrogen Enthalpies A. Preparation of Curves B-5 B. Enthalpy of Hydrogen Graphs B-8 III Nitrogen Enthalpies A. Source of Information B-10 Page B. Extrapolation to Higher Pressures B-13 C. Preparation and Use of Nitrogen Graphs B-17 D. Enthalpy of Nitrogen Graphs B-18 IV Ammonia Enthalpies A. List of Correlated Data B-24 B. Transposing Data to Report Basis B-24 C. Obtaining the Zero Pressure Line B-26 D. Plotting the Saturated Vapor and Liquid Lines B-30 E. Use of the Beatlie--Bridgeman Equation of State B-34 F. Completion of Superheated Curves by Grahl's Data B-38 G. Enthalpy of Compressed Liquid Ammonia B-41 H. Construction of the Ammonia Graphs B-44 I. Enthalpy of Ammonia Graphs B-45 V. Bibliography B-59 Supplement C Thermodynamic Equilibria for Ammonia Synthesis and Cracking 1. Introduction C-1 2. Sources of Information C-1 3. Calculation of Equilibrium Constants C-2 4. Calculation of Equilibrium Ammonia Mole Fraction C-3 5. Bibliography C-8 Page Supplement D Prediction of Plate Efficiency in the Hydrogea Deuterium--Ammonia Exchange Reaction I. Introduction D-1. II. Effect of a Chemical Reaction on the Mass Transfer Rate A. General Theory D-1 B. Determination of 0 for the HD(l)- NH 3 (1) Exchange Reaction D-3 III. Efficiency Correlation A. Literature Survey D-8 B. Modification of the A.I.Ch.E. Correlation D-8 IV. Absorption System Design A. Choice of Operating Conditions D-18 B. Physical and Phase Properties D-20 C. Determination of Flow Rates in Exchange Towers D-21 D. Tray Characteristics D-22 E. Evaluation of the Efficiency Prediction and Comparison with Experiment D- 23 V. Conclusions D-26 VI. References D-26 Page Supplement E Analysis of Stirred Contactors for Gas-Liquid Exchange Reactors 1. Introduction E-1 2. Proposed Model E-2 3. Mass Transfer with Chemical Reaction 3.1 Model E-6 3.2 Solution E-6 3.3 Determination of E-10 3.4 Bubble Gas Distribution Function E-11 4. Possible Design Numbers E-13 5. References E-14 Supplement F Chemically Ref luxed Water-Hydrogen Sulfide Exchange Process 1. Process Description F-1 2. Survey of Possible Metal Sulfide-Oxide Pairs F-3 3. Evaluation of- Energy Requirements F-21 List of Tables Page Supplement A Table 1. Values of Henry's Law Constants: Liquid Phase Data From LeFrancois and Vaniscotti A-7 Table 2. Values of Henry's Law Constants: Liquid Phase Data From Larson and Black A-8 Table 3. Sample Computations for Henry's Law Constants at 0.0 0C For Three Pressures A-9 Table 4. Ammonia Content of Vapor Expressed As YNHfr. Data From LeFrancois and Vaniscotti A- 10 Table 5. Ammonia. Content of Vapor Expressed as YNH3 r. Data From Larson and Black A-11 Table 6. Ammonia Content of Vapor Expressed Ab YNH3Y. Data from Michels, et. al. A-12 Supplement B Table 1. Comparison of Hydrogen Enthalpies From Canadian Graphs and From NBS Circular 564 B-6 Table 2. Values of Nitrogen Enthalpies Based On Absolute Zero Temperature B-11 Table 3. Extrapolation to Higher Pressures at 422 0 F. An Illustration of the Method of Second Differences B-13 Table 4. Nitrogen Enthalpies Extrapolated For Higher Pressures B-15 Page Table 5. Ammonia Enthalpies at Zero Pressure, From Ammonia Tables B-27 Table 6. Ammonia Enthalpies at Zero Pressure, From Tsoiman Equation B-29 Table 7. Ammonia Enthalpies for Saturated Vapor and Liquid Lines, from Ammonia Tables B-31 Table 8. Saturated Vapor Line Up to Critical Point, from Grahl's Thesis B-33 Table 9. Saturated Liquid Line Up to Critical Point, from Grahl's Thesis B-33 Table 10. Superheated Ammonia Enthalpies, from the Beattie-Bridgeman Equation of State B-37 Table 11. Superheated Ammonia Enthalpies, from Grahl's Thesis: 1200 to 3000 psia B-39 200 to 1000 psia B-40 Table 12. Correction Term for Compressed Liquid Ammonia B-43 Supplement C Table 1. Ideal Gas Equilibrium Constant K C-5 Table 2. Values of K or Constant Relating Fugacity Coefficients C-5 Table 3. Values of K or Constant Relating Mole Fractions of Components C-6 Table 4. Values of yNH , Equilibrium Ammonia 3 Mole Fraction C-6 Page Supplement D Table I. Proposed Operating Conditions of Reference Design D-18 Table II Design Data for Exchange Tower D-20 Table III Inlet and Exit Compositions In Exchange Tower D-21 Table IV Physical Characteristics of Proposed Tray Design D-23 Table V Exchange Tower Operating Parameters D-23 Supplement F Table 1 Equilibrium Constant for Reaction F-5,6 IMO n+ H2 S M1Sn+n+120 List of Figures Page Supplement A. Figure 1. Henry's Law Constant of H2 in Liquid NH3 vs. Temperature toC A- 13 Figure 2. Cross-plot of Henry's Constants of H2 in Liquid NH3 vs . TT Atm. A- 14 Figure 3. Henry's Law Constant of N2 in Liquid NH3 vs. Temperature toC A-15 Figure 4. Cross-Plot of Henry's Constants of N2 in Liquid NH3 vs. r Atm. A-16 Figure 5. Ammonia Content of Vapor yNH VS. l/T OK~ A- 17 Figure 6. Cross-Plot of Ammonia Vapor yNH 3 vs. 7 Atm. A- 18 Supplement B Figure 1-1 Enthalpy of Hydrogen B-8 Figure 1-2 Enthalpy of Hydrogen B-9 Figure 1-3 Enthalpy of Nitrogen: -80 to 2000F B-18 Figure 1-4 Enthalpy of Nitrogen: 100 to 420 0F B-19 Figure 1-5 Enthalpy of Nitrogen: 400 to 720'F B-20 Figure 1-6 Enthalpy of Nitrogen: 700 to 9800F B-21 Figure 1-7 Enthalpy of Nitrogen: 960 to 1280 B-22 Figure 1-8 Enthalpy of Nitrogen: 1240 to 1560 F B-23 Figure 1-9 Enthalpy of Ammonia First Index: -100 to 700FF B- 45 Page Figure 1-10 Enthalpy of Ammonia Second Index: 6000F to 10000F B-46 Figure 1-11 Enthalpy of Ammonia Third Index: 1000 to 1400 0F B-47 Figure 1-12 Enthalpy of Ammonia Graph I: -Liquid Phase, 180 to 340 0F B-48 Figure 1-13 Enthalpy of Ammonia Graph II: Critical Region, 180 to 380 0 F B-49 Figure 1-14 Enthalpy of Ammonia Graph III: Saturated Vapor Region, -100 to 180 0F B-50 Figure 1-15 Enthalpy of Ammonia Graph IV: Vapor Phase, 180 to 460 0 F B-51 Figure 1-16 Enthalpy of Ammonia Graph V: Vapor Phase, 140 to 4600F B-52 Figure 1-17 Enthalpy of Ammonia Graph VI: Vapor Phase, 340 to 620 0F B-53 Figure 1-18 Enthalpy of Ammonia Graph VII: Vapor Phase, 460 to 700 0F B-54 Figure 1-19 Enthalpy of Ammonia Graph VIII: Vapor Phase, 680 to 880 0F B-55 Figure 1-20 Enthalpy of Ammonia Graph IX: Vapor Phase, 800 to 1080 0 F B-5C Figure 1-21 Enthalpy of Ammonia Graph X: Vapor Phase, 1000 to 12400 F B-57 Page Figure 1-22 Enthalpy of Ammonia Graph XI: Vapor Phase, 1200 to 1400 F B-58 Supplement C Figure 1. Equilibrium Ammonia Mole Fraction yNH' vs. t, 0F C-7 Supplement D Figure 1. Tray Model In Vapor Terms D- 15a Supplement E Figure 1. Spherical Gas-Liquid Model E- 15 Supplement F Figure 1. Chemically Refluxed Water-Hydrogen Sulfide Exchange Process F-9 I-1 INTRODUCTORY NOTE The six topical reports contained in this volume supple- ment the final report (1) of a research project whose ob- jective was to evaluate the use of chemical reflux in processes for deuterium extraction. The studies were carried out by the Department of Nuclear Engineering at the Massachusetts Institute of Technology for the U. S.